Science.gov

Sample records for phase equilibria modification

  1. Phase Equilibria Diagrams Database

    National Institute of Standards and Technology Data Gateway

    SRD 31 NIST/ACerS Phase Equilibria Diagrams Database (PC database for purchase)   The Phase Equilibria Diagrams Database contains commentaries and more than 21,000 diagrams for non-organic systems, including those published in all 21 hard-copy volumes produced as part of the ACerS-NIST Phase Equilibria Diagrams Program (formerly titled Phase Diagrams for Ceramists): Volumes I through XIV (blue books); Annuals 91, 92, 93; High Tc Superconductors I & II; Zirconium & Zirconia Systems; and Electronic Ceramics I. Materials covered include oxides as well as non-oxide systems such as chalcogenides and pnictides, phosphates, salt systems, and mixed systems of these classes.

  2. Phase Equilibria and Crystallography of Ceramic Oxides

    PubMed Central

    Wong-Ng, W.; Roth, R. S.; Vanderah, T. A.; McMurdie, H. F.

    2001-01-01

    Research in phase equilibria and crystallography has been a tradition in the Ceramics Division at National Bureau of Standards/National Institute of Standatrds and Technology (NBS/NIST) since the early thirties. In the early years, effort was concentrated in areas of Portland cement, ceramic glazes and glasses, instrument bearings, and battery materials. In the past 40 years, a large portion of the work was related to electronic materials, including ferroelectrics, piezoelectrics, ionic conductors, dielectrics, microwave dielectrics, and high-temperature superconductors. As a result of the phase equilibria studies, many new compounds have been discovered. Some of these discoveries have had a significant impact on US industry. Structure determinations of these new phases have often been carried out as a joint effort among NBS/NIST colleagues and also with outside collaborators using both single crystal and neutron and x-ray powder diffraction techniques. All phase equilibria diagrams were included in Phase Diagrams for Ceramists, which are collaborative publications between The American Ceramic Society (ACerS) and NBS/NIST. All x-ray powder diffraction patterns have been included in the Powder Diffraction File (PDF). This article gives a brief account of the history of the development of the phase equilibria and crystallographic research on ceramic oxides in the Ceramics Division. Represented systems, particularly electronic materials, are highlighted. PMID:27500068

  3. Multicomponent three-phase equilibria

    SciTech Connect

    Ho, C.K.

    1995-06-01

    This paper presents the relations that describe thermodynamic equilibrium in a three-phase system. Multiple components, including air, water, and oil components, are considered in three phases: (1) aqueous, (2) oil, and (3) gas. Primary variables are specified for each of seven possible phase combinations. These primary variables are then used to determine the necessary secondary variables to completely describe the system. Criteria are also developed to check the stability of each phase configuration and determine possible transitions from one phase configuration to another phase configuration via phase appearances and disappearances.

  4. Thermodynamics of mantle minerals - II. Phase equilibria

    NASA Astrophysics Data System (ADS)

    Stixrude, Lars; Lithgow-Bertelloni, Carolina

    2011-03-01

    We complete the development and description of a thermodynamic method for the computation of phase equilibria and physical properties of multiphase mantle assemblages. Our previous paper focused on the computation of physical properties. In this paper, our focus shifts to the phase equilibria. We further develop our theory to specify the ideal and excess contributions to solution properties and derive properties of multiphase assemblages. We discuss our global inversion strategy for determining the values of the free parameters in our theory and compare inverted parameter values with expectations based on scaling arguments. Comparisons between our method and experimental phase equilibria data encompass the pressure-temperature regime of Earth's mantle. Finally, we present applications of our method that illustrate how it may be used to explore the origins of mantle structure and mantle dynamics. Continuing rapid advances in experimental and theoretical petrology and mineral physics have motivated an expansion of the scope of our model via the addition of several new phases, and of the soda component: an appendix lists all parameters in our model and references to the experimental and theoretical studies that constrain them. Our algorithm for global minimization of the Gibbs free energy is embodied in a code called HeFESTo, and is detailed in a second appendix.

  5. Phase equilibria for complex fluid mixtures

    SciTech Connect

    Prausnitz, J.M.

    1983-04-01

    After defining complex mixtures, attention is given to the canonical procedure used for the thermodynamics of fluid mixtures: first, we establish a suitable, idealized reference system and then we establish a perturbation (or excess function) which corrects the idealized system for real behavior. For complex mixtures containing identified components (e.g. alcohols, ketones, water) discussion is directed at possible techniques for extending to complex mixtures our conventional experience with reference systems and perturbations for simple mixtures. Possible extensions include generalization of the quasi-chemical approximation (local compositions) and superposition of chemical equilibria (association and solvation) on a physical equation of state. For complex mixtures containing unidentified components (e.g. coal-derived fluids), a possible experimental method is suggested for characterization; conventional procedures can then be used to calculate phase equilibria using the concept of pseudocomponents whose properties are given by the characterization data. Finally, as an alternative to the pseudocomponent method, a brief introduction is given to phase-equilibrium calculations using continuous thermodynamics.

  6. Phase Equilibria, Phase Diagrams and Phase Transformations - 2nd Edition

    NASA Astrophysics Data System (ADS)

    Hillert, Mats

    2006-03-01

    Computational tools allow material scientists to model and analyze increasingly complicated systems to appreciate material behavior. Accurate use and interpretation however, requires a strong understanding of the thermodynamic principles that underpin phase equilibrium, transformation and state. This fully revised and updated edition covers the fundamentals of thermodynamics, with a view to modern computer applications. The theoretical basis of chemical equilibria and chemical changes is covered with an emphasis on the properties of phase diagrams. Starting with the basic principles, discussion moves to systems involving multiple phases. New chapters cover irreversible thermodynamics, extremum principles, and the thermodynamics of surfaces and interfaces. Theoretical descriptions of equilibrium conditions, the state of systems at equilibrium and the changes as equilibrium is reached, are all demonstrated graphically. With illustrative examples - many computer calculated - and worked examples, this textbook is an valuable resource for advanced undergraduates and graduate students in materials science and engineering. Fully revised and updated edition covering the fundamentals of thermodynamics with a view to modern computer applications such as Thermo-Calc Emphasis is placed on phase diagrams, the key application of thermodynamics Contains numerous illustrative examples, many computer-calculated and some for real systems, and worked examples to help demonstrate the principles

  7. Experimental methods for phase equilibria at high pressures.

    PubMed

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

    2012-01-01

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

  8. State-of-the-art review of phase equilibria

    SciTech Connect

    Prausnitz, J.M.

    1980-03-01

    High-pressure phase-equilibrium calculations using an equation of state are more sensitive to the mixing rules than to details in the effect of density or temperature on pressure. Attention must be given to the problem of how to extend equations of state to mixtures. One possible technique is provided by perturbation theory; another by superposition of chemical equilibria. At low or moderate pressures, vapor-phase corrections are often important. When specific intermolecular forces produce formation of molecular aggregates, strong deviations from ideal-gas behavior can be significant even at pressures well below 1 bar. When vapor-liquid equilibrium data are reduced using conventional expressions for the excess Gibbs energy, the resulting binary parameters tend to be partially correlated, it difficult, but no impossible, to calculate ternary liquid-liquid equilibria using binary parameters only. New models for calculating properties of liquid-phase mixtures mist allow for changes in free volume to give consideration to the effect of mixing on changes in rotational and vibrational degrees of freedom. Liquid-phase volumetric effects are also important in describing the solubilities of gases in solvent mixtures. Therefore, future liquid-phase models should incorporate a liquid-phase equation of state, either of the van der Waals type or, perhaps, as given by the direct-correlation function theory of liquids.

  9. Phosphorus Equilibria Among Mafic Silicate Phases

    NASA Technical Reports Server (NTRS)

    Berlin, Jana; Xirouchakis, Dimitris

    2002-01-01

    Phosphorus incorporation in major rock-forming silicate minerals has the following implications: (1) Reactions between phosphorus-hosting major silicates and accessory phosphates, which are also major trace element carriers, may control the stability of the latter and thus may affect the amount of phosphorus and other trace elements released to the coexisting melt or fluid phase. (2) Less of a phosphate mineral is needed to account for the bulk phosphorus of planetaty mantles. (3) During partial melting of mantle mineral assemblages or equilibrium fractional crystallization of basaltic magmas, and in the absence or prior to saturation with a phosphate mineral, silicate melts may become enriched in phosphorus, especially in the geochemically important low melt fraction regime, Although the small differences in the ionic radii of IVp5+, IVSi4+, and IV Al3+ makes phosphoms incorporation into crystalline silicates perhaps unsurprising, isostructural silicate and phosphate crystalline solids do not readily form solutions, e.g., (Fe, Mg)2SiO4 vs. LiMgPO4, SiO)2 VS. AlPO4. Nonetheless, there are reports of, poorly characterized silico-phosphate phases in angrites , 2-4 wt% P2O5 in olivine and pyroxene grains in pallasites and reduced terestrial basalts which are little understood but potentially useful, and up to 17 wt% P2O5 in olivine from ancient slags. However, such enrichments are rare and only underscore the likelihood of phosphoms incorporation in silicate minerals. The mechanisms that allow phosphorus to enter major rock-forming silicate minerals (e.g., Oliv, Px, Gt) remain little understood and the relevant data base is limited. Nonetheless, old and new high-pressure (5-10 GPa) experimental data suggest that P2O5 wt% decreases from silica-poor to silica-rich compositions or from orthosilicate to chain silicate structures (garnet > olivine > orthopyroxene) which implies that phosphorus incorporation in silicates is perhaps more structure-than site-specific. The

  10. Furnace refractory corrosion and phase equilibria in electric smelting

    SciTech Connect

    Kaibicheva, M.N.

    1985-07-01

    By calculating the melting curves in smelting, in accordance with the phase equilibria in the FeO-Fe/sub 2/O/sub 3/-SiO/sub 2/ system, it is shown that at the approach to the ternary points (1140, 1150 and 1456/sup 0/C), the amount of liquid phase in the samples of smelting dust reaches 47%. The dust from all the compositions is wholly transferred into the melt at 1560/sup 0/C. The components of the smelting dust interact with the phases of the refractory where there is a temperature gradient and cause the formation of zones in the components and wear in the lining of the electric furnaces by chipping. The smelting dust causes a change in the chemical composition of the refractory which leads to a reduction in the refractoriness of the working layer and to wear on this layer by flashing off.

  11. Electronic structure and phase equilibria in ternary substitutional alloys

    SciTech Connect

    Traiber, A.J.S.; Allen, S.M.; Turchi, P.E.A.; Waterstrat, R.M.

    1996-04-26

    A reliable, consistent scheme to study phase equilibria in ternary substitutional alloys based on the tight-binding approximation is presented. With electronic parameters from linear muffin-tin orbital calculations, the computed density of states and band structures compare well with those from more accurate {ital ab}{ital initio} calculations. Disordered alloys are studied within the tight-binding coherent-potential approximation extended to alloys; energetics of ordered systems are obtained through effective pair interactions computed with the general perturbation method; and partially ordered alloys are studied with a novel simplification of the molecular coherent-potential approximation combined with the general perturbation method. The formalism is applied to bcc-based Zr-Ru-Pd alloys which are promising candidates for medical implant devices. Using energetics obtained from the above scheme, we apply the cluster- variation method to study phase equilibria for particular pseudo- binary alloys and show that results are consistent with observed behavior of electronic specific heat coefficient with composition for Zr{sub 0.5}(Ru, Pd){sub 0.5}.

  12. Modeling phase equilibria in mixtures containing hydrogen fluoride and halocarbons

    SciTech Connect

    Lencka, M. ); Anderko, A. Polish Academy of Sciences, Warszawa )

    1993-03-01

    Recently, much attention has been focused on the production of environmentally acceptable refrigerants, which not only offer desirable physico-chemical properties, but do not deplete the ozone layer and do not cause the greenhouse effect. The production of such refrigerants involves the separation of multicomponent mixtures containing hydrogen fluoride, hydrogen chloride, and various chlorinated and fluorinated hydrocarbons. Therefore, it is indispensable to know the phase behavior of these mixtures. While the phase behavior of refrigerant mixtures can be adequately modeled in the absence of HF using standard thermodynamic techniques, drastically increases the complexity of the mixture because of its unusually strong association. The association of HF manifests itself in its significantly reduced gas-phase compressibility factor and the strong nonideality of mixtures containing HF and hydrocarbons or halocarbons. In this work, the authors develop an accurate, yet simple, association model for HF and compare it with simulation data. The model is combined with a simple equation of state to yield a closed-form expression that is applicable to both pure fluids and mixtures. In addition to representing the pure-component data for HF, the theory accurately predicts phase equilibria in HF + halocarbon systems.

  13. Metamorphism and partial melting of ordinary chondrites: Calculated phase equilibria

    NASA Astrophysics Data System (ADS)

    Johnson, T. E.; Benedix, G. K.; Bland, P. A.

    2016-01-01

    Constraining the metamorphic pressures (P) and temperatures (T) recorded by meteorites is key to understanding the size and thermal history of their asteroid parent bodies. New thermodynamic models calibrated to very low P for minerals and melt in terrestrial mantle peridotite permit quantitative investigation of high-T metamorphism in ordinary chondrites using phase equilibria modelling. Isochemical P-T phase diagrams based on the average composition of H, L and LL chondrite falls and contoured for the composition and abundance of olivine, ortho- and clinopyroxene, plagioclase and chromite provide a good match with values measured in so-called equilibrated (petrologic type 4-6) samples. Some compositional variables, in particular Al in orthopyroxene and Na in clinopyroxene, exhibit a strong pressure dependence when considered over a range of several kilobars, providing a means of recognising meteorites derived from the cores of asteroids with radii of several hundred kilometres, if such bodies existed at that time. At the low pressures (<1 kbar) that typify thermal metamorphism, several compositional variables are good thermometers. Although those based on Fe-Mg exchange are likely to have been reset during slow cooling, those based on coupled substitution, in particular Ca and Al in orthopyroxene and Na in clinopyroxene, are less susceptible to retrograde diffusion and are potentially more faithful recorders of peak conditions. The intersection of isopleths of these variables may allow pressures to be quantified, even at low P, permitting constraints on the minimum size of parent asteroid bodies. The phase diagrams predict the onset of partial melting at 1050-1100 °C by incongruent reactions consuming plagioclase, clinopyroxene and orthopyroxene, whose compositions change abruptly as melting proceeds. These predictions match natural observations well and support the view that type 7 chondrites represent a suprasolidus continuation of the established petrologic

  14. Correlation of three-liquid-phase equilibria involving ionic liquids.

    PubMed

    Rodríguez-Escontrela, I; Arce, A; Soto, A; Marcilla, A; Olaya, M M; Reyes-Labarta, J A

    2016-08-01

    The difficulty in achieving a good thermodynamic description of phase equilibria is finding a model that can be extended to a large variety of chemical families and conditions. This problem worsens in the case of systems containing more than two phases or involving complex compounds such as ionic liquids. However, there are interesting applications that involve multiphasic systems, and the promising features of ionic liquids suggest that they will play an important role in many future processes. In this work, for the first time, the simultaneous correlation of liquid-liquid and liquid-liquid-liquid equilibrium data for ternary systems involving ionic liquids has been carried out. To that end, the phase diagram of the water + [P6 6 6 14][DCA] + hexane system has been determined at 298.15 K and 323.15 K and atmospheric pressure. The importance of this system lies in the possibility of using the surface active ionic liquid to improve surfactant enhanced oil recovery methods. With those and previous measurements, thirteen sets of equilibrium data for water + ionic liquid + oil ternary systems have been correlated. The isoactivity equilibrium condition, using the NRTL model, and some pivotal strategies are proposed to correlate these complex systems. Good agreement has been found between experimental and calculated data in all the regions (one triphasic and two biphasic) of the diagrams. The geometric aspects related to the Gibbs energy of mixing function obtained using the model, together with the minor common tangent plane equilibrium condition, are valuable tools to check the consistency of the obtained correlation results.

  15. Correlation of three-liquid-phase equilibria involving ionic liquids.

    PubMed

    Rodríguez-Escontrela, I; Arce, A; Soto, A; Marcilla, A; Olaya, M M; Reyes-Labarta, J A

    2016-08-01

    The difficulty in achieving a good thermodynamic description of phase equilibria is finding a model that can be extended to a large variety of chemical families and conditions. This problem worsens in the case of systems containing more than two phases or involving complex compounds such as ionic liquids. However, there are interesting applications that involve multiphasic systems, and the promising features of ionic liquids suggest that they will play an important role in many future processes. In this work, for the first time, the simultaneous correlation of liquid-liquid and liquid-liquid-liquid equilibrium data for ternary systems involving ionic liquids has been carried out. To that end, the phase diagram of the water + [P6 6 6 14][DCA] + hexane system has been determined at 298.15 K and 323.15 K and atmospheric pressure. The importance of this system lies in the possibility of using the surface active ionic liquid to improve surfactant enhanced oil recovery methods. With those and previous measurements, thirteen sets of equilibrium data for water + ionic liquid + oil ternary systems have been correlated. The isoactivity equilibrium condition, using the NRTL model, and some pivotal strategies are proposed to correlate these complex systems. Good agreement has been found between experimental and calculated data in all the regions (one triphasic and two biphasic) of the diagrams. The geometric aspects related to the Gibbs energy of mixing function obtained using the model, together with the minor common tangent plane equilibrium condition, are valuable tools to check the consistency of the obtained correlation results. PMID:27427420

  16. Phase Equilibria and Compressibility of bastnaesite-(La)

    NASA Astrophysics Data System (ADS)

    Rowland, R. L., II; Burnley, P. C.

    2015-12-01

    Bastnaesite (Ce,La,Y)CO3(F,OH) is a rare earth element (REE) bearing ore mineral. REEs are more common in the Earth's crust than precious metals like gold or platinum, but are not commonly concentrated in economically viable ore deposits. For over a decade, China has been the world's leading supplier of REEs. Recent export restrictions from China have necessitated the search for new deposits. Determining basic material properties such as phase equilibria and the equation of state for bastnaesite helps in understanding the processes that form REE ore deposits and thereby assist in locating new deposits. For this study we focus on the lanthanum-fluoride variant of bastnaesite (LaCO3F) since it can be easily synthesized in the laboratory. Previous work by others determined that in both open and closed systems at atmospheric pressure bastnaesite decomposes to lanthanum oxyfluoride and carbon dioxide (LaOF + CO2) above 325°C; at 100 MPa bastnaesite decomposes above 860°C (Hsu, 1992). Using a Griggs-type modified piston cylinder apparatus, we pressurized samples of synthetic bastnaesite-(La) to conditions ranging from 250 MPa to 1.2 GPa, and then subjected each sample to constant temperatures ranging from 700°C to 1050°C for a minimum of five hours. We then analyzed the samples with X-ray powder diffraction to identify phases present and determined that bastnaesite-(La) is stable at 250 MPa up to approximately 800°C and at 1.0 GPa up to approximately 900°C. Reversal experiments are underway. In order to develop an equation of state for bastnaesite-(La), we studied single crystals via monochromatic synchrotron X-ray diffraction in the diamond anvil cell at HPCAT (Sector 16), Advanced Photon Source (APS), Argonne National Laboratory. Measurements were made at pressures ranging from ambient to nearly 4 GPa. From these diffraction patterns, we determine the structure of bastnaesite-(La), and the change in unit cell volume as a function of pressure can be fit to a Birch

  17. Determination of phase equilibria in confined systems by open pore cell Monte Carlo method.

    PubMed

    Miyahara, Minoru T; Tanaka, Hideki

    2013-02-28

    We present a modification of the molecular dynamics simulation method with a unit pore cell with imaginary gas phase [M. Miyahara, T. Yoshioka, and M. Okazaki, J. Chem. Phys. 106, 8124 (1997)] designed for determination of phase equilibria in nanopores. This new method is based on a Monte Carlo technique and it combines the pore cell, opened to the imaginary gas phase (open pore cell), with a gas cell to measure the equilibrium chemical potential of the confined system. The most striking feature of our new method is that the confined system is steadily led to a thermodynamically stable state by forming concave menisci in the open pore cell. This feature of the open pore cell makes it possible to obtain the equilibrium chemical potential with only a single simulation run, unlike existing simulation methods, which need a number of additional runs. We apply the method to evaluate the equilibrium chemical potentials of confined nitrogen in carbon slit pores and silica cylindrical pores at 77 K, and show that the results are in good agreement with those obtained by two conventional thermodynamic integration methods. Moreover, we also show that the proposed method can be particularly useful for determining vapor-liquid and vapor-solid coexistence curves and the triple point of the confined system.

  18. Phase equilibria in the Ni-Al-Ti system at 1173 k

    NASA Astrophysics Data System (ADS)

    Nash, P.; Liang, W. W.

    1985-03-01

    The phase equilibria at 1173 K have been determined in the Ni-AI-Ti system for Al contents less than 50 at. pct. The extent of the H (Ni2AlTi) phase field has been established as well as the extent of solubility in the binary compounds γ (Ni3Al), ν(Ni3Ti), β2(NiTi), NiTi2, and ζ(AlTi3). Substantial differences were found between the phase equilibria determined in this study and previous studies, in part due to the large solubility of Al in NiTi2.

  19. Phase Equilibria Impetus For Large-Volume Explosive Volcanic Eruptions

    NASA Astrophysics Data System (ADS)

    Fowler, S. J.; Spera, F. J.; Bohrson, W. A.; Ghiorso, M. S.

    2006-12-01

    We have investigated the phase equilibria and associated variations in melt and magma thermodynamic and transport properties of seven large-volume silicic explosive volcanic systems through application of the MELTS (Ghiorso &Sack, 1995) algorithm. Each calculation is based on fractional crystallization along an oxygen buffer at low-pressure (0.1 - 0.3 GPa), starting from a mafic parental liquid. Site-specific geological constraints provide starting conditions for each system. We have performed calculations for seven tuffs; the Otowi (~400 km3) and Tshirege (~200 km3) members of the Bandelier Tuff, the ~600 km3 Bishop Tuff, and the 2500, 300, and 1000 km3 Yellowstone high-silica rhyolite tuffs. These represent the six largest eruptions within North America over the past ~2 million years. The seventh tuff, the 39.3 ka Campanian Ignimbrite, a 200 km3 trachytic to phonolitic ignimbrite located near Naples, Italy, is the largest explosive eruption in the Mediterranean area in the last 200 kyr. In all cases, MELTS faithfully tracks the liquid line of descent as well as the identity and composition of phenocrysts. The largest discrepancy between predicted and observed melt compositions is for CaO in all calculations. A key characteristic for each system is a pseudoinvariant temperature, Tinv, where abrupt shifts in crystallinity (1-fm, where fm is the fraction of melt), volume fraction of supercritical fluid (θ), magma compressibility, melt and magma density, and viscosity occur over a small temperature interval of order 1 - 10 K. In particular, the volume fraction of vapor increases from θ ~0.1 just below Tinv to θ >0.7 just above Tinv for each case. The rheological transition between melt-dominated (high viscosity) and bubble-dominated (low viscosity) magma occurs at θ ~0.6. We emphasize that this effect is observed under isobaric conditions and is distinct from the oft-studied phenomenon of volatile exsolution accompanying magma decompression and subsequent

  20. New investigation of phase equilibria in the system Al–Cu–Si

    PubMed Central

    Ponweiser, Norbert; Richter, Klaus W.

    2012-01-01

    The phase equilibria and invariant reactions in the system Al–Cu–Si were investigated by a combination of optical microscopy, powder X-ray diffraction (XRD), differential thermal analysis (DTA) and electron probe micro analysis (EPMA). Isothermal phase equilibria were investigated within two isothermal sections. The isothermal section at 500 °C covers the whole ternary composition range and largely confirms the findings of previous phase diagram investigations. The isothermal section at 700 °C describes phase equilibria only in the complex Cu-rich part of the phase diagram. A new ternary compound τ was found in the region between (Al,Cu)-γ1 and (Cu,Si)-γ and its solubility range was determined. The solubility of Al in κ-CuSi was found to be extremely high at 700 °C. In contrast, no ternary solubility in the β-phase of Cu–Al was found, although this phase is supposed to form a complete solid solution according to previous phase diagram assessments. Two isopleths, at 10 and 40 at.% Si, were investigated by means of DTA and a partial ternary reaction scheme (Scheil diagram) was constructed, based on the current work and the latest findings in the binary systems Al–Cu and Cu–Si. The current study shows that the high temperature equilibria in the Cu-rich corner are still poorly understood and additional studies in this area would be favorable. PMID:22287828

  1. The Representation of Highly Non-Ideal Phase Equilibria Using Computer Graphics.

    ERIC Educational Resources Information Center

    Charos, Georgios N.; And Others

    1986-01-01

    Previous work focused on use of computer graphics in teaching thermodynamic phase equilibria for classes I and II. Extends this work to include the considerably more non-ideal phase behavior shown by classes III, IV, and V. Student and instructor response has been overwhelmingly positive about the approach. (JN)

  2. Phase equilibria in the neodymium–cadmium binary system

    PubMed Central

    Skołyszewska-Kühberger, Barbara; Reichmann, Thomas L.; Ipser, Herbert

    2014-01-01

    The equilibrium phase diagram of the neodymium–cadmium system has been established by thermal, metallographic and X-ray analysis based on a study of 70 alloys. The system contains three congruently melting intermetallic compounds, i.e. NdCd (1040 °C), NdCd2 (995 °C), Nd11Cd45 (855 °C), and four incongruently melting compounds NdCd3 (860 °C), Nd13Cd58 (740 °C), NdCd6 (655 °C) and NdCd11 (520 °C). Four eutectic reactions are found in this binary system, i.e. at ∼25 at.% Cd and 770 °C, at 58 at.% Cd and 955 °C, at 79 at.% Cd and 850 °C, and very close to pure Cd at 318 °C, as well as one eutectoid reaction at ∼15 at.% Cd and 500 °C. The solid solubility of Nd in Cd is negligible. Dilatometric curves were recorded for three Nd–Cd compositions up to 4 at.% Cd, to accurately determine phase transitions between the solid solutions of Cd in the low- and high-temperature modification of Nd. PMID:25197164

  3. Study of Phase Equilibria of Petrochemical Fluids using Gibbs Ensemble Monte Carlo Methods

    NASA Astrophysics Data System (ADS)

    Nath, Shyamal

    2001-03-01

    Knowledge of phase behavior of hydrocarbons and related compounds are highly of interest to chemical and petrochemical industries. For example, design of processes such as supercritical fluid extraction, petroleum refining, enhanced oil recovery, gas treatment, and fractionation of wax products. A precise knowledge of the phase equilibria of alkanes, alkenes and related compounds and their mixtures are required for efficient design of these processes. Experimental studies to understand the related phase equilibria often become unsuitable for various reasons. With the advancement of simulation technology, molecular simulations could provide a useful complement and alternative in the study and description of phase behavior of these systems. In this work we study vapor-liquid phase equilibria of pure hydrocarbons and their mixtures using Gibbs ensemble simulation. Insertion of long and articulated chain molecules are facilitated in our simulations by means of configurational bias and expanded ensemble methods. We use the newly developed NERD force field in our simulation. In this work NERD force field is extended to provide coverage for hydrocarbons with any arbitrary architecture. Our simulation results provide excellent quantitative agreement with available experimental phase equilibria data for both the pure components and mixtures.

  4. Phase and chemical equilibria in the transesterification reaction of vegetable oils with supercritical lower alcohols

    NASA Astrophysics Data System (ADS)

    Anikeev, V. I.; Stepanov, D. A.; Ermakova, A.

    2011-08-01

    Calculations of thermodynamic data are performed for fatty acid triglycerides, free fatty acids, and fatty acid methyl esters, participants of the transesterification reaction of vegetable oils that occurs in methanol. Using the obtained thermodynamic parameters, the phase diagrams for the reaction mixture are constructed, and the chemical equilibria of the esterification reaction of free fatty acids and the transesterification reaction of fatty acid triglycerides attained upon treatment with supercritical methanol are determined. Relying on our analysis of the obtained equilibria for the esterification reaction of fatty acids and the transesterification reaction of triglycerides attained upon treatment with lower alcohols, we select the optimum conditions for performing the reaction in practice.

  5. Transport and Phase Equilibria Properties for Steam Flooding of Heavy Oils

    SciTech Connect

    Gabitto, Jorge; Barrufet, Maria

    2001-12-18

    The objectives of this research included experimental determination and rigorous modeling and computation of phase equilibria, volumetric, and transport properties of hydrocarbon/CO2/water mixtures at pressures and temperatures typical of steam injection processes for thermal recovery of heavy oils.

  6. Phase transitions and connectivity in three-dimensional vortex equilibria

    SciTech Connect

    Akao, J.H.

    1994-05-01

    The statistical mechanics of collections of closed self avoiding vortex loops on a lattice are studied. The system is related to the vortex form of the three dimensional XY model and to lattice vortex equilibrium models of turbulence. The system exhibits vortex connectivity and screening effects, and models in vorticity variables the superfluid transition. The equilibrium states of the system are simulated by a grand canonical Monte Carlo method. A set of geometric transformations for self-avoiding loops is developed. The numerical method employs histogram sampling techniques and utilizes a modification to the Metropolis flow which enhances efficiency. Results are given for a region in the temperature-chemical potential plane, where the chemical potential is related to the vortex fugacity. A line of second order transitions is identified at low temperature. The transition is shown to be a percolation threshold at which connected vortex loops of infinite size appear in the system. The nature of the transition supports the assumption that the lambda transition in bulk superfluid helium is driven by vortices. An asymptotic analysis is performed for the energy and entropy scaling of the system as functions of the system size and the lattice spacing. These estimates indicate that the infinite temperature line is a phase boundary between small scale fractal vortices and large scale smooth vortices. A suggestion is made that quantum vortices have uniform structure on the scale of the lattice spacing and lie in the positive temperature regime, while classical vortices have uniform structure on the scale of the domain and lie in the negative temperature regime.

  7. Thermodynamic calculations in the system CH4-H2O and methane hydrate phase equilibria

    USGS Publications Warehouse

    Circone, S.; Kirby, S.H.; Stern, L.A.

    2006-01-01

    Using the Gibbs function of reaction, equilibrium pressure, temperature conditions for the formation of methane clathrate hydrate have been calculated from the thermodynamic properties of phases in the system CH4-H 2O. The thermodynamic model accurately reproduces the published phase-equilibria data to within ??2 K of the observed equilibrium boundaries in the range 0.08-117 MPa and 190-307 K. The model also provides an estimate of the third-law entropy of methane hydrate at 273.15 K, 0.1 MPa of 56.2 J mol-1 K-1 for 1/n CH4??H 2O, where n is the hydrate number. Agreement between the calculated and published phase-equilibria data is optimized when the hydrate composition is fixed and independent of the pressure and temperature for the conditions modeled. ?? 2006 American Chemical Society.

  8. Development of the Transferable Potentials for Phase Equilibria Model for Hydrogen Sulfide.

    PubMed

    Shah, Mansi S; Tsapatsis, Michael; Siepmann, J Ilja

    2015-06-11

    The transferable potentials for phase equilibria force field is extended to hydrogen sulfide. The pure-component and binary vapor-liquid equilibria with methane and carbon dioxide and the liquid-phase relative permittivity are used for the parametrization of the Lennard-Jones (LJ) and Coulomb interactions, and models with three and four interaction sites are considered. For the three-site models, partial point charges are placed on the sites representing the three atoms, while the negative partial charge is moved to an off-atom site for the four-site models. The effect of molecular shape is probed using either only a single LJ interaction site on the sulfur atom or adding sites also on the hydrogen atoms. This procedure results in four distinct models, but only those with three LJ sites can accurately reproduce all properties considered for the parametrization. These two are further assessed for predictions of the liquid-phase structure, the lattice parameters and relative permittivity for the face-centered-cubic solid, and the triple point. An effective balance between LJ interactions and the dipolar and quadrupolar terms of the first-order electrostatic interactions is struck in order to obtain a four-site model that describes the condensed-phase properties and the phase equilibria with high accuracy. PMID:25981731

  9. Development of the Transferable Potentials for Phase Equilibria Model for Hydrogen Sulfide.

    PubMed

    Shah, Mansi S; Tsapatsis, Michael; Siepmann, J Ilja

    2015-06-11

    The transferable potentials for phase equilibria force field is extended to hydrogen sulfide. The pure-component and binary vapor-liquid equilibria with methane and carbon dioxide and the liquid-phase relative permittivity are used for the parametrization of the Lennard-Jones (LJ) and Coulomb interactions, and models with three and four interaction sites are considered. For the three-site models, partial point charges are placed on the sites representing the three atoms, while the negative partial charge is moved to an off-atom site for the four-site models. The effect of molecular shape is probed using either only a single LJ interaction site on the sulfur atom or adding sites also on the hydrogen atoms. This procedure results in four distinct models, but only those with three LJ sites can accurately reproduce all properties considered for the parametrization. These two are further assessed for predictions of the liquid-phase structure, the lattice parameters and relative permittivity for the face-centered-cubic solid, and the triple point. An effective balance between LJ interactions and the dipolar and quadrupolar terms of the first-order electrostatic interactions is struck in order to obtain a four-site model that describes the condensed-phase properties and the phase equilibria with high accuracy.

  10. Effects of gravity reduction on phase equilibria. Part 1: Unary and binary isostructural solids

    NASA Technical Reports Server (NTRS)

    Larson, D. J., Jr.

    1975-01-01

    Analysis of the Skylab II M553 Experiment samples resulted in the hypothesis that the reduced gravity environment was altering the melting and solidification reactions. A theoretical study was conducted to define the conditions under which such alteration of phase relations is feasible, determine whether it is restricted to space processing, and, if so, ascertain which alloy systems or phase reactions are most likely to demonstrate such effects. Phase equilibria of unary and binary systems with a single solid phase (unary and isomorphous) were considered.

  11. Phase and chemical equilibria in multicomponent fluid systems with a chemical reaction

    NASA Astrophysics Data System (ADS)

    Toikka, A. M.; Samarov, A. A.; Toikka, M. A.

    2015-04-01

    Studies of the phase and chemical equilibria in the systems with chemical reaction cover a wide range of problems related to both experimental determination of physicochemical characteristics of these systems and various aspects of thermodynamic analysis of the phase and chemical processes occurring there. The main goal of this review consists in systematization and analysis of available experimental data concerning the vapour-liquid and liquid-liquid equilibria in multicomponent systems where chemical reactions occur. The studies considered here have been mainly published in recent years, and they include rather detailed data on physicochemical properties, phase transitions and chemical processes in fluid systems, i.e., the data which are essential for thermodynamic analysis. Available approaches to the thermodynamic analysis of heterogeneous systems with chemical reactions are also discussed. Particular attention is paid to the studies of the simultaneous phase and chemical equilibria. We hope that this review could be useful both for fundamental studies of heterogeneous reactive systems and for solving applied problems on the design of combined reactive and mass-transfer processes. The bibliography includes 79 references.

  12. Phase equilibria in a system of 'breathing' molecules

    SciTech Connect

    Wu, Jianzhong; Prausnitz, John

    2001-09-30

    It is now well known that details in the intermolecular potential can significantly affect the qualitative features of a phase diagram where temperature is plotted against density for the coexistence curves among fluid and solid phases. While previous calculations of phase diagrams have assumed a time-invariant potential function, this report concerns the phase diagram for ''breathing'' molecules, i.e., molecules whose strength of intermolecular attraction fluctuates in time. Such fluctuations can occur in biomacromolecules where an active site can switch between ''on'' and ''off'' positions. Phase-equilibrium calculations were performed for molecules that have a periodic (breathing) attractive force in addition to the conventional intermolecular forces. The phase diagram for such molecules is as expected when the ''breathing'' properties are independent of density. However, when (more realistically), the ''breathing'' properties are density dependent, the phase diagram exhibits dramatic changes. These calculations may be useful for interpreting experimental data for protein precipitation, for plaque formation in blood vessels and for scaffold-supported tissue formation.

  13. Partitioning and phase equilibria of PEGylated excipients in fluorinated liquids.

    PubMed

    Paul, Alison; Talbot, Gemma L; Bowles, James W; James, Jennifer; Griffiths, Peter C; Rogueda, Philippe G

    2010-03-15

    Mixtures of common polymeric excipients and hydrofluoroalkane (HFA) liquids show rich and complex phase behaviour. Phase diagrams and phase compositions are reported for poly(ethylene glycol)s with varying levels of end-group methylation in mixed solvent systems consisting of the model propellant 2H,3H-perfluoropentane (HPFP) and the fully fluorinated analogue perfluoropentane (PFP). Studies have been performed as a function of molecular weight as well as end group chemistry (monomethyl, MM; dimethyl, DM; and dihydroxyl, DH), and for binary polymer mixtures in HPFP/PFP solvent systems. The solvent composition required to induce phase separation by addition of the non-hydrogen bonding PFP is strongly dependent on end-group concentrations. It shows a linear increase with increasing methylation, whilst remaining insensitive to OH group concentration in dihydroxylated PEG systems. For single polymer systems it is observed that strong partitioning of the polymer is observed, and changes in polymer concentration occurring across the phase diagram are a result of changing solvent partitioning between upper and lower phases. These solvent effects are dependent on the composition (wt% PFP) in the solvent mixture. The linear dependence of solvent composition required to induce phase separation at fixed polymer concentration on end group concentrations can be used to predict the phase behaviour for mixtures of monomethylated PEG with either dimethyl or dihydroxyl PEGs, whereas mixtures of dihydroxyl with dimethyl end-capped PEGs show a deviation from linear behaviour with dominance of the dihydroxyl end groups, which is reflected in the obtained phase diagrams. This study hence progresses understanding of factors that influence solubility of PEG-type polymers in HFAs and will facilitate the identification of predictive methodologies for formulation.

  14. Phase equilibria and crystal chemistry of rubidium niobates and rubidium tantalates

    NASA Technical Reports Server (NTRS)

    Minor, D. B.; Roth, R. S.; Parker, H. S.; Brower, W. S.

    1977-01-01

    The phase equilibria relations and crystal chemistry of portions of the Rb2O-Nb2O5 and Rb2O-Ta2O5 systems were investigated for structures potentially useful as ionic conductors. A hexagonal tungsten bronze-type (HTB) structure was found in both systems as well as three hexagonal phases with mixed HTB-pyrochlore type structures. Ion exchange experiments between various alkali ions are described for several phases. Unit cell dimensions and X-ray diffraction powder patterns are reported.

  15. High-pressure phase equilibria with compressed gases.

    PubMed

    Ren, Wei; Scurto, Aaron M

    2007-12-01

    An apparatus is described that is capable of determining high-pressure vapor-liquid equilibrium, liquid-liquid equilibrium, solid-liquid-vapor equilibrium, vapor-liquid-liquid equilibrium, and mixture critical points and transitions. The device is capable of temperatures to 150 degrees C and pressures to 300 bars (higher with slight modifications). The construction and operation are described in detail and do not require the use of mercury. This method requires very low sample volumes and no analytical equipment nor system-specific calibration. The apparatus was verified by comparison with literature data for the decane-CO(2) mixture and CO(2)-ionic liquid [1-hexyl-3-methyl-imidazolium bis(trifyl)imide)] systems. The experimental data have excellent agreement with the literature data that used different experimental methods. A rigorous error analysis of the system is also presented.

  16. Integral equation theory description of phase equilibria in classical fluids

    NASA Astrophysics Data System (ADS)

    Caccamo, C.

    1996-09-01

    We review the present status of applications of integral equation theories (IETs) for the radial distribution function g( r), to the determination of phase diagrams and stability conditions of simple and charged classical fluids. After having recalled some basic concepts and definitions in the structural description of fluid systems, a number of IETs are examined by reporting the constituting equations and solution procedures; these last are discussed also in relationship with the actual calculation of coexistence lines and description of the critical behavior of each envisaged theory. In this context, the crucial role played by the fulfilment of thermodynamic consistency in the improvement of the performances of the various approximations, is highlighted. Then, a number of results of phase diagram determinations, phase stability investigations, and estimates of critical exponents, are reported for several neutral and charged model fluids (and their mixtures) such as the hard sphere fluid, the square-well fluid, the hard-core Yukawa fluid, the Lennard-Jones fluid, and charged hard spheres in different regimes of density, sizes and charges. Calculations of the phase diagram of a rigid molecule model of C 60 are also reported. Besides their theoretical interest, these models are investigated by many authors also because they can reasonably mimic real systems like rare gas liquids, electrolyte solutions, molten salts, neutral and charged micellar systems, and colloidal solutions. The related experimental evidence is therefore frequently referred, and comparison with experimental results is also performed in some case. Theoretical results are usually presented in parallel with the available computer simulation data, which are extensively quoted both with the aim of a systematic assessment of the theories, and in order to offer a more complete scenario of phase behavior calculations in classical fluids. Perspectives and advantages of future extensions and applications

  17. Phase equilibria in water-(1-, 2-, iso-)butanol-18-crown-6 systems

    NASA Astrophysics Data System (ADS)

    Kovalenko, N. A.; Golovina, N. B.; Bogachev, A. G.; Uspenskaya, I. A.

    2011-09-01

    We present the results from measuring the solubility of 18-crown-6 in isobutanol in the temperature interval of 280-308 K and information about liquid-liquid equilibria in water-(1-, 2-, iso-)butanol-18-crown-6 systems at 298 K. The parameter values of the extended UNIQUAC model were determined on the basis of information about the thermodynamic properties and phase equilibria in the binary systems. It is shown that we must use parameters of ternary interaction in addition to binary parameters to adequately describe the miscibility gap on the basis of the results of turbidimetric titration in ternary water-(1-,2-, iso)butanol-18-crown-6 systems.

  18. Phase equilibria in an athermal solution of platelike particles

    PubMed

    Sokolowska; Moscicki

    2000-10-01

    A molecular frame lattice theory of athermal solutions of platelike particles is presented. Steric repulsion between the particles is assumed to be the sole interaction present in the system (the athermal limit). The theory is developed for flat rectangular parallelepipeds, and examined in detail for two opposite shape anisotropy limits: rods and square boards. Numerical calculations show that in a pure system of either long rods or square boards, a nematic phase is formed once the shape anisotropy exceeds some critical value: for rods the critical aspect ratio x(crit)(r) is 8. 019, and for boards x(crit)(d) is 3.742. For higher values of the ratio, a narrow concentration region of coexistence for the nematic and isotropic phases, which separates the isotropic (low concentration) from the nematic (high concentration) solution, is found on dilution of each system. PMID:11089050

  19. Phase equilibria and thermodynamics of p-hydroxybenzoic acid.

    PubMed

    Nordström, Fredrik L; Rasmuson, Ake C

    2006-04-01

    The prevalence of phases and associated solubilities of p-hydroxybenzoic acid have been investigated in methanol, acetonitrile, acetic acid, acetone, water, and ethyl acetate at temperatures from 10 to 50 degrees C. Thermodynamic data was acquired through determination of van't Hoff enthalpy of solution, enthalpy of fusion, and melting temperature. Indications of polymorphic enantiotropy were found primarily through solubility analysis and FTIR-ATR. A comprehensive thermodynamic investigation disclosed correlation between the van't Hoff enthalpy of solution and the solubility in different solvents. A higher solubility is linked to a lower van't Hoff enthalpy of solution. A thermodynamic analysis to discriminate between different solid phases is presented.

  20. Floating zone crystal growth and phase equilibria - A review

    NASA Astrophysics Data System (ADS)

    Kimura, Shigeyuki; Kitamura, Kenji

    1992-06-01

    The thermal-imaging floating zone technique can be used to grow crystals of yttrium iron garnet aluminum-doped yttrium orthoferrite and magnetite, which represent peritectic compounds, solid-solution crytals, and atmosphere-sensitive materials, respectively. The reactions involved in floating zone crystal growth are explained on the basis of phase diagrams. A review of crystal growth reports, including unpublished findings by the present authors, demonstrates how the crystallization processes, the reaction with the ambient atmosphere, and the composition variation in the obtained crystals can be explained or controlled on the basis of phase equilibrium. The floating zone technique is applicable to a variety of materials and remains a handy tool for materials research; however, its industrial application may be limited.

  1. Phase equilibria of size-asymmetric primitive model electrolytes.

    PubMed

    Yan, Q; de Pablo, J J

    2001-03-01

    The low-temperature phase coexistence of size-asymmetric primitive model electrolyte solutions has been investigated by means of Monte Carlo simulations. Binodal curves and critical parameters are reported as a function of size ratio lambda = sigma(+)/sigma(-) in the range 0.05 to 1. Both the critical temperature and the critical density are found to decrease as lambda decreases. These trends are in conflict with available theoretical predictions. For highly asymmetric systems, the depression of the critical parameters is accompanied by the formation of large chainlike and ringlike structures, thereby giving rise to considerable finite-size effects.

  2. Thermodynamic properties and phase equilibria of selected Heusler compounds

    NASA Astrophysics Data System (ADS)

    Yin, Ming

    Heusler compounds are ternary intermetallics with many promising properties such as spin polarization and magnetic shape memory effect. A better understanding of their thermodynamic properties facilitates future design and development. Therefore, standard enthalpies of formation and heat capacities from room temperature to 1500 K of selected Heusler compounds X2YZ (X = Co, Fe, Ni, Pd, Rh, Ru; Y = Co, Cu, Fe, Hf, Mn, Ni, Ti, V, Zr; Z = Al, Ga, In, Si, Ge, Sn) and half-Heusler compounds XYSn (X = Au, Co, Fe, Ir, Ni, Pd, Pt, Rh; Y = Hf, Mn, Ti, Zr) were measured using high temperature direct reaction calorimetry. The measured standard enthalpies of formation were compared with those predicted from ab initio calculations and the extended semi-empirical Miedema's model. Trends in standard enthalpy of formation with respect to the periodic classification of elements were discussed. The effect of a fourth element (Co, Cu, Fe, Pd; Ti, V; Al, Ga, In, Si, Ge) on the standard enthalpy of formation of Ni2MnSn was also investigated. Lattice parameters of the compounds with an L21 structure were determined using X-ray powder diffraction analysis. Differential scanning calorimetry was used to determine melting points and phase transformation temperatures. Phase relationships were investigated using scanning electron microscopy with an energy dispersive spectrometer. The isothermal section of the Fe-Sn-Ti ternary system at 873 K was established using equilibrated alloys. Three ternary compounds including the Heusler compound Fe2SnTi were observed. A new ternary compound Fe5Sn9Ti 6 was reported and the crystal structure of FeSnTi2 was determined for the first time.

  3. Phase equilibria of H2SO4, HNO3, and HCl hydrates and the composition of polar stratospheric clouds

    NASA Technical Reports Server (NTRS)

    Wooldridge, Paul J.; Zhang, Renyi; Molina, Mario J.

    1995-01-01

    Thermodynamic properties and phase equilibria behavior for the hydrates and coexisting pairs of hydrates of common acids which exist in the stratosphere are assembled from new laboratory measurements and standard literature data. The analysis focuses upon solid-vapor and solid-solid-vapor equilibria at temperatures around 200 K and includes new calorimetric and vapor pressure data. Calculated partial pressures versus 1/T slopes for the hydrates and coexisting hydrates agree well with experimental data where available.

  4. Phase Equilibria of H2SO4, HNO3, and HCl Hydrates and the Composition of Polar Stratospheric Clouds

    NASA Technical Reports Server (NTRS)

    Wooldridge, Paul J.; Zhang, Renyi; Molina, Mario J.

    1995-01-01

    Thermodynamic properties and phase equilibria behavior for the hydrates and coexisting pairs of hydrates of common acids which exist in the stratosphere are assembled from new laboratory measurements and standard literature data. The analysis focuses upon solid-vapor and solid-solid-vapor equilibria at temperatures around 200 K and includes new calorimetric and vapor pressure data. Calculated partial pressures versus 1/T slopes for the hydrates and coexisting hydrates agree well with experimental data where available.

  5. Monte carlo simulation of carboxylic acid phase equilibria.

    PubMed

    Clifford, Scott; Bolton, Kim; Ramjugernath, Deresh

    2006-11-01

    Configurational-bias Monte Carlo simulations were carried out in the Gibbs ensemble to generate phase equilibrium data for several carboxylic acids. Pure component coexistence densities and saturated vapor pressures were determined for acetic acid, propanoic acid, 2-methylpropanoic acid, and pentanoic acid, and binary vapor-liquid equilibrium (VLE) data for the propanoic acid + pentanoic acid and 2-methylpropanoic acid + pentanoic acid systems. The TraPPE-UA force field was used, as it has recently been extended to include parameters for carboxylic acids. To simulate the branched compound 2-methylpropanoic acid, certain minor assumptions were necessary regarding angle and torsion terms involving the -CH- pseudo-atom, since parameters for these terms do not exist in the TraPPE-UA force field. The pure component data showed good agreement with the available experimental data, particularly with regard to the saturated liquid densities (mean absolute errors were less than 1.1%). On average, the predicted critical temperature and density were within 1% of the experimental values. All of the binary simulations showed good agreement with the experimental x-y data. However, the TraPPE-UA force field predicts saturated vapor pressures of pure components that are larger than the experimental values, and consequently the P-x-y and T-x-y data of the binary systems also deviate from the measured data.

  6. 10 kbar phase equilibria in the Y-Ba-Cu oxide system at 950 C

    SciTech Connect

    Lawanier, J.P.; Meen, J.K.; Elthon, D.

    1996-02-01

    Phase equilibria in the YO{sub 1.5}BaO-CuO system have been determined at 950 C at 10 kbar using a piston-cylinder apparatus. The oxide phases stable under these conditions are Y{sub 2}O{sub 3}, Y{sub 2}Cu{sub 2}O{sub 5}, CuO, Y{sub 2}BaCuO{sub 5}, YBa{sub 2}Cu{sub 3}O{sub 6.5}, BaCuO{sub 2}, Y{sub 2}BaO{sub 4}, Y{sub 2}Ba{sub 3}O{sub 6}, and YBa{sub 4}Cu{sub 2}O{sub 7.5}. The phase stabilities observed at 950 C at 10 kbar are identical to those observed at 950 C in air or oxygen at 1 atm for compositions with < 40% Ba of the cations. In more Ba-rich portions of the phase diagram, carbonates and oxycarbonates are stabilized and a systematic determination of the phase equilibria has not been successful.

  7. Artificial multiple criticality and phase equilibria: an investigation of the PC-SAFT approach.

    PubMed

    Yelash, Leonid; Müller, Marcus; Paul, Wolfgang; Binder, Kurt

    2005-11-01

    The perturbed-chain statistical associating fluid theory (PC-SAFT) is studied for a wide range of temperature, T, pressure, p, and (effective) chain length, m, to establish the generic phase diagram of polymers according to this theory. In addition to the expected gas-liquid coexistence, two additional phase separations are found, termed "gas-gas" equilibrium (at very low densities) and "liquid-liquid" equilibrium (at densities where the system is expected to be solid already). These phase separations imply that in one-component polymer systems three critical points occur, as well as equilibria of three fluid phases at triple points. However, Monte Carlo simulations of the corresponding system yield no trace of the gas-gas and liquid-liquid equilibria, and we conclude that the latter are just artefacts of the PC-SAFT approach. Using PC-SAFT to correlate data for polybutadiene melts, we suggest that discrepancies in modelling the polymer density at ambient temperature and high pressure can be related to the presumably artificial liquid-liquid phase separation at lower temperatures. Thus, particular care is needed in engineering applications of the PC-SAFT theory that aims at predicting properties of macromolecular materials.

  8. Diffusion, phase equilibria and partitioning experiments in the Ni-Fe-Ru system

    NASA Technical Reports Server (NTRS)

    Blum, Joel D.; Wasserburg, G. J.; Hutcheon, I. D.; Beckett, J. R.; Stolper, E. M.

    1989-01-01

    Results are presented on thin-film diffusion experiments designed to investigate phase equilibria in systems containing high concentrations of Pt-group elements, such as Ni-Fe-Ru-rich systems containing Pt, at temperatures of 1273, 1073, and 873 K. The rate of Ru diffusion in Ni was determined as a function of temperature, and, in addition, the degree of Pt and Ir partitioning between phases in a Ni-Fe-Ru-rich system and of V between phases in a Ni-Fe-O-rich system at 873 were determined. It was found that Pt preferentially partitions into the (gamma)Ni-Fe phase, whereas Ir prefers the (epsilon)Ru-Fe phase. V partitions strongly into Fe oxides relative to (gamma)Ni-Fe. These results have direct application to the origin and thermal history of the alloys rich in Pt-group elements in meteorites.

  9. Phases, phase equilibria, and phase rules in low-dimensional systems

    SciTech Connect

    Frolov, T.; Mishin, Y.

    2015-07-28

    We present a unified approach to thermodynamic description of one, two, and three dimensional phases and phase transformations among them. The approach is based on a rigorous definition of a phase applicable to thermodynamic systems of any dimensionality. Within this approach, the same thermodynamic formalism can be applied for the description of phase transformations in bulk systems, interfaces, and line defects separating interface phases. For both lines and interfaces, we rigorously derive an adsorption equation, the phase coexistence equations, and other thermodynamic relations expressed in terms of generalized line and interface excess quantities. As a generalization of the Gibbs phase rule for bulk phases, we derive phase rules for lines and interfaces and predict the maximum number of phases than may coexist in systems of the respective dimensionality.

  10. Phase equilibria in the condensed system n-docosane-cyclododecane- n-decane

    NASA Astrophysics Data System (ADS)

    Shamitov, A. A.; Garkushin, I. K.; Kolyado, A. V.

    2016-07-01

    Phase equilibria in the system n-docosane-cyclododecane-n-decane are studied by means of differential thermal analysis. It is found that the system is of the eutectic type. The temperature of eutectic melting is found to be-34.9°C, the n-docosane content is 3.5 wt %, the n-decane content is 86.5 wt %, and the cyclododecane content is 10.0 wt %. It is concluded that the results can be used to create new optimal heatstorage materials.

  11. Phase equilibria and plate-fluid interfacial tensions for associating hard sphere fluids confined in slit pores.

    PubMed

    Fu, Dong; Li, Xiao-Sen

    2006-08-28

    The excess Helmholtz free energy functional for associating hard sphere fluid is formulated by using a modified fundamental measure theory [Y. X. Yu and J. Z. Wu, J. Chem. Phys. 117, 10156 (2002)]. Within the framework of density functional theory, the thermodynamic properties including phase equilibria for both molecules and monomers, equilibrium plate-fluid interfacial tensions and isotherms of excess adsorption, average molecule density, average monomer density, and plate-fluid interfacial tension for four-site associating hard sphere fluids confined in slit pores are investigated. The phase equilibria inside the hard slit pores and attractive slit pores are determined according to the requirement that temperature, chemical potential, and grand potential in coexistence phases should be equal and the plate-fluid interfacial tensions at equilibrium states are predicted consequently. The influences of association energy, fluid-solid interaction, and pore width on phase equilibria and equilibrium plate-fluid interfacial tensions are discussed.

  12. Phase equilibria in a three-component water-soap-alcohol system. A thermodynamic model

    SciTech Connect

    Joensson, B.; Wennerstroem, H.

    1987-01-15

    A thermodynamic model is presented for ternary systems consisting of ionic surfactant-long-chain alcohol-water. The important contributions to the model free energy are (i) an electrostatic term; (ii) a free energy term; (iii) four entropy terms; (iv) constraints imposed by molecular packing restrictions; and (v) a hydration force. The free energy expressions are developed for (spherical) micellar solutions, normal hexagonal liquid crystals, lamellar liquid crystals, reversed hexagonal liquid crystals, and inverted (spherical) micellar solutions. For all these types of phases the aggregate geometries are optimized and the relative stabilities are determined. The phase equilibria are determined by deriving explicit expressions for the chemical potentials of the three components and using the criterion that they should be equal for phases in equilibrium. The model gives a nearly quantitative description of the equilibria in the test system potassium decanoate-octanol-water. The general conclusions are (i) at high ratios of ionic surfactant to alcohol the dominating factor is the electrostatics, with an additional effect from the fact that the alcohol decreases the free energy of the polar-apolar interface; (ii) the stability of the inverted micellar system is greatly influenced by the entropy of mixing between the palisade layer and the bulk alcohol medium; (iii) at low water contents one has to invoke the occurrence of a hydration force.

  13. Solid-liquid phase equilibria from free-energy perturbation calculations

    NASA Astrophysics Data System (ADS)

    Angioletti-Uberti, Stefano; Asta, Mark; Finnis, Mike W.; Lee, P. D.

    2008-10-01

    A method for calculating free-energy differences based on a free-energy perturbation (FEP) formalism in an alloy system described by two different Hamiltonians is reported. The intended application is the calculation of solid-liquid phase equilibria in alloys with the accuracy of first-principles electronic density-functional theory (DFT). For this purpose free energies are derived with a classical interatomic potential, and FEP calculations are used to compute corrections to these reference values. For practical applications of this approach, due to the relatively high computational cost of DFT calculations, it is critical that the FEP calculations converge rapidly in terms of the number of samples used to estimate relevant ensemble averages. This issue is investigated in the current study employing two classical interatomic-potential models for Ni-Cu. These models yield differences in predicted phase-boundary temperatures of approximately 100 K, comparable to those that might be expected between a DFT Hamiltonian and a well-fit classical potential. We show that for pure elements the FEP calculations converge rapidly with the number of samples, yielding free-energy differences converged to within a fraction of a meV/atom in a few dozen energy calculations. For a concentrated equiatomic alloy similar precision requires roughly a hundred samples. The results suggest that the proposed methodology could provide a computationally tractable framework for calculating solid-liquid phase equilibria in concentrated alloys with DFT accuracy.

  14. Landau resonant modification of multiple kink mode contributions to 3D tokamak equilibria

    DOE PAGES

    King, J. D.; Strait, E. J.; Ferraro, N. M.; Hanson, J. M.; Haskey, S. R.; Lanctot, M. J.; Liu, Y. Q.; Logan, N.; Paz-Soldan, C.; Shiraki, D.; et al

    2015-12-17

    Detailed measurements of the plasma's response to applied magnetic perturbations provide experimental evidence that the form of three-dimensional (3D) tokamak equilibria, with toroidal mode number n = 1, is determined by multiple stable kink modes at high-pressure. For pressures greater than the ideal magnetohydrodynamic (MHD) stability limit, as calculated without a stabilizing wall, the 3D structure transitions in a way that is qualitatively predicted by an extended MHD model that includes kinetic wave-particle interactions. These changes in poloidal mode structure are correlated with the proximity of rotation profiles to thermal ion bounce and the precession drift frequencies suggesting that thesemore » kinetic resonances are modifying the relative amplitudes of the stable modes. These results imply that each kink may eventually be independently controlled.« less

  15. Landau resonant modification of multiple kink mode contributions to 3D tokamak equilibria

    SciTech Connect

    King, J. D.; Strait, E. J.; Ferraro, N. M.; Hanson, J. M.; Haskey, S. R.; Lanctot, M. J.; Liu, Y. Q.; Logan, N.; Paz-Soldan, C.; Shiraki, D.; Turnbull, A. D.

    2015-12-17

    Detailed measurements of the plasma's response to applied magnetic perturbations provide experimental evidence that the form of three-dimensional (3D) tokamak equilibria, with toroidal mode number n = 1, is determined by multiple stable kink modes at high-pressure. For pressures greater than the ideal magnetohydrodynamic (MHD) stability limit, as calculated without a stabilizing wall, the 3D structure transitions in a way that is qualitatively predicted by an extended MHD model that includes kinetic wave-particle interactions. These changes in poloidal mode structure are correlated with the proximity of rotation profiles to thermal ion bounce and the precession drift frequencies suggesting that these kinetic resonances are modifying the relative amplitudes of the stable modes. These results imply that each kink may eventually be independently controlled.

  16. On the question of phase equilibria in the succinonitrile-(D)camphor system

    NASA Astrophysics Data System (ADS)

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

    2013-07-01

    Alloys from the succinonitrile-(D)camphor (SCN-DC) system are widely used as model alloys for the in situ investigation of solidification using light optical microscopy, but literature on the binary phase diagram is contradictory with respect to the solubility limit of DC in (SCN). Phase equilibria of the system were therefore revisited experimentally and critically assessed in the present work. The results prove that the maximum solubility of DC in the succinonitrile solid solution (SCN) is far less 1 wt% and the volume fraction of the (DC) phase in the eutectic solid is 23.3%. On this basis and on recently reported experimental data the CALPHAD description of the SCN-DC system was re-optimized.

  17. Phase equilibria and thermodynamic modeling of ethane and propane hydrates in porous silica gels.

    PubMed

    Seo, Yongwon; Lee, Seungmin; Cha, Inuk; Lee, Ju Dong; Lee, Huen

    2009-04-23

    In the present study, we examined the active role of porous silica gels when used as natural gas storage and transportation media. We adopted the dispersed water in silica gel pores to substantially enhance active surface for contacting and encaging gas molecules. We measured the three-phase hydrate (H)-water-rich liquid (L(W))-vapor (V) equilibria of C(2)H(6) and C(3)H(8) hydrates in 6.0, 15.0, 30.0, and 100.0 nm silica gel pores to investigate the effect of geometrical constraints on gas hydrate phase equilibria. At specified temperatures, the hydrate stability region is shifted to a higher pressure region depending on pore size when compared with those of bulk hydrates. Through application of the Gibbs-Thomson relationship to the experimental data, we determined the values for the C(2)H(6) hydrate-water and C(3)H(8) hydrate-water interfacial tensions to be 39 +/- 2 and 45 +/- 1 mJ/m(2), respectively. By using these values, the calculation values were in good agreement with the experimental ones. The overall results given in this study could also be quite useful in various fields, such as exploitation of natural gas hydrate in marine sediments and sequestration of carbon dioxide into the deep ocean.

  18. Phase equilibria of carbon dioxide hydrate system in the presence of sucrose, glucose, and fructose

    SciTech Connect

    Chun, M.K.; Lee, H.

    1999-09-01

    The three-phase (H-L{sub w}-V) equilibria of the carbon dioxide hydrate formation system in aqueous solutions containing sucrose, glucose, and fructose were experimentally determined at pressures ranging from 1.580 to 4.355 MPa and at temperatures between 273.6 and 281.7 K. The upper quadruple points (H-L{sub w}-L{sub CO{sub 2}}-V) were also measured at concentrations of 10, 20, and 30 mass % sucrose, glucose, and fructose. The addition of carbohydrates exhibited a similar inhibition effect as that observed for electrolytes and alcohols. A thermodynamic model predicting the three- and four-phase hydrate equilibria while accounting for the inhibition effect of carbohydrates was developed on the basis of the van der Waals-Platteeuw model and the Redlich-Kwong-Soave equation of state with a modified version of the Huron-Vidal mixing rule. The calculated results were found to be in good agreement with the experimental data.

  19. Molecular modeling at interfaces: Phase equilibria of complex fluids, and mechanical properties of nanostructures

    NASA Astrophysics Data System (ADS)

    Rivera-Rojas, Jose Luis

    Molecular simulation is a very powerful technique that allows us to predict thermodynamic and transport properties of bulk and confined phases, as well as phase equilibria and interfacial properties. These properties are often crucial to the design of chemical and related industrial processes. Molecular simulation can predict these properties over a wide range of conditions, in contrast with experiments, which at extreme conditions (e.g., high temperature and/or high pressure) are often very difficult and in some cases dangerous. Furthermore, semi-empirical and empirical engineering models can frequently only be used for the specific systems to which they are fitted---that is, they are interpolative rather than predictive. Therefore molecular modeling methods, including simulation, can play a very useful role in the design of new processes, as well as the prediction of new phenomena. In this thesis, we applied molecular simulation methods to four separate problems: vapor-liquid equilibrium for a polarizable model of water, liquid-liquid interfacial properties, phase equilibrium in confined systems, and mechanical properties of nano scale systems. The first three problems imply the study of phases in equilibrium under different conditions. The most simple is the vapor-liquid equilibrium of a single component. Thermophysical properties such as coexistence densities, vapor pressure, surface tension, and interfacial thickness were obtained for a polarizable model of water and compared with other simpler potential models and experimental results. Using the same methodology, the interfacial properties of binary and ternary mixtures with polar and non-polar fluids exhibiting liquid-liquid equilibrium were studied. The dependence of the interfacial properties with increasing molecular size of one compound was studied. For ternary mixtures, the presence of a surfactant molecule was studied at different concentrations of the surfactant. Phase equilibria inside single carbon

  20. Liquid-vapor phase equilibria and the thermodynamic properties of 2-methylpropanol- n-alkyl propanoate solutions

    NASA Astrophysics Data System (ADS)

    Suntsov, Yu. K.; Goryunov, V. A.; Chuikov, A. M.; Meshcheryakov, A. V.

    2016-08-01

    The boiling points of solutions of five binary systems are measured via ebulliometry in the pressure range of 2.05-103.3 kPa. Equilibrium vapor phase compositions, the values of the excess Gibbs energies, enthalpies, and entropies of solution of these systems are calculated. Patterns in the changes of phase equilibria and thermodynamic properties of solutions are established, depending on the compositions and temperatures of the systems. Liquid-vapor equilibria in the systems are described using the equations of Wilson and the NRTL (Non-Random Two-Liquid Model).

  1. Phase equilibria of the magnesium sulfate-water system to 4 kbars

    NASA Technical Reports Server (NTRS)

    Hogenboom, D. L.; Kargel, J. S.; Ganasan, J. P.; Lee, L.

    1993-01-01

    Magnesium sulfate is the most abundant salt in carbonaceous chondrites, and it may be important in the low-temperature igneous evolution and aqueous differentiation of icy satellites and large chondritic asteroids. Accordingly, we are investigating high-pressure phase equilibria in MgSO4-H2O solutions under pressures up to four kbars. An initial report was presented two years ago. This abstract summarizes our results to date including studies of solutions containing 15.3 percent, 17 percent, and 22 percent MgSO4. Briefly, these results demonstrate that increasing pressure causes the eutectic and peritectic compositions to shift to much lower concentrations of magnesium sulfate, and the existence of a new low-density phase of magnesium sulfate hydrate.

  2. MTDATA and the Prediction of Phase Equilibria in Oxide Systems: 30 Years of Industrial Collaboration

    NASA Astrophysics Data System (ADS)

    Gisby, John; Taskinen, Pekka; Pihlasalo, Jouni; Li, Zushu; Tyrer, Mark; Pearce, Jonathan; Avarmaa, Katri; Björklund, Peter; Davies, Hugh; Korpi, Mikko; Martin, Susan; Pesonen, Lauri; Robinson, Jim

    2016-09-01

    This paper gives an introduction to MTDATA, Phase Equilibrium Software from the National Physical Laboratory (NPL), and describes the latest advances in the development of a comprehensive database of thermodynamic parameters to underpin calculations of phase equilibria in large oxide, sulfide, and fluoride systems of industrial interest. The database, MTOX, has been developed over a period of thirty years based upon modeling work at NPL and funded by industrial partners in a project co-ordinated by Mineral Industry Research Organisation. Applications drawn from the fields of modern copper scrap smelting, high-temperature behavior of basic oxygen steelmaking slags, flash smelting of nickel, electric furnace smelting of ilmenite, and production of pure TiO2 via a low-temperature molten salt route are discussed along with calculations to assess the impact of impurities on the uncertainty of fixed points used to realize the SI unit of temperature, the kelvin.

  3. Phase liquid-vapor equilibria and thermodynamic properties of solutions of n-propanol-aliphatic ketones

    NASA Astrophysics Data System (ADS)

    Suntsov, Yu. K.; Vlasov, M. V.; Chuikov, A. M.

    2015-06-01

    The boiling points of solutions of five binary systems are measured using the ebulliometric method in the pressure range of 4.4-101.3 kPa. Compositions of the equilibrium vapor phases of systems are calculated, based on the constructed pressure isotherms of saturated vapor. The values of excess Gibbs energy and the enthalpy and entropy of solutions are calculated from the data on the liquid-vapor equilibrium. The patterns of change in the phase equilibria and thermodynamic properties of the solutions are established, based on the composition and temperature of the systems. The liquid-vapor equilibrium of systems is described using the equations of Wilson and the NRTL (Non-Random Two-Liquid model).

  4. Critical comparison of classical and quantum mechanical treatments of the phase equilibria of water

    SciTech Connect

    Wick, Collin D.; Schenter, Gregory K.

    2006-03-17

    The Gibbs ensemble Monte Carlo simulation technique was used to compare the phase equilibria of the rigid TIP4P water model [J.\\ Chem.\\ Phys.\\ {\\bf 79}, 926, (1983)] utilizing classical and quantum statistical mechanical treatments. The quantum statistical mechanical treatment generally resulted in lower liquid densities and higher vapor densities, showing a narrowing in the phase envelope. As a result, the calculated critical temperature and normal boiling point were higher from the quantum simulations than the classical by 20~and 17~K, respectively, but the critical densities were very close. A semiclassical treatment, involving a low order expansion in Plank's constant, resulted in densities and vapor pressures that fluctuated between the values for the classical and quantum statistical mechanics values, with no definite agreement with either.

  5. Solid state phase equilibria and intermetallic compounds of the Al-Cr-Ho system

    SciTech Connect

    Pang, Mingjun; Zhan, Yongzhong; Du, Yong

    2013-02-15

    The solid state phase equilibria of the Al-Cr-Ho ternary system at 500 Degree-Sign C were experimentally investigated. The phase relations at 500 Degree-Sign C are governed by 14 three-phase regions, 29 two-phase regions and 15 single-phase regions. The existences of 10 binary compounds and 2 ternary phases have been confirmed. Al{sub 11}Cr{sub 2}, Al{sub 11}Cr{sub 4} and Al{sub 17}Ho{sub 2} were not found at 500 Degree-Sign C. Crystal structures of Al{sub 9}Cr{sub 4} and Al{sub 8}Cr{sub 4}Ho were determined by the Rietveld X-ray powder data refinement. Al{sub 9}Cr{sub 4} was found to exhibit cubic structure with space group I4-bar 3m (no. 217) and lattice parameters a=0.9107(5) nm. Al{sub 8}Cr{sub 4}Ho crystallizes in ThMn{sub 12} structure type with space group I4/mmm (no. 139) and lattice parameters a=0.8909(4) nm, c=0.5120(5) nm. It is concluded that the obtained Al{sub 4}Cr phase in this work should be {mu}-Al{sub 4}Cr by comparing with XRD pattern of the hexagonal {mu}-Al{sub 4}Mn compound. - Graphical abstract: The solid state phase equilibria of the Al-Cr-Ho ternary system at 500 Degree-Sign C. Highlights: Black-Right-Pointing-Pointer Al-Cr-Ho system has been investigated. Black-Right-Pointing-Pointer Al{sub 9}Cr{sub 4} has cubic structure with space group I4-bar 3m. Black-Right-Pointing-Pointer Al{sub 8}Cr{sub 4}Ho crystallizes in ThMn{sub 12} type with space group I4/mmm. Black-Right-Pointing-Pointer Al{sub 4}Cr phase is {mu}-type at 500 Degree-Sign C.

  6. The systems Sr-Zn-{l_brace}Si,Ge{r_brace}: Phase equilibria and crystal structure of ternary phases

    SciTech Connect

    Romaka, V.V.; Falmbigl, M.; Grytsiv, A.; Rogl, P.

    2012-02-15

    Phase relations have been established by electron probe microanalysis (EPMA) and X-ray powder diffraction (XPD) for the Sr-poor part of the ternary systems Sr-Zn-Si at 800 Degree-Sign C and Sr-Zn-Ge at 700 Degree-Sign C. In the Sr-Zn-Si system one new ternary compound SrZn{sub 2+x}Si{sub 2-x} (0{<=}x{<=}0.45) with CeAl{sub 2}Ga{sub 2} structure and a statistical mixture of Zn/Si in the 4e site was found. Neither a type-I nor a type-IX clathrate phase was encountered. This system is characterized by formation of two further phases, i.e. SrZn{sub 1-x}Si{sub 1+x} with ZrBeSi-type (0.16{<=}x{<=}0.22) and SrZn{sub 1-x}Si{sub 1+x} with AlB{sub 2}-type (0.35{<=}x{<=}0.65) with a random distribution of Zn/Si atoms in the 2c site. For the Sr-Zn-Ge system, the homogeneity regions of the isotypic phases SrZn{sub 1-x}Ge{sub 1+x} with ZrBeSi-type (0{<=}x{<=}0.17) and AlB{sub 2}-type (0.32{<=}x{<=}0.56), respectively, have been determined. Whereas the germanide SrZn{sub 2+x}Ge{sub 2-x} (CeAl{sub 2}Ga{sub 2}-type) is characterized by a homogeneity region (0{<=}x{<=}0.5), the clathrate type-I phase Sr{sub 8}Zn{sub 8}Ge{sub 38} shows a point composition. - Graphical abstract: Phase equilibria of ternary compounds in the Sr-Zn-Si-system at 800 Degree-Sign C. Highlights: Black-Right-Pointing-Pointer Phase equilibria in the Sr-Zn-Si-system are established at 800 Degree-Sign C. Black-Right-Pointing-Pointer Phase equilibria in the Sr-Zn-Ge-system are established at 700 Degree-Sign C. Black-Right-Pointing-Pointer Crystal structures of the ternary compounds were confirmed by X-ray powder diffraction. Black-Right-Pointing-Pointer All ternary compounds except the clathrate-I in the Ge-system are characterized by a homogeneity region.

  7. Gaseous phase coal surface modification

    SciTech Connect

    Okoh, J.M.; Pinion, J.; Thiensatit, S.

    1992-05-07

    In this report, we present an improved, feasible and potentially cost effective method of cleaning and beneficiating ultrafine coal. Increased mechanization of mining methods and the need towards depyritization, and demineralization have led to an increase in the quantity of coal fines generated in recent times. For example, the amount of {minus}100 mesh coal occurring in coal preparation plant feeds now typically varies from 5 to 25% of the total feed. Environmental constraints coupled with the greatly increased cost of coal have made it increasingly important to recover more of these fines. Our method chemically modifies the surface of such coals by a series of gaseous phase treatments employing Friedel-Crafts reactions. By using olefins (ethene, propene and butene) and hydrogen chloride catalyst at elevated temperature, the surface hydrophobicity of coal is enhanced. This increased hydrophobicity is manifest in surface phenomena which reflect conditions at the solid/liquid interphase (zeta potential) and those which reflect conditions at the solid/liquid/gas interphases (contact angle, wettability and floatability).

  8. Selected thermal properties of beryllium and phase equilibria in beryllium systems relevant for nuclear fusion reactor blankets

    NASA Astrophysics Data System (ADS)

    Kleykamp, Heiko

    2001-04-01

    Enthalpies of the hcp-bcc transformation ΔtrH and melting ΔmH of Be were measured by anisothermal calorimetry which gave ΔtrH=6100 J/mol and ΔmH=7200 J/mol. The high value of ΔtrH is explained by the strongly reduced c/ a-axis ratio of the hcp modification. Maximum solubilities of the metallic impurities Al, Cr, Fe, Mg and Si in different Be qualities which annealed at about 800°C are 0.01 mol% or less in each case. In the Al-Be-Fe system, Be(Al, Fe) is in equilibrium with Al 5Fe 2 at 870°C. The phases AlFeBe 4 and Al 2FeBe 2.3 were not observed. The Be-C-Si system is marked by two two-phase equilibria Be 2C-Si and Be 2C-SiC at 900°C. The phase diagram of the pseudo-ternary BeO-Li 2O-SiO 2 system was established on the basis of in-pile Be-BeO-Li 4SiO 4-Li 2SiO 3 compatibility studies at about 450°C. The system is characterised by Li 2BeSiO 4 which is in equilibrium with BeO, Be 2SiO 4,SiO 2,Li 2Si 2O 5,Li 2SiO 3 and Li 4SiO 4. The latter phase is also in equilibrium with Li 2Be 2O 3.

  9. Phase and extraction equilibria in water-polyethyleneglycol ethers of monoethanolamides of synthetic fatty acid-ammonium chloride systems

    NASA Astrophysics Data System (ADS)

    Lesnov, A. E.; Golovkina, A. V.; Kudryashova, O. S.; Denisova, S. A.

    2016-08-01

    Phase equilibria in layering systems of water, polyethyleneglycol ethers of monoethanolamides of synthetic fatty acids (SFAs) (synthamide-5), and ammonium chloride are studied. The possibility of using such systems for the liquid extraction of metal ions is evaluated. The effect the nature of salting-out agents has on the processes of segregation of the systems has been considered.

  10. Planet Alsioff - A problem set for students of phase equilibria or metamorphic petrology

    NASA Technical Reports Server (NTRS)

    Burt, Donald M.

    1988-01-01

    This paper presents a problem set that contains questions for students of phase equilibria or metamorphic petrology concerning a hypothetical planet Alsioff, for which incomplete data are given. On this panet, the SiF4 is the major volatile and Al, Si, O, and F are the only elements present. Progressive metamorphism on Alsioff mainly involves devolatilization of fluid SiF4. The problem set includes ten questions. Some of these are concerned with possible chemical reactions that should affect water, wollastonite, or Ca-SiO3 exposed to the atmosphere of Alsioff; the mechanism of controls of the O2 and F2 contents of the Alsioffian atmosphere; and the devolatilization reactions involving SiF4 with progressive thermal metamorphism.

  11. Extension of the transferable potentials for phase equilibria force field to dimethylmethyl phosphonate, sarin, and soman.

    PubMed

    Sokkalingam, Nandhini; Kamath, Ganesh; Coscione, Maria; Potoff, Jeffrey J

    2009-07-30

    The transferable potentials for phase equilibria force field is extended to dimethylmethylphosphonate (DMMP), sarin, and soman by introducing a new interaction site representing the phosphorus atom. Parameters for the phosphorus atom are optimized to reproduce the liquid densities at 303 and 373 K and the normal boiling point of DMMP. Calculations for sarin and soman are performed in predictive mode, without further parameter optimization. Vapor-liquid coexistence curves, critical properties, vapor pressures and heats of vaporization are predicted over a wide range of temperatures with histogram reweighting Monte Carlo simulations in the grand canonical ensemble. Excellent agreement with experiment is achieved for all compounds, with unsigned errors of less than 1% for vapor pressures and normal boiling points and under 5% for heats of vaporization and liquid densities at ambient conditions.

  12. Biomolecular simulations with the transferable potentials for phase equilibria: extension to phospholipids.

    PubMed

    Bhatnagar, Navendu; Kamath, Ganesh; Potoff, Jeffrey J

    2013-08-29

    The Transferable Potentials for Phase Equilibria (TraPPE) is extended to zwitterionic and charged lipids including phosphatidylcholine (PC), phosphatidylethanolamine (PE), phosphatidylserine (PS), and phosphatidylglycerol (PG). The performance of the force field is validated through isothermal-isobaric ensemble (NPT) molecular dynamics simulations of hydrated lipid bilayers performed with the aforementioned head groups combined with saturated and unsaturated alkyl tails containing 12-18 carbon atoms. The effects of water model and sodium ion parameters on the performance of the lipid force field are determined. The predictions of the TraPPE force field for the area per lipid, bilayer thickness, and volume per lipid are within 1-5% of experimental values. Key structural properties of the bilayer, such as order parameter splitting in the sn-2 chain and X-ray form factors, are found to be in close agreement with experimental data.

  13. Phase equilibria constraints on the chemistry of hot spring fluids at mid-ocean ridges

    SciTech Connect

    Seyfried, W.E. Jr.; Ding, K.; Berndt, M.E. )

    1991-12-01

    Recent advances in experimental and theoretical geochemistry have made it possible to assess both homogeneous and heterogeneous equilibria involving a wide range of aqueous species at temperatures and pressures appropriate to model hydrothermal alteration processes at mid-ocean ridges. The authors have combined selected aspects of the chemistry of hot spring fluids with constraints imposed by a geologically reasonable assemblage of minerals in the system Na{sub 2}O-K{sub 2}O-CaO-MgO-FeO-Fe{sub 2}O{sub 3}-Al{sub 2}O{sub 3}-SiO{sub 2}-H{sub 2}O-HCl-H{sub 2}S to assess the effect of temperature on the composition of the aqueous phase and the activities of mineral components in plagioclase and epidote solid solutions. Assuming fO{sub 2(g)} and fS{sub 2(g)} controlled by pyrite-pyrrhotite-magnetite equilibria, a constant dissolved Ca concentration, and a dissolved Cl concentration equivalent to that of seawater, increasing temperature from 250 to 400C at 500 bars results in systematic changes in the composition of mineral phases, which in turn constrain pH and the distribution of aqueous species. The model predicts that dissolved concentrations of Fe, SiO{sub 2}, K, H{sub 2}S, and H{sub 2} increase, while Na and pH{sub (25C)} decrease with increasing temperature. That many hot springs vent fluids are characterized by variable degrees of conductive heat loss renders measured temperatures unreliable as indicators of the maximum temperature of subseafloor hydrothermal alteration processes. The implications of this are significant for hot spring fluids which reveal large Cl variations relative to seawater, since likely mechanisms to account for such variability typically require temperatures in excess of those inferred for subseafloor reaction zones by simply correcting measured temperatures for the effects of adiabatic cooling.

  14. Phase Equilibria Experiments on Nisyros, Greece:``the Right Stuff" in -``the Right Stuff" out

    NASA Astrophysics Data System (ADS)

    Pyle, D. M.; Hunt, C. A.; Barclay, J.; Charlier, B. L.

    2005-12-01

    To extract meaningful information from phase equilibrium experiments the starting composition must be made of ``the right stuff'' and the results compared with the ``real phenocrysts''. Nisyros island is one of the most active volcanic centres on the South Aegean Volcanic Arc. Pleistocene to recent volcanism has evolved from submarine to sub-aerial in style, culminating in the large caldera-forming eruptions at ca. 33 ka. Post caldera activity has been confined to the extrusion of viscous domes, which fill almost half of the caldera, and hydrothermal eruptions. Studies on the sub-volcanic plumbing dynamics of Nisyros have shown that it is a complex and poorly constrained system, and the need to constrain these parameters is gaining impetus given that Nisyros is showing signs of unrest. The domes are dacitic (SiO2 68 wt. %). Phenocryst phases in decreasing order of abundance are plagioclase, clinopyroxene, orthopyroxene and Fe-Ti oxides. Amphibole is present only as a xenocryst phase, derived from the disaggregation of andesitic magmatic inclusions which are prominent in the dome rocks. There are no eruption dates for the post-caldera activity, but the domes are probably Holocene in age. Age differentiation between the domes is based solely on the extent of weathering and position relative to adjacent domes. Preliminary U/Th investigations of zircons from the ca. 33 ka caldera phase by ion probe have shown that these are inherited, with ages of 92, +35/-27 ka. Low zircon saturation temperatures (731-769 °C) for the post-caldera domes suggest similarly that any zircons present will have been inherited. Extensive geochemical evidence for magma mixing indicates the need for caution in choosing an appropriate starting composition for the phase equilibria experiments. Simple major element modelling suggests limited bulk mixing between silicic and andesitic end-members. There is also little evidence to suggest that the dacite has been hybridised by the andesitic

  15. Phase equilibria and transformations in the Ti-Al-Nb system

    NASA Astrophysics Data System (ADS)

    Mishurda, Joseph Constantine

    The phase equilibria and transformations in the Nb-Ti-Al system in the vicinity of the Sigma phase field have been examined with respect to the Liquidus Surface (Phase 1), the Phase Equilibria and Equilibrium Transformations (Phase II), and the Phase Transformations, Mechanisms and Kinetics (Phase III). Eight alloy compositions were produced by arc melting. The alloys were characterized by differential thermal analysis, metallography, X-ray diffraction, scanning electron microscopy (BSEI), electron probe microanalysis and transmission electron microscopy. The liquidus examination shed new light on previous microstructural interpretations, opening up new possibilities for microstructural development and control of multiphase alloys. Differential thermal analysis has identified the existence of a beta to sigma + gamma transformation in an alloy where it was not previously thought to exist. The results differed from the calculated diagram by higher titanium solubility in the sigma and delta phases than predicted at lower temperatures and a lower solubility of alpha2 and gamma. The high temperature betao transforms to gamma + sigma in a eutectoid fashion resulting in a desirable lamellar structure of sigma and gamma. The existence of a new body centered tetragonal crystal structure ao = 5.11A and co 28.12A with a point group symmetry of P4/mmm, at 700°C was discovered. A plethel section was found for the sigma + beta two phase alloys. A betao + O + sigma three phase field passes through the alloys between 981 and 1000°C. The plethel section at the transformation has an eutectoid characteristic, however, the nature of the transformation changes to a peritectoid. At temperatures below 970°C, the first transformation to occur is the decomposition of the metastable betao phase to an intermediate metastable phase O'. Reasonable values for Q were obtained, applicable to the diffusion limited region of the TTT-curve. The microstructure evolution of the sigma + beta

  16. The heat-capacity of ilmenite and phase equilibria in the system Fe-T-O

    USGS Publications Warehouse

    Anovitz, Lawrence M.; Treiman, A.H.; Essene, E.J.; Hemingway, B.S.; Westrum, E.F.; Wall, V.J.; Burriel, R.; Bohlen, S.R.

    1985-01-01

    Low temperature adiabatic calorimetry and high temperature differential scanning calorimetry have been used to measure the heat-capacity of ilmenite (FeTiO3) from 5 to 1000 K. These measurements yield S2980 = 108.9 J/(mol ?? K). Calculations from published experimental data on the reduction of ilmenite yield ??2980(I1) = -1153.9 kJ/(mol ?? K). These new data, combined with available experimental and thermodynamic data for other phases, have been used to calculate phase equilibria in the system Fe-Ti-O. Calculations for the subsystem Ti-O show that extremely low values of f{hook}O2 are necessary to stabilize TiO, the mineral hongquiite reported from the Tao district in China. This mineral may not be TiO, and it should be re-examined for substitution of other elements such as N or C. Consideration of solid-solution models for phases in the system Fe-Ti-O allows derivation of a new thermometer/oxybarometer for assemblages of ferropseudobrookite-pseudobrookitess and hematite-ilmenitess. Preliminary application of this new thermometer/oxybarometer to lunar and terrestrial lavas gives reasonable estimates of oxygen fugacities, but generally yields subsolidus temperatures, suggesting re-equilibration of one or more phases during cooling. ?? 1985.

  17. Phase Equilibria of the Fe-Ni-Sn Ternary System at 270°C

    NASA Astrophysics Data System (ADS)

    Huang, Tzu-Ting; Lin, Shih-Wei; Chen, Chih-Ming; Chen, Pei Yu; Yen, Yee-Wen

    2016-07-01

    The Fe-42 wt.% Ni alloy, also known as a 42 invar alloy (Alloy 42), is used as a lead-frame material because its thermal expansion coefficient is much closer to Si substrate than Cu or Ni substrates. In order to enhance the wettability between the substrate and solder, the Sn layer was commonly electroplated onto the Alloy 42 surface. A clear understanding of the phase equilibria of the Fe-Ni-Sn ternary system is necessary to ensure solder-joint reliability between Sn and Fe-Ni alloys. To determine the isothermal section of the Fe-Ni-Sn ternary system at 270°C, 26 Fe-Ni-Sn alloys with different compositions were prepared. The experimental results confirmed the presence of the Fe3Ni and FeNi phases at 270°C. Meanwhile, it observed that the isothermal section of the Fe-Ni-Sn ternary system was composed of 11 single-phase regions, 19 two-phase regions and nine tie-triangles. Moreover, no ternary compounds were found in the Fe-Ni-Sn system at 270°C.

  18. Calculation of liquid water-hydrate-methane vapor phase equilibria from molecular simulations.

    PubMed

    Jensen, Lars; Thomsen, Kaj; von Solms, Nicolas; Wierzchowski, Scott; Walsh, Matthew R; Koh, Carolyn A; Sloan, E Dendy; Wu, David T; Sum, Amadeu K

    2010-05-01

    Monte Carlo simulation methods for determining fluid- and crystal-phase chemical potentials are used for the first time to calculate liquid water-methane hydrate-methane vapor phase equilibria from knowledge of atomistic interaction potentials alone. The water and methane molecules are modeled using the TIP4P/ice potential and a united-atom Lennard-Jones potential, respectively. The equilibrium calculation method for this system has three components, (i) thermodynamic integration from a supercritical ideal gas to obtain the fluid-phase chemical potentials, (ii) calculation of the chemical potential of the zero-occupancy hydrate system using thermodynamic integration from an Einstein crystal reference state, and (iii) thermodynamic integration to obtain the water and guest molecules' chemical potentials as a function of the hydrate occupancy. The three-phase equilibrium curve is calculated for pressures ranging from 20 to 500 bar and is shown to follow the Clapeyron behavior, in agreement with experiment; coexistence temperatures differ from the latter by 4-16 K in the pressure range studied. The enthalpy of dissociation extracted from the calculated P-T curve is within 2% of the experimental value at corresponding conditions. While computationally intensive, simulations such as these are essential to map the thermodynamically stable conditions for hydrate systems.

  19. Electronic Structure and Phase Equilibria in Ternary Substitutional Alloys: a Tight-Binding Approach

    NASA Astrophysics Data System (ADS)

    Traiber, Ariel Javier Sebastian

    1995-01-01

    The goal of this thesis is to develop and apply alloy theory methods to transition metals and alloys (particularly ternary systems) based on the tight-binding (TB) model of atomic cohesion in studies of stability and phase equilibria. At least two factors make this kind of formalism desirable: it can bring a clear understanding of the underlying physical mechanisms that many times get obscured in first-principles calculations, and it is easily adapted to complex problems and multicomponent solutions, at low computational cost. The original physical insight given by the TB method is demonstrated by the study of the relation between the atomic local environment and the relative stability of simple phases, through the calculation of the moments of the electronic density of states. We show that the relative stability of phases related to the Bain transformation is mainly controlled by the moment of order five, and we have identified the main contributions to this moment. We present a model for cohesive energy based on the assumption that it can be written as the sum of a band -structure contribution and a repulsive short-range contribution. We have calculated the band contribution using a TB Hamiltonian with d states and applied the linearized Green's function method based on the recursion technique. For the repulsive part of the energy we employ a Born-Mayer potential. The model was used to study total energies for Mo. We show that a six-moment approximation to the band energy is sufficient to reproduce more accurate results, using the standard recursion method, for the energetics of this transition metal. We describe a reliable and consistent scheme to study phase equilibria in ternary substitutional alloys based on the TB approximation. The TB electronic parameters are obtained from linear muffin-tin orbital calculations. The transfer integrals are scaled in distance with an orbital -dependent exponential decay parametrization, while the on-site energies are scaled

  20. Direct molecular dynamics simulation of liquid-solid phase equilibria for a three-component plasma.

    PubMed

    Hughto, J; Horowitz, C J; Schneider, A S; Medin, Zach; Cumming, Andrew; Berry, D K

    2012-12-01

    The neutron-rich isotope ²²Ne may be a significant impurity in carbon and oxygen white dwarfs and could impact how the stars freeze. We perform molecular dynamics simulations to determine the influence of ²²Ne in carbon-oxygen-neon systems on liquid-solid phase equilibria. Both liquid and solid phases are present simultaneously in our simulation volumes. We identify liquid, solid, and interface regions in our simulations using a bond angle metric. In general we find good agreement for the composition of liquid and solid phases between our MD simulations and the semianalytic model of Medin and Cumming. The trace presence of a third component, neon, does not appear to strongly impact the chemical separation found previously for two-component carbon and oxygen systems. This suggests that small amounts of ²²Ne may not qualitatively change how the material in white dwarf stars freezes. However, we do find systematically lower melting temperatures (higher Γ) in our MD simulations compared to the semianalytic model. This difference seems to grow with impurity parameter Q_{imp} and suggests a problem with simple corrections to the linear mixing rule for the free energy of multicomponent solid mixtures that is used in the semianalytic model. PMID:23368065

  1. Direct molecular dynamics simulation of liquid-solid phase equilibria for a three-component plasma.

    PubMed

    Hughto, J; Horowitz, C J; Schneider, A S; Medin, Zach; Cumming, Andrew; Berry, D K

    2012-12-01

    The neutron-rich isotope ²²Ne may be a significant impurity in carbon and oxygen white dwarfs and could impact how the stars freeze. We perform molecular dynamics simulations to determine the influence of ²²Ne in carbon-oxygen-neon systems on liquid-solid phase equilibria. Both liquid and solid phases are present simultaneously in our simulation volumes. We identify liquid, solid, and interface regions in our simulations using a bond angle metric. In general we find good agreement for the composition of liquid and solid phases between our MD simulations and the semianalytic model of Medin and Cumming. The trace presence of a third component, neon, does not appear to strongly impact the chemical separation found previously for two-component carbon and oxygen systems. This suggests that small amounts of ²²Ne may not qualitatively change how the material in white dwarf stars freezes. However, we do find systematically lower melting temperatures (higher Γ) in our MD simulations compared to the semianalytic model. This difference seems to grow with impurity parameter Q_{imp} and suggests a problem with simple corrections to the linear mixing rule for the free energy of multicomponent solid mixtures that is used in the semianalytic model.

  2. Interpretation of trace element and isotope features of basalts: relevance of field relations, petrology, major element data, phase equilibria, and magma chamber modeling in basalt petrogenesis

    NASA Astrophysics Data System (ADS)

    O'Hara, M. J.; Herzberg, C.

    2002-06-01

    explain the chemical variation between fertile and residual peridotite in natural ultramafic rock suites. The subtleties of magma chamber partial crystallization processes can produce an astounding array of "pseudospidergrams," a small selection of which have been explored here. Major modification of the trace element geochemistry and trace element ratios, even those of the highly incompatible elements, must always be entertained whenever the evidence suggests the possibility of partial crystallization. At one extreme, periodically recharged, periodically tapped magma chambers might undergo partial crystallization by ˜95% consolidation of a succession of small packets of the magma. Refluxing of the 5% residual melts from such a process into the main body of melt would lead to eventual discrimination between highly incompatible elements in that residual liquid comparable with that otherwise achieved by 0.1 to 0.3% liquid extraction in equilibrium partial melting. Great caution needs to be exercised in attempting the reconstruction of more primitive compositions by addition of troctolite, gabbro, and olivine to apparently primitive lava compositions. Special attention is focussed on the phase equilibria involving olivine, plagioclase (i.e., troctolite), and liquid because a high proportion of erupted basalts carry these two phases as phenocrysts, yet the equilibria are restricted to crustal pressures and are only encountered by wide ranges of basaltic compositions at pressures less than 0.5 GPa. The mere presence of plagioclase phenocrysts may be sufficient to disqualify candidate primitive magmas. Determination of the actual contributions of crustal processes to petrogenesis requires a return to detailed field, experimental, and forensic petrologic studies of individual erupted basalt flows; of a multitude of cumulate gabbros and their contacts; and of upper-mantle outcrops.

  3. Postperovskite phase equilibria in the MgSiO3-Al2O3 system.

    PubMed

    Tsuchiya, Jun; Tsuchiya, Taku

    2008-12-01

    We investigate high-P,T phase equilibria of the MgSiO(3)-Al(2)O(3) system by means of the density functional ab initio computation methods with multiconfiguration sampling. Being different from earlier studies based on the static substitution properties with no consideration of Rh(2)O(3)(II) phase, present calculations demonstrate that (i) dissolving Al(2)O(3) tends to decrease the postperovskite transition pressure of MgSiO(3) but the effect is not significant ( approximately -0.2 GPa/mol% Al(2)O(3)); (ii) Al(2)O(3) produces the narrow perovskite+postperovskite coexisting P,T area (approximately 1 GPa) for the pyrolitic concentration (x(Al2O3) approximately 6 mol%), which is sufficiently responsible to the deep-mantle D'' seismic discontinuity; (iii) the transition would be smeared (approximately 4 GPa) for the basaltic Al-rich composition (x(Al2O3) approximately 20 mol%), which is still seismically visible unless iron has significant effects; and last (iv) the perovskite structure spontaneously changes to the Rh(2)O(3)(II) with increasing the Al concentration involving small displacements of the Mg-site cations.

  4. Phase equilibria constraints on the chemical and physical evolution of the campanian ignimbrite

    USGS Publications Warehouse

    Fowler, S.J.; Spera, F.J.; Bohrson, W.A.; Belkin, H.E.; de Vivo, B.

    2007-01-01

    The Campanian Ignimbrite is a > 200 km3 trachyte-phonolite pyroclastic deposit that erupted at 39.3 ?? 0.1 ka within the Campi Flegrei west of Naples, Italy. Here we test the hypothesis that Campanian Ignimbrite magma was derived by isobaric crystal fractionation of a parental basaltic trachyandesitic melt that reacted and came into local equilibrium with small amounts (5-10 wt%) of crustal rock (skarns and foid-syenites) during crystallization. Comparison of observed crystal and magma compositions with results of phase equilibria assimilation-fractionation simulations (MELTS) is generally very good. Oxygen fugacity was approximately buffered along QFM+1 (where QFM is the quartz-fayalite-magnetite buffer) during isobaric fractionation at 0.15 GPa (???6 km depth). The parental melt, reconstructed from melt inclusion and host clinopyroxene compositions, is found to be basaltic trachyandesite liquid (51.1 wt% SiO2, 9.3 wt% MgO, 3 wt% H2O). A significant feature of phase equilibria simulations is the existence of a pseudo-invariant temperature, ???883??C, at which the fraction of melt remaining in the system decreases abruptly from ???0.5 to < 0.1. Crystallization at the pseudo-invariant point leads to abrupt changes in the composition, properties (density, dissolved water content), and physical state (viscosity, volume fraction fluid) of melt and magma. A dramatic decrease in melt viscosity (from 1700 Pa s to ???200 Pa s), coupled with a change in the volume fraction of water in magma (from ??? 0.1 to 0.8) and a dramatic decrease in melt and magma density acted as a destabilizing eruption trigger. Thermal models suggest a timescale of ??? 200 kyr from the beginning of fractionation until eruption, leading to an apparent rate of evolved magma generation of about 10-3 km3/year. In situ crystallization and crystal settling in density-stratified regions, as well as in convectively mixed, less evolved subjacent magma, operate rapidly enough to match this apparent

  5. Petrogenesis of Mt. Baker basalts (Cascade arc): Constraints from thermobarometry, phase equilibria, trace elements and isotopes

    NASA Astrophysics Data System (ADS)

    Mullen, E. K.; McCallum, I. S.

    2010-12-01

    Primitive arc basalts provide information on sub-arc mantle compositions and processes. The relative abundance of basalts in the Cascade arc decreases northward, and basalts are rare in the most northerly segment of the arc (Garibaldi belt) where the Mt. Baker volcanic field (MBVF) is located. Following reconstruction of the compositions of the primary basalts at MBVF (olivine addition ± plag subtraction), we have applied phase equilibria and forward-modeled trace element abundances and isotope ratios to obtain petrogenetic constraints. The most primitive lavas are the Sulphur Cr, Lk Shannon, and Park Butte basalts and the Hogback, Tarn Plateau, and Cathedral Crag basaltic andesites, ranging from 716 to 10 ka. Most erupted peripheral to the major centers. Spinel/olivine and Fe-Ti oxide oxybarometry indicate redox states of ~QFM + 1 corresponding to Fe3+/ΣFe = 0.20. Mg# ranges from 51 to 71. The lavas are medium-K and similar to calc-alkaline basalts and high-Mg basaltic andesites from the High Cascades. MBVF basalts have higher MgO and lower CaO and Al2O3 than typical CAB and HAOT, grading to alkalic compositions with TiO2 and Na2O of up to 1.65 and 5.4 wt%, respectively (Sulphur Cr). Phenocryst contents are 5 to 33% (plag + olivine ± cpx) and the lavas are holo- or hypocrystalline with glass contents of up to 15%. The whole rocks are close to equilibrium with olivine cores (range Fo 87-68). Plagioclase cores range from An 88-68. Reconstructed primary basalt compositions give liquidus T and P values (from olivine-liquid equilibria and silica activities) ranging from 1280°C and 1 GPa (Tarn Plateau) to 1350°C and 1.4 GPa (Sulphur Cr), corresponding to the upper mantle above the core of the mantle wedge. These estimates take into account the 1 to 3 wt% initial H2O contents of the basalts calculated using plagioclase cores. Phase equilibria of the primary basalts indicate a similar pressure range of 1-2 GPa and indicate a residual mantle assemblage of harzburgite

  6. Phase equilibria in fullerene-containing systems as a basis for development of manufacture and application processes for nanocarbon materials

    NASA Astrophysics Data System (ADS)

    Semenov, K. N.; Charykov, N. A.; Postnov, V. N.; Sharoyko, V. V.; Murin, I. V.

    2016-01-01

    This review is the first attempt to integrate the available data on all types of phase equilibria (solubility, extraction and sorption) in systems containing light fullerenes (C60 and C70). In the case of solubility diagrams, the following types of phase equilibria are considered: individual fullerene (C60 or C70)–solvent under polythermal and polybaric conditions; C60–C70–solvent, individual fullerene–solvent(1)–solvent(2), as well as multicomponent systems comprising a single fullerene or an industrial mixture of fullerenes and vegetable oils, animal fats or essential oils under polythermal conditions. All published experimental data on the extraction equilibria in C60–C70–liquid phase(1)–liquid phase(2) systems are described systematically and the sorption characteristics of various materials towards light fullerenes are estimated. The possibility of application of these experimental data for development of pre-chromatographic and chromatographic methods for separation of fullerene mixtures and application of fullerenes as nanomodifiers are described. The bibliography includes 87 references.

  7. Phase equilibria in fullerene-containing systems as a basis for development of manufacture and application processes for nanocarbon materials

    NASA Astrophysics Data System (ADS)

    Semenov, K. N.; Charykov, N. A.; Postnov, V. N.; Sharoyko, V. V.; Murin, I. V.

    2016-01-01

    This review is the first attempt to integrate the available data on all types of phase equilibria (solubility, extraction and sorption) in systems containing light fullerenes (C60 and C70). In the case of solubility diagrams, the following types of phase equilibria are considered: individual fullerene (C60 or C70)-solvent under polythermal and polybaric conditions; C60-C70-solvent, individual fullerene-solvent(1)-solvent(2), as well as multicomponent systems comprising a single fullerene or an industrial mixture of fullerenes and vegetable oils, animal fats or essential oils under polythermal conditions. All published experimental data on the extraction equilibria in C60-C70-liquid phase(1)-liquid phase(2) systems are described systematically and the sorption characteristics of various materials towards light fullerenes are estimated. The possibility of application of these experimental data for development of pre-chromatographic and chromatographic methods for separation of fullerene mixtures and application of fullerenes as nanomodifiers are described. The bibliography includes 87 references.

  8. Visual investigation of solid-liquid phase equilibria for nonflammable mixed refrigerant

    NASA Astrophysics Data System (ADS)

    Lee, C.; Yoo, J.; Park, I.; Park, J.; Cha, J.; Jeong, S.

    2015-12-01

    Non-flammable mixed refrigerant (NF-MR) Joule Thomson (J-T) refrigerators have desirable characteristics and wide cooling temperature range compared to those of pure J-T refrigerators. However, the operating challenge due to freezing is a critical issue to construct this refrigerator. In this paper, the solid-liquid phase equilibria (i.e. freezing point) of the NF-MR which is composed of Argon, R14 (CF4), and R218 (C3F8), has been experimentally investigated by a visualized apparatus. Argon, R14 and R218 mixtures are selected to be effectively capable of reaching 100 K in the MR J-T refrigerator system. Freezing points of the mixtures have been measured with the molar compositions from 0.1 to 0.8 for each component. Each test result is simultaneously acquired by a camcorder for visual inspection and temperature measurement during a warming process. Experimental results show that the certain mole fraction of Argon, R14, and R218 mixture can achieve remarkably low freezing temperature even below 77 K. This unusual freezing point depression characteristic of the MR can be a useful information for designing a cryogenic MR J-T refrigerator to reach further down to 77 K.

  9. An efficient and general approach for implementing thermodynamic phase equilibria information in geophysical and geodynamic studies

    NASA Astrophysics Data System (ADS)

    Afonso, Juan Carlos; Zlotnik, Sergio; Díez, Pedro

    2015-10-01

    We present a flexible, general, and efficient approach for implementing thermodynamic phase equilibria information (in the form of sets of physical parameters) into geophysical and geodynamic studies. The approach is based on Tensor Rank Decomposition methods, which transform the original multidimensional discrete information into a separated representation that contains significantly fewer terms, thus drastically reducing the amount of information to be stored in memory during a numerical simulation or geophysical inversion. Accordingly, the amount and resolution of the thermodynamic information that can be used in a simulation or inversion increases substantially. In addition, the method is independent of the actual software used to obtain the primary thermodynamic information, and therefore, it can be used in conjunction with any thermodynamic modeling program and/or database. Also, the errors associated with the decomposition procedure are readily controlled by the user, depending on her/his actual needs (e.g., preliminary runs versus full resolution runs). We illustrate the benefits, generality, and applicability of our approach with several examples of practical interest for both geodynamic modeling and geophysical inversion/modeling. Our results demonstrate that the proposed method is a competitive and attractive candidate for implementing thermodynamic constraints into a broad range of geophysical and geodynamic studies. MATLAB implementations of the method and examples are provided as supporting information and can be downloaded from the journal's website.

  10. A reduced basis approach for implementing thermodynamic phase-equilibria information in geophysical and geodynamic studies

    NASA Astrophysics Data System (ADS)

    Afonso, J. C.; Zlotnik, S.; Diez, P.

    2015-12-01

    We present a flexible, general and efficient approach for implementing thermodynamic phase equilibria information (in the form of sets of physical parameters) into geophysical and geodynamic studies. The approach is based on multi-dimensional decomposition methods, which transform the original multi-dimensional discrete information into a dimensional-separated representation. This representation has the property of increasing the number of coefficients to be stored linearly with the number of dimensions (opposite to a full multi-dimensional cube requiring exponential storage depending on the number of dimensions). Thus, the amount of information to be stored in memory during a numerical simulation or geophysical inversion is drastically reduced. Accordingly, the amount and resolution of the thermodynamic information that can be used in a simulation or inversion increases substantially. In addition, the method is independent of the actual software used to obtain the primary thermodynamic information, and therefore it can be used in conjunction with any thermodynamic modeling program and/or database. Also, the errors associated with the decomposition procedure are readily controlled by the user, depending on her/his actual needs (e.g. preliminary runs vs full resolution runs). We illustrate the benefits, generality and applicability of our approach with several examples of practical interest for both geodynamic modeling and geophysical inversion/modeling. Our results demonstrate that the proposed method is a competitive and attractive candidate for implementing thermodynamic constraints into a broad range of geophysical and geodynamic studies.

  11. High temperature phase equilibria studies in the Bi-Sr-Ca-Cu-O-Ag system

    SciTech Connect

    Margulies, Lawrence

    1999-11-08

    A variety of experimental techniques were utilized to examine the high temperature phase equilibria in the Bi-Sr-Ca-Cu-O-Ag system. Quenching studies were used to determine the liquid solubility of Ag in the Bi{sub 2}Sr{sub 2}CaCu{sub 2}O{sub 8} (Bi2212) melt and the details of the peritectic decomposition pathway of Bi2212 as a function on Ag content and oxygen partial pressure (PO{sub 2}). A liquid immiscibility region between oxide and Ag liquids in the 8--98 at% range was found above 900 C. Two eutectics were found in the Bi2212-Ag pseudobinary. On the oxide rich side, a eutectic exists at approximately 4 at% Ag. On the Ag rich side, a eutectic exists at approximately 98 at% Ag at a temperature of 15 C below the melting point of pure Ag. Six distinct solid phases were found to be in equilibrium with the partial melt within the Ag content and PO{sub 2} range studied. The stability of these solid phases were found to be highly sensitive to PO{sub 2}, and to a much lesser extent Ag content. High temperature x-ray diffraction (HTXRD) studies of this system are in conflict with these results. It is suggested that these discrepancies are due to experimental artifacts caused by the significant thermal gradients and lack of full bulk sampling which is inherent in conventional HTXRD designs. In part 2, a new furnace design compatible with synchrotron radiation sources is introduced to address these problems. This design allows for full bulk sampling in a low thermal gradient environment using Debye-Scherrer transmission geometry. Sample spinning is also introduced in the design to eliminate preferred orientation and incomplete powder averaging and allow for quantitative phase analysis and structural refinement. Studies on model systems are presented to demonstrate the capabilities for high resolution structural studies (Al{sub 2}O{sub 3}) and time resolved phase transformation studies (SrCO{sub 3}). Finally, the Bi2212 system is examined to confirm the quenching results

  12. Phase equilibria of binary liquid crystal mixtures involving induced ordered phases

    NASA Astrophysics Data System (ADS)

    Huang, Tsang-Min

    A phenomenological model for elucidating phase diagrams of hexagonal columnar/nematic liquid crystal mixtures has been developed on the basis of the combination of the Flory-Huggins (FH) free energy of isotropic mixing, Maier-Saupe (MS) free energy for nematic ordering, and Chandrasekhar-Clark free energy for hexagonal ordering. Self-consistent calculations show the theory is capable of predicting the various phase diagrams, covering nematic, hexagonal columnar, and isotropic phases. The model has been tested with the eutectic phase diagram of hexagonal columnar liquid crystal, 2, 3, 6, 7, 10, 11-hexapentyloxy triphenylene (HPTP)/reactive nematic mesogens, 4-(3-acryloyloxypropyloxy)-benzoic acid 2-methyl-1, 4-phenylene ester (RM257) mixtures determined by using DSC, polarized optical microscope (POM), and wide-angle X-ray diffraction (WAXD). The self-consistent calculation displays isotropic (I), nematic (N), hexagonal columnar (Colh), N + I, and Colh + I, and Colh + N coexistence regions. These phase regions has been confirmed by thermal quenching various compositions from the isotropic melt to different phase regions. Guided by the established phase diagram of HPTP/RM257 mixtures, photo-polymerization of the mixture has been carried out in different phase regions. The as-cured HPTP/p-(RM257) composites fabricated at isotropic phase (130 °C) remains single isotropic phase under optical microscope, whereas the SEM and TEM results show the bead-like microstructure with sub-micrometer scale. Polymerization-induced mesophase transition experiments have been carried out at isotropic temperatures slightly above the clearing point of the mixtures. Of particular interest is the development of liquid crystalline spherulites. Moreover, the fixation of the morphology is observed when the photopolymerization is carried out in the N, N + I, and N + Colh region. A generalized thermodynamic model for describing smectic A and smectic B ordering has been developed based on

  13. Phase Equilibria of the Sn-Ni-Si Ternary System and Interfacial Reactions in Sn-(Cu)/Ni-Si Couples

    NASA Astrophysics Data System (ADS)

    Fang, Gu; Chen, Chih-chi

    2015-07-01

    Interfacial reactions in Sn/Ni-4.5 wt.%Si and Sn-Cu/Ni-4.5 wt.%Si couples at 250°C, and Sn-Ni-Si ternary phase equilibria at 250°C were investigated in this study. Ni-Si alloys, which are nonmagnetic, can be regarded as a diffusion barrier layer material in flip chip packaging. Solder/Ni-4.5 wt.%Si interfacial reactions are crucial to the reliability of soldered joints. Phase equilibria information is essential for development of solder/Ni-Si materials. No ternary compound is present in the Sn-Ni-Si ternary system at 250°C. Extended solubility of Si in the phases Ni3Sn2 and Ni3Sn is 3.8 and 6.1 at.%, respectively. As more Si dissolves in these phases their lattice constants decrease. No noticeable ternary solubility is observed for the other intermetallics. Interfacial reactions in solder/Ni-4.5 wt.%Si are similar to those for solder/Ni. Si does not alter the reaction phases. No Si solubility in the reaction phases was detected, although rates of growth of the reaction phases were reduced. Because the alloy Ni-4.5 wt.%Si reacts more slowly with solders than pure Ni, the Ni-4.5 wt.%Si alloy could be a potential new diffusion barrier layer material for flip chip packaging.

  14. Experimental Investigation and Thermodynamic Calculation of the Phase Equilibria in the Mg-Gd-Mn Ternary System

    NASA Astrophysics Data System (ADS)

    Zhang, Fan; Hu, Biao; Xu, Honghui; Liu, Shuhong; Zhou, Tao; Jin, Zhanpeng

    2015-10-01

    The phase equilibria of the Mg-Gd-Mn system at 773 K (500 °C) were investigated with sixteen alloys, by means of X-ray diffraction technique and electron probe microanalyses. Eight three-phase equilibria were accurately determined. No ternary compound was observed at 773 K (500 °C). The solubility of the third elements in the binary phases was measured. The isothermal section of the Mg-Gd-Mn system at 773 K (500 °C) was firstly established. It is worth mentioning that the three-phase field GdMg3-GdMg5-( αMn) was experimentally observed and is different from the three-phase field GdMg3-GdMg5-GdMn12 predicted using only the binary interaction parameters. Using the CALPHAD method, a thermodynamic modeling of the Mg-Gd-Mn system has been carried out in order to reasonably describe the experimental observations. The substitutional solution and sublattice models were used to describe the solution phases and intermediate phases. Comprehensive comparison between the calculated and measured isothermal sections shows that the experimental information is satisfactorily accounted for by the present thermodynamic modeling.

  15. Thermodynamics and Phase Equilibria of Concurrent Assimilation and Fractional Crystallization (AFC) in Crustal Magma Bodies

    NASA Astrophysics Data System (ADS)

    Creamer, J. B.; Spera, F. J.; Bohrson, W. A.; Ghiorso, M. S.

    2009-12-01

    Mafic magmas generated by partial melting of mantle peridotites, eclogites or clinopyroxenites are hotter than, compositionally distinct from and have higher liquidus temperatures than the crustal rocks through which they ascend or are emplaced. The low thermal conductivity of crystalline and molten silicates implies that steep thermal gradients along the margins of propagating melt-filled fractures and stagnant magma bodies can develop and lead to crustal anatexis especially at depths >~10 km. Small differences in ambient deviatoric stresses within the crust can lead to the percolation of anatectic melts into adjacent magma. The magnitude of contamination is strongly dependant upon permeability which in turn depends upon the square of the volume fraction of anatectic melt, itself controlled by local phase equilibria. From the thermochemical vantage, AFC processes may be quantified using the Magma Chamber Simulator (MCS) by studying the variables that define the extent of AFC: thermal interaction mass ratio (ratio of pristine magma mass to mass of wallrock), bulk composition (including volatiles) of pristine magma and wallrock, the mean pressure and prevailing oxygen fugacity at which AFC occurs. Here we present MCS phase equilibria and major element solutions for a number of scenarios in which the sensible variables defining the extent of assimilation have been systematically varied. In particular, initial magma and wallrock temperatures, relative masses of wallrock and magma, oxygen fugacity and the mean pressure of AFC interaction are defined. The sub-systems are then allowed to proceed towards thermodynamic (thermal and chemical potential) equilibrium. Incremental enthalpy changes associated with magma cooling and crystallization are transferred to wallrock where heating and possible partial melting can occur. Fractional crystallization occurs in the magma and once the wallrock temperature exceeds its solidus, equilibrium melting in wallrock is enabled. When

  16. Transferable potentials for phase equilibria. 8. United-atom description for thiols, sulfides, disulfides, and thiophene.

    PubMed

    Lubna, Nusrat; Kamath, Ganesh; Potoff, Jeffrey J; Rai, Neeraj; Siepmann, J Ilja

    2005-12-22

    An extension of the transferable potentials for phase equilibria united-atom (TraPPE-UA) force field to thiol, sulfide, and disulfide functionalities and thiophene is presented. In the TraPPE-UA force field, nonbonded interactions are governed by a Lennard-Jones plus fixed point charge functional form. Partial charges are determined through a CHELPG analysis of electrostatic potential energy surfaces derived from ab initio calculations at the HF/6-31g+(d,p) level. The Lennard-Jones well depth and size parameters for four new interaction sites, S (thiols), S(sulfides), S(disulfides), and S(thiophene), were determined by fitting simulation data to pure-component vapor-equilibrium data for methanethiol, dimethyl sulfide, dimethyl disulfide, and thiophene, respectively. Configurational-bias Monte Carlo simulations in the grand canonical ensemble combined with histogram-reweighting methods were used to calculate the vapor-liquid coexistence curves for methanethiol, ethanethiol, 2-methyl-1-propanethiol, 2-methyl-2-propanethiol, 2-butanethiol, pentanethiol, octanethiol, dimethyl sulfide, diethyl sulfide, ethylmethyl sulfide, dimethyl disulfide, diethyl disulfide, and thiophene. Excellent agreement with experiment is achieved, with unsigned errors of less than 1% for saturated liquid densities and less than 3% for critical temperatures. The normal boiling points were predicted to within 1% of experiment in most cases, although for certain molecules (pentanethiol) deviations as large as 5% were found. Additional calculations were performed to determine the pressure-composition behavior of ethanethiol+n-butane at 373.15 K and the temperature-composition behavior of 1-propanethiol+n-hexane at 1.01 bar. In each case, a good reproduction of experimental vapor-liquid equilibrium separation factors is achieved; both of the coexistence curves are somewhat shifted because of overprediction of the pure-component vapor pressures.

  17. Phase Equilibria of the Ternary Sn-Zn-Co System at 250°C and 500°C

    NASA Astrophysics Data System (ADS)

    Wang, Chao-hong; Huang, Sheng-en; Huang, Po-yen

    2015-12-01

    The isothermal sections of the ternary Sn-Zn-Co system (<60 at.% Co) at 250°C and 500°C have been experimentally determined. A series of Sn-Zn-Co alloys of various compositions were prepared and annealed at the respective temperatures to reach phase equilibrium. The equilibrium phases in these alloys were examined metallographically and characterized by electron probe microanalysis and x-ray diffraction. In this system, the ternary solubilities of all the binary Sn-Co and Co-Zn intermetallic compounds (IMCs) are very limited. For the phase equilibria at 250°C, two ternary IMCs, T1 and T2, were found, whose compositions were Sn-25 at.%Zn-25 at.%Co and Sn-15 at.%Zn-41 at.%Co, respectively. For the phase equilibria at 500°C, in addition to the T2 phase, another ternary IMC, namely T3 (Sn-18 at.%Zn-37 at.%Co), was also found. Moreover, the phase stability of the T1 and T3 phases was investigated at temperatures of 260°C to 400°C in detail. The equilibrium phase was the T1 phase below 300°C, and changed to the T3 phase at 400°C. The crystal structures of these three ternary IMCs were also studied. The T1 phase has a cubic structure ( Pm3m), and the T2 and T3 phases are orthorhombic in space group Cmcm and Pnma, respectively.

  18. Heat capacity and phase equilibria of almandine, Fe 3Al 2Si 3O 12

    NASA Astrophysics Data System (ADS)

    Anovitz, L. M.; Essene, E. J.; Metz, G. W.; Bohlen, S. R.; Westrum, E. F., Jr.; Hemingway, B. S.

    1993-09-01

    The heat capacity of a synthetic almandine, Fe 3Al 2Si 3O 12, was measured from 6 to 350 K using equilibrium, intermittent-heating quasi-adiabatic calorimetry and from 420 to 1000 K using differential scanning calorimetry. These measurements yield Cp298 = 342.80 ± 1.4 J/mol · K and S298o = 342.60 J/mol · K. Mössbauer characterizations show the almandine to contain less than 2 ± 1% of the total iron as Fe 3+. X-ray diffraction studies of this synthetic almandine yield a = 11.521 ± 0.001 Å and V298o = 115.11 +- 0.01 cm 3/mol, somewhat smaller than previously reported. The low-temperature Cp data indicate a lambda transition at 8.7 K related to an antiferromagnetic-paramagnetic transition with TN = 7.5 K. Modeling of the lattice contribution to the total entropy suggests the presence of entropy in excess of that attributable to the effects of lattice vibrations and the magnetic transition. This probably arises from a low-temperature electronic transition (Schottky contribution). Combination of the Cp data with existing thermodynamic and phase equilibrium data on almandine yields ΔGf,298 o = -4938.3 kJ/mol and ΔHf,298 o= - 5261.3 kJ/mol for almandine when calculated from the elements. The equilibrium almandine = hercynite + fayalite + quartz limits the upper T/P for almandine and is metastably located at ca. 570°C at P = 1 bar, with a dP/dT of +17 bars/°C. This agrees well with reversed experiments on almandine stability when they are corrected for magnetite and hercynite solid-solutions. In ‖ O2- T space, almandine oxidizes near QFM by the reactions almandine + O2 = magnetite + sillimanite + quartzandalmandine + 02 = hercynite + magnetite + quartz. With suitable correction for reduced activities of solid phases, these equilibria provide useful oxygen barometers for medium- to high-grade metamorphic rocks.

  19. Heat capacity and phase equilibria of almandine, Fe3Al2Si3O12

    USGS Publications Warehouse

    Anovitz, Lawrence M.; Essene, E.J.; Metz, G.W.; Bohlen, S.R.; Westrum, E.F.; Hemingway, B.S.

    1993-01-01

    The heat capacity of a synthetic almandine, Fe3Al2Si3O12, was measured from 6 to 350 K using equilibrium, intermittent-heating quasi-adiabatic calorimetry and from 420 to 1000 K using differential scanning calorimetry. These measurements yield Cp298 = 342.80 ?? 1.4 J/mol ?? K and S298o = 342.60 J/mol ?? K. Mo??ssbauer characterizations show the almandine to contain less than 2 ?? 1% of the total iron as Fe3+. X-ray diffraction studies of this synthetic almandine yield a = 11.521 ?? 0.001 A?? and V298o = 115.11 +- 0.01 cm3/mol, somewhat smaller than previously reported. The low-temperature Cp data indicate a lambda transition at 8.7 K related to an antiferromagnetic-paramagnetic transition with TN = 7.5 K. Modeling of the lattice contribution to the total entropy suggests the presence of entropy in excess of that attributable to the effects of lattice vibrations and the magnetic transition. This probably arises from a low-temperature electronic transition (Schottky contribution). Combination of the Cp data with existing thermodynamic and phase equilibrium data on almandine yields ??Gf,298o = -4938.3 kJ/mol and ??Hf,298o= -5261.3 kJ/mol for almandine when calculated from the elements. The equilibrium almandine = hercynite + fayalite + quartz limits the upper T P for almandine and is metastably located at ca. 570??C at P = 1 bar, with a dP dT of +17 bars/??C. This agrees well with reversed experiments on almandine stability when they are corrected for magnetite and hercynite solid-solutions. In {norm of matrix}O2-T space, almandine oxidizes near QFM by the reactions almandine + O2 = magnetite + sillimanite + quartz and almandine + 02 = hercynite + magnetite + quartz. With suitable correction for reduced activities of solid phases, these equilibria provide useful oxygen barometers for medium- to high-grade metamorphic rocks. ?? 1993.

  20. Effect of Fluorine on Near-Liquidus Phase Equilibria of Basalts

    NASA Technical Reports Server (NTRS)

    Filiberto, Justin; Wood, Justin; Loan, Le; Dasgupta, Rajdeep; Shimizu, Nobumichi; Treiman, Allan H.

    2010-01-01

    Volatile species such as H2O, CO2, F, and Cl have significant impact in generation and differentiation of basaltic melts. Thus far experimental work has primarily focused on the effect of water and carbon dioxide on basalt crystallization, liquid-line of descent, and mantle melting [e.g., 1, 2] and the effects of halogens have received far less attention [3-4]. However, melts in the planetary interiors can have non-negligible chlorine and fluorine concentrations. Here, we explore the effects of fluorine on near-liquidus phase equilibria of basalt. We have conducted nominally anhydrous piston cylinder experiments using graphite capsules at 0.6 - 1.5 GPa on an Fe-rich model basalt composition. 1.75 wt% fluorine was added to the starting mix in the form of AgF2. Fluorine in the experimental glass was measured by SIMS and major elements of glass and minerals were analyzed by EPMA. Nominally volatile free experiments yield a liquidus temperature from 1330 C at 0.8GPa to 1400 at 1.6GPa and an olivine(Fo72)-pyroxene(En68)-liquid multiple saturation point at 1.25 GPa and 1375 C. The F-bearing experiments yield a liquiudus temperature from 1260 C at 0.6GPa to 1305 at 1.5GPa and an ol(Fo66)-pyx(En64)-MSP at 1 GPa and 1260 C. This shows that F depresses the basalt liquidus, extends the pyroxene stability field to lower pressure, and forces the liquidus phases to be more Fe-rich. KD(Fe-Mg/mineral-melt) calculated for both pyroxenes and olivines show an increase with increasing F content of the melt. Therefore, we infer that F complexes with Mg in the melt and thus increases the melt s silica activity, depressing the liquidus and changing the composition of the crystallizing minerals. Our study demonstrates that on a weight percent basis, the effect of fluorine is similar to the effect of H2O [1] and Cl [3] on freezing point depression of basalts. But on an atomic fraction basis, the effect of F on liquidus depression of basalts is xxxx compared to the effect of H. Future

  1. Prediction of the phase equilibria of methane hydrates using the direct phase coexistence methodology

    SciTech Connect

    Michalis, Vasileios K.; Costandy, Joseph; Economou, Ioannis G.; Tsimpanogiannis, Ioannis N.; Stubos, Athanassios K.

    2015-01-28

    The direct phase coexistence method is used for the determination of the three-phase coexistence line of sI methane hydrates. Molecular dynamics (MD) simulations are carried out in the isothermal–isobaric ensemble in order to determine the coexistence temperature (T{sub 3}) at four different pressures, namely, 40, 100, 400, and 600 bar. Methane bubble formation that results in supersaturation of water with methane is generally avoided. The observed stochasticity of the hydrate growth and dissociation processes, which can be misleading in the determination of T{sub 3}, is treated with long simulations in the range of 1000–4000 ns and a relatively large number of independent runs. Statistical averaging of 25 runs per pressure results in T{sub 3} predictions that are found to deviate systematically by approximately 3.5 K from the experimental values. This is in good agreement with the deviation of 3.15 K between the prediction of TIP4P/Ice water force field used and the experimental melting temperature of ice Ih. The current results offer the most consistent and accurate predictions from MD simulation for the determination of T{sub 3} of methane hydrates. Methane solubility values are also calculated at the predicted equilibrium conditions and are found in good agreement with continuum-scale models.

  2. Prediction of the phase equilibria of methane hydrates using the direct phase coexistence methodology

    NASA Astrophysics Data System (ADS)

    Michalis, Vasileios K.; Costandy, Joseph; Tsimpanogiannis, Ioannis N.; Stubos, Athanassios K.; Economou, Ioannis G.

    2015-01-01

    The direct phase coexistence method is used for the determination of the three-phase coexistence line of sI methane hydrates. Molecular dynamics (MD) simulations are carried out in the isothermal-isobaric ensemble in order to determine the coexistence temperature (T3) at four different pressures, namely, 40, 100, 400, and 600 bar. Methane bubble formation that results in supersaturation of water with methane is generally avoided. The observed stochasticity of the hydrate growth and dissociation processes, which can be misleading in the determination of T3, is treated with long simulations in the range of 1000-4000 ns and a relatively large number of independent runs. Statistical averaging of 25 runs per pressure results in T3 predictions that are found to deviate systematically by approximately 3.5 K from the experimental values. This is in good agreement with the deviation of 3.15 K between the prediction of TIP4P/Ice water force field used and the experimental melting temperature of ice Ih. The current results offer the most consistent and accurate predictions from MD simulation for the determination of T3 of methane hydrates. Methane solubility values are also calculated at the predicted equilibrium conditions and are found in good agreement with continuum-scale models.

  3. Prediction of the phase equilibria of methane hydrates using the direct phase coexistence methodology.

    PubMed

    Michalis, Vasileios K; Costandy, Joseph; Tsimpanogiannis, Ioannis N; Stubos, Athanassios K; Economou, Ioannis G

    2015-01-28

    The direct phase coexistence method is used for the determination of the three-phase coexistence line of sI methane hydrates. Molecular dynamics (MD) simulations are carried out in the isothermal-isobaric ensemble in order to determine the coexistence temperature (T3) at four different pressures, namely, 40, 100, 400, and 600 bar. Methane bubble formation that results in supersaturation of water with methane is generally avoided. The observed stochasticity of the hydrate growth and dissociation processes, which can be misleading in the determination of T3, is treated with long simulations in the range of 1000-4000 ns and a relatively large number of independent runs. Statistical averaging of 25 runs per pressure results in T3 predictions that are found to deviate systematically by approximately 3.5 K from the experimental values. This is in good agreement with the deviation of 3.15 K between the prediction of TIP4P/Ice water force field used and the experimental melting temperature of ice Ih. The current results offer the most consistent and accurate predictions from MD simulation for the determination of T3 of methane hydrates. Methane solubility values are also calculated at the predicted equilibrium conditions and are found in good agreement with continuum-scale models. PMID:25637989

  4. Prediction of the phase equilibria of methane hydrates using the direct phase coexistence methodology.

    PubMed

    Michalis, Vasileios K; Costandy, Joseph; Tsimpanogiannis, Ioannis N; Stubos, Athanassios K; Economou, Ioannis G

    2015-01-28

    The direct phase coexistence method is used for the determination of the three-phase coexistence line of sI methane hydrates. Molecular dynamics (MD) simulations are carried out in the isothermal-isobaric ensemble in order to determine the coexistence temperature (T3) at four different pressures, namely, 40, 100, 400, and 600 bar. Methane bubble formation that results in supersaturation of water with methane is generally avoided. The observed stochasticity of the hydrate growth and dissociation processes, which can be misleading in the determination of T3, is treated with long simulations in the range of 1000-4000 ns and a relatively large number of independent runs. Statistical averaging of 25 runs per pressure results in T3 predictions that are found to deviate systematically by approximately 3.5 K from the experimental values. This is in good agreement with the deviation of 3.15 K between the prediction of TIP4P/Ice water force field used and the experimental melting temperature of ice Ih. The current results offer the most consistent and accurate predictions from MD simulation for the determination of T3 of methane hydrates. Methane solubility values are also calculated at the predicted equilibrium conditions and are found in good agreement with continuum-scale models.

  5. Phase equilibria, crystal structure and oxygen content of intermediate phases in the Y-Ba-Co-O system

    NASA Astrophysics Data System (ADS)

    Urusova, A. S.; Cherepanov, V. A.; Aksenova, T. V.; Gavrilova, L. Ya.; Kiselev, E. A.

    2013-06-01

    The phase equilibria in the Y-Ba-Co-O system were systematically studied at 1373 K in air. The intermediate phases formed in the Y-Ba-Co-O system at 1373 K in air were: YBaCo2O5+δ, YBaCo4O7 and BaCo1-yYyO3-δ (0.09≤y≤0.42). It was shown that YBaCo2O5+δ possesses tetragonal structure with the 3ap×3ap×2ap superstructure (sp. gr. P4/mmm). High-temperature X-ray diffraction analysis of the YBaCo2O5+δ in the temperature range from 298 K up to 1073 K under Po2=0.21 аtm has not shown any phase transformations. The value of oxygen content for the YBaCo2O5+δ at room temperature was estimated as 5.40 and at 1323 K it was equal to 5.04. Thermal expansion of sample shows a linear characteristics and the average thermal expansion coefficient (TEC) is about 13.8×10-6, K-1 in the temperature range 298-1273 K. The homogeneity range and crystal structure of the BaCo1-yYyO3-δ (0.09≤y≤0.42) solid solutions were determined by X-ray diffraction of quenched samples. All BaCo1-yYyO3-δ solid solutions were found to have cubic structure (sp. gr. Pm3m). The unit cell parameters were refined using Rietveld full-profile analysis. Oxygen nonstoichiometry of BaCo1-yYyO3-δ solid solutions with 0.1≤y≤0.4 was measured by means of thermogravimetric technique within the temperature range 298-1373 K in air. Thermal expansion of BaCo1-yYyO3-δ (у=0.0; 0.1; 0.2; 0.3) samples was studied within the temperature range 298-1200 K in air. The projection of isothermal-isobaric phase diagram for the Y-Ba-Co-O system to the compositional triangle of metallic components was presented.

  6. Calculation of Phase Equilibria in the Y2O3-Yb2O3-ZrO2 System

    NASA Technical Reports Server (NTRS)

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

    2001-01-01

    Rare earth oxide stabilized zirconias find a wide range of applications. An understanding of phase equilibria is essential to all applications. In this study, the available phase boundary data and thermodynamic data is collected and assessed. Calphad-type databases are developed to completely describe the Y2O3-ZrO2, Yb2O3-ZrO2, and Y2O3-Yb2O3 systems. The oxide units are treated as components and regular and subregular solution models are used. The resultant calculated phase diagrams show good agreement with the experimental data. Then the binaries are combined to form the database for the Y2O3-Yb2O3-ZrO2 psuedo-ternary.

  7. DEVELOPMENT OF A HIGH-TEMPERATURE CERAMIC BRAZE: ANALYSIS OF PHASE EQUILIBRIA IN THE Pd-Ag-CuOx SYSTEM

    SciTech Connect

    Weil, K. Scott; Darsell, Jens T.

    2006-01-18

    This paper describes the effects of small palladium additions on the phase equilibria in the Ag-CuOx system. Below a concentration of 5 mol%, palladium was found to increase the temperature of the eutectic reaction present in the pseudobinary system, but have little effect on a higher temperature monotectic reaction. However once enough palladium was added to increase the pseudoternary solidus temperature to that of the lower boundary for this three-phase field (~970°C), the lower boundary begins to increase in temperature as well. The addition of palladium also causes the original eutectic point to move to lower silver concentrations, which also causes a convergence of the two new three-phase fields, CuOx + L1 + L2 and CuOx + α + L1. This suggests that with higher palladium concentrations, a peritectic reaction, α + L1 + L2 → CuOx, may eventually be observed in the system.

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

    PubMed

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

    2011-05-26

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

  9. The role of intermolecular interactions in the prediction of the phase equilibria of carbon dioxide hydrates.

    PubMed

    Costandy, Joseph; Michalis, Vasileios K; Tsimpanogiannis, Ioannis N; Stubos, Athanassios K; Economou, Ioannis G

    2015-09-01

    The direct phase coexistence methodology was used to predict the three-phase equilibrium conditions of carbon dioxide hydrates. Molecular dynamics simulations were performed in the isobaric-isothermal ensemble for the determination of the three-phase coexistence temperature (T3) of the carbon dioxide-water system, at pressures in the range of 200-5000 bar. The relative importance of the water-water and water-guest interactions in the prediction of T3 is investigated. The water-water interactions were modeled through the use of TIP4P/Ice and TIP4P/2005 force fields. The TraPPE force field was used for carbon dioxide, and the water-guest interactions were probed through the modification of the cross-interaction Lennard-Jones energy parameter between the oxygens of the unlike molecules. It was found that when using the classic Lorentz-Berthelot combining rules, both models fail to predict T3 accurately. In order to rectify this problem, the water-guest interaction parameters were optimized, based on the solubility of carbon dioxide in water. In this case, it is shown that the prediction of T3 is limited only by the accuracy of the water model in predicting the melting temperature of ice. PMID:26342376

  10. The role of intermolecular interactions in the prediction of the phase equilibria of carbon dioxide hydrates.

    PubMed

    Costandy, Joseph; Michalis, Vasileios K; Tsimpanogiannis, Ioannis N; Stubos, Athanassios K; Economou, Ioannis G

    2015-09-01

    The direct phase coexistence methodology was used to predict the three-phase equilibrium conditions of carbon dioxide hydrates. Molecular dynamics simulations were performed in the isobaric-isothermal ensemble for the determination of the three-phase coexistence temperature (T3) of the carbon dioxide-water system, at pressures in the range of 200-5000 bar. The relative importance of the water-water and water-guest interactions in the prediction of T3 is investigated. The water-water interactions were modeled through the use of TIP4P/Ice and TIP4P/2005 force fields. The TraPPE force field was used for carbon dioxide, and the water-guest interactions were probed through the modification of the cross-interaction Lennard-Jones energy parameter between the oxygens of the unlike molecules. It was found that when using the classic Lorentz-Berthelot combining rules, both models fail to predict T3 accurately. In order to rectify this problem, the water-guest interaction parameters were optimized, based on the solubility of carbon dioxide in water. In this case, it is shown that the prediction of T3 is limited only by the accuracy of the water model in predicting the melting temperature of ice.

  11. The role of intermolecular interactions in the prediction of the phase equilibria of carbon dioxide hydrates

    NASA Astrophysics Data System (ADS)

    Costandy, Joseph; Michalis, Vasileios K.; Tsimpanogiannis, Ioannis N.; Stubos, Athanassios K.; Economou, Ioannis G.

    2015-09-01

    The direct phase coexistence methodology was used to predict the three-phase equilibrium conditions of carbon dioxide hydrates. Molecular dynamics simulations were performed in the isobaric-isothermal ensemble for the determination of the three-phase coexistence temperature (T3) of the carbon dioxide-water system, at pressures in the range of 200-5000 bar. The relative importance of the water-water and water-guest interactions in the prediction of T3 is investigated. The water-water interactions were modeled through the use of TIP4P/Ice and TIP4P/2005 force fields. The TraPPE force field was used for carbon dioxide, and the water-guest interactions were probed through the modification of the cross-interaction Lennard-Jones energy parameter between the oxygens of the unlike molecules. It was found that when using the classic Lorentz-Berthelot combining rules, both models fail to predict T3 accurately. In order to rectify this problem, the water-guest interaction parameters were optimized, based on the solubility of carbon dioxide in water. In this case, it is shown that the prediction of T3 is limited only by the accuracy of the water model in predicting the melting temperature of ice.

  12. Petrogenesis of Mt. Baker Basalts and Andesites: Constraints From Mineral Chemistry and Phase Equilibria

    NASA Astrophysics Data System (ADS)

    Mullen, E.; McCallum, I. S.

    2009-12-01

    Basalts in continental arcs are volumetrically subordinate to andesites and this is the case for Mt. Baker in the northern Cascade magmatic arc. However, basalts provide indirect evidence on mantle compositions and processes that produce magmas parental to the abundant andesites and dacites of the stratocones. Basalts at Mt. Baker erupted from monogenetic vents peripheral to the andesitic stratocone. Flows are variable in composition; some samples would more appropriately be classified as basaltic andesites. The “basalts” have relatively low Mg/(Mg+Fe) indicating that they have evolved from their original compositions. Samples studied are Park Butte, Tarn Plateau, Lk. Shannon, Sulphur Cr. basalts, and Cathedral Crag, Hogback, and Rankin Ridge basaltic andesites. Mt. Baker lavas belong to the calc-alkaline basalt suite (CAB) defined by Bacon et al. (1997) and preserve arc geochemical features. High alumina olivine tholeiite (HAOT) are absent. Equilibrium mineral pairs and whole rock compositions were used to calculate pre-eruptive temperatures, water contents, and redox states of the “basalts.” All samples have zoned olivine phenocrysts with Fo68 to Fo87 cores and chromite inclusions. Cpx and zoned plagioclase occur in all flows, but opx occurs only in Cathedral Crag, Rankin Ridge, and Tarn Plateau. Ti-magnetite and ilmenite coexist in all flows except for Sulphur Cr., Lk. Shannon and Hogback, which contain a single Fe-Ti oxide. Liquidus temperatures range from 1080 to 1232°C and are negatively correlated with water contents. Water contents estimated using liquidus depression due to H2O (0.8 to 5.4 wt.%) agree well with plag core-whole rock equilibria estimates (1.2 to 3.9 wt.%). Park Butte, Sulphur Cr. and Lk. Shannon had <1.5 wt.% H2O, and Cathedral Crag is most hydrous. Redox states from ol-chr pairs (QFM +0.1 to +2.8) and Fe-Ti oxide pairs (QFM -0.6 to +1.8) indicate that Park Butte and Sulphur Cr. are most oxidized and Cathedral Crag most reduced

  13. Applying Lu-Hf garnet geochronology and inverse phase equilibria modeling to migmatites

    NASA Astrophysics Data System (ADS)

    Yakymchuk, C.; Brown, M.; Vervoort, J. D.

    2013-12-01

    Garnet-bearing assemblages are common in HT metamorphic rocks and are widely used to determine P-T conditions. Garnet is also a host for accessory minerals that may be used to determine the timing of garnet growth or breakdown. However, using accessory minerals to date garnet in HT metamorphic rocks may produce ambiguous or erroneous age results if these minerals were grown or modified subsequently due to fluid or melt infiltration along microfractures. Direct dating of garnet using the Sm-Nd and/or Lu-Hf isotope systems potentially avoids these problems. However, at temperatures above the solidus, the Sm-Nd isotope composition of garnet may become homogenized during post-peak cooling and evidence of prograde growth may be removed. The Lu-Hf isotope system in garnet is more robust and less susceptible to diffusion-controlled re-equilibration. Therefore, Lu-Hf dating of garnet has the potential to constrain the period of prograde garnet growth in HT metamorphic rocks. In the Fosdick migmatite-granite complex of West Antarctica, two episodes of HT garnet growth have been proposed based on U-Pb monazite ages from garnet-bearing migmatitic paragneisses and orthogneisses and U-Pb zircon ages from spatially associated peraluminous granites. Cores of monazite inclusions in garnet yield Carboniferous ages whereas the rims yield Cretaceous ages, and the garnet itself records Cretaceous Sm-Nd ages. The Sm-Nd ages were interpreted to represent diffusional resetting during the Cretaceous of garnet that grew in the Carboniferous. In this study, Lu-Hf garnet geochronology is used to test the hypothesis that garnet in the migmatitic paragneisses and orthogneisses is Carboniferous in age. We also assess the utility of the Lu-Hf system for dating garnet growth in rocks that have experienced superimposed HT metamorphic events. In addition, inverse phase equilibria modeling of open system melting is used to constrain the P-T conditions of garnet growth in migmatitic paragneisses and

  14. Phase equilibria, crystal structure and oxygen content of intermediate phases in the Y–Ba–Co–O system

    SciTech Connect

    Urusova, A.S.; Cherepanov, V.A. Aksenova, T.V.; Gavrilova, L.Ya.; Kiselev, E.A.

    2013-06-01

    The phase equilibria in the Y–Ba–Co–O system were systematically studied at 1373 K in air. The intermediate phases formed in the Y–Ba–Co–O system at 1373 K in air were: YBaCo₂O5+δ, YBaCo₄O₇ and BaCo1–yYyO3–δ (0.09≤y≤0.42). It was shown that YBaCo₂O5+δ possesses tetragonal structure with the 3aₚ×3aₚ×2aₚ superstructure (sp. gr. P4/mmm). High-temperature X-ray diffraction analysis of the YBaCo₂O5+δ in the temperature range from 298 K up to 1073 K under Po₂=0.21 atm has not shown any phase transformations. The value of oxygen content for the YBaCo₂O5+δ at room temperature was estimated as 5.40 and at 1323 K it was equal to 5.04. Thermal expansion of sample shows a linear characteristics and the average thermal expansion coefficient (TEC) is about 13.8×10⁻⁶, K⁻¹ in the temperature range 298–1273 K. The homogeneity range and crystal structure of the BaCo1–yYyO3–δ (0.09≤y≤0.42) solid solutions were determined by X-ray diffraction of quenched samples. All BaCo1–yYyO3–δ solid solutions were found to have cubic structure (sp. gr. Pm3m). The unit cell parameters were refined using Rietveld full-profile analysis. Oxygen nonstoichiometry of BaCo1–yYyO3–δ solid solutions with 0.1≤y≤0.4 was measured by means of thermogravimetric technique within the temperature range 298–1373 K in air. Thermal expansion of BaCo1–yYyO3–δ (y=0.0; 0.1; 0.2; 0.3) samples was studied within the temperature range 298–1200 K in air. The projection of isothermal–isobaric phase diagram for the Y–Ba–Co–O system to the compositional triangle of metallic components was presented. - Graphical abstract: A projection of isobaric isothermal phase diagram of the Y–Ba–Co–O system to the metallic components

  15. Phase and extraction equilibria in water-syntamide-5-ammonium sulfate and water-syntamide-5k-ammonium sulfate systems

    NASA Astrophysics Data System (ADS)

    Golovkina, A. V.; Kudryashova, O. S.; Lesnov, A. E.; Denisova, S. A.

    2013-09-01

    Phase equilibria in ternary aqueous layering systems containing a commercial nonionogen surfactant (Surf.) syntamide-5 or syntamide-5k and an inorganic salting-out agent ammonium sulfate were studied. The potential application of the systems for liquid extraction of metal ions was assessed.

  16. Phase equilibria in the iron oxide-cobalt oxide-phosphorus oxide system

    NASA Technical Reports Server (NTRS)

    De Guire, Mark R.; Prasanna, T. R. S.; Kalonji, Gretchen; O'Handley, Robert C.

    1987-01-01

    Two novel ternary compounds are noted in the present study of 1000 C solid-state equilibria in the Fe-Co-P-O system's Fe2O3-FePO4-Co3(Po4)2-CoO region: CoFe(PO4)O, which undergoes incongruent melting at 1130 C, and Co3Fe4(PO4)6, whose incongruent melting occurs at 1080 C. The liquidus behavior-related consequences of rapidly solidified cobalt ferrite formation from cobalt ferrite-phosphate melts are discussed with a view to spinel formation. It is suggested that quenching from within the spinel-plus-liquid region may furnish an alternative to quenching a homogeneous melt.

  17. Mie potentials for phase equilibria calculations: application to alkanes and perfluoroalkanes.

    PubMed

    Potoff, Jeffrey J; Bernard-Brunel, Damien A

    2009-11-01

    Transferable united-atom force fields, based on n - 6 Lennard-Jones potentials, are presented for normal alkanes and perfluorocarbons. It is shown that by varying the repulsive exponent the range of the potential can be altered, leading to improved predictions of vapor pressures while also reproducing saturated liquid densities to high accuracy. Histogram-reweighting Monte Carlo simulations in the grand canonical ensemble are used to determine the vapor liquid coexistence curves, vapor pressures, heats of vaporization, and critical points for normal alkanes methane through tetradecane, and perfluorocarbons perfluoromethane through perfluorooctane. For all molecules studied, saturated liquid densities are reproduced to within 1% of experiment. Vapor pressures for normal alkanes and perfluorocarbons were predicted to within 3% and 6% of experiment, respectively. Calculations performed for binary mixture vapor-liquid equilibria for propane + pentane show excellent agreement with experiment, while slight deviations are observed for the ethane + perfluoroethane mixture.

  18. Phase equilibria and volumetric properties of aqueous CaCl{sub 2} by an equation of state

    SciTech Connect

    Jiang, S.; Pitzer, K.S. |

    1996-02-01

    A comprehensive equation of state was developed to represent the phase equilibria and volumetric properties of aqueous calcium chloride solutions at temperatures above 523 K. The equation consists of a reference part and a perturbation contribution. The reference function is developed from the statistical mechanical theory for mixtures of dipolar and quadrupolar hard spheres, which agrees well with the Monte carlo simulation results. In this treatment, calcium chloride is described by the completely undissociated model. The empirical perturbation function is a truncated series of virial expansion terms. Thus, mixing rules are guided by those of virial coefficients, which are derived rigorously from statistical mechanics. The equation reproduces experimental saturated vapor pressures and volumetric data within experimental uncertainty for temperatures to 623 K. At higher temperatures, few and less accurate experimental data are available, but values of the saturated vapor pressures of the liquid have been reported and are represented satisfactorily.

  19. Phase equilibria and structural investigations in the Ni-poor part of the system Al–Ge–Ni

    PubMed Central

    Reichmann, Thomas L.; Duarte, Liliana I.; Effenberger, Herta S.; Leinenbach, Christian; Richter, Klaus W.

    2012-01-01

    The ternary phase diagram Al–Ge–Ni was investigated between 0 and 50 at.% Ni by a combination of differential thermal analysis (DTA), powder- and single-crystal X-ray diffraction (XRD), metallography and electron probe microanalysis (EPMA). Ternary phase equilibria and accurate phase compositions of the equilibrium phases were determined within two partial isothermal sections at 400 and 700 °C, respectively. The two binary intermediate phases AlNi and Al3Ni2 were found to form extended solid solutions with Ge in the ternary. Three new ternary phases were found to exist in the Ni-poor part of the phase diagram which were designated as τ1 (oC24, CoGe2-type), τ2 (at approximately Al67.5Ge18.0Ni14.5) and τ3 (cF12, CaF2-type). The ternary phases show only small homogeneity ranges. While τ1 was investigated by single crystal X-ray diffraction, τ2 and τ3 were identified from their powder diffraction pattern. Ternary phase reactions and melting behaviour were studied by means of DTA. A total number of eleven invariant reactions could be derived from these data, which are one ternary eutectic reaction, six transition reactions, three ternary peritectic reactions and one maximum. Based on the measured DTA values three vertical sections at 10, 20 and 35 at.% Ni were constructed. Additionally, all experimental results were combined to a ternary reaction scheme (Scheil diagram) and a liquidus surface projection. PMID:27087753

  20. Phase equilibria in the oxide system Nd 2O 3-K 2O-P 2O 5

    NASA Astrophysics Data System (ADS)

    Szczygieł, Irena; Znamierowska, Teresa; Mizer, Dagmara

    2010-07-01

    A phase equilibria diagram of the partial system NdPO 4-K 3PO 4-KPO 3 has been developed as part of the research aimed at determining the phase equilibrium relationships in the oxide system Nd 2O 3-K 2O-P 2O 5. The investigations were conducted using thermoanalytical techniques, X-ray powder diffraction analysis and reflected-light microscopy. Three isopleths existing between: K 3Nd(PO 4) 2-K 4P 2O 7, NdPO 4-K 5P 3O 10 and NdPO 4-K 4P 2O 7 have been identified in the partial NdPO 4-K 3PO 4-KPO 3 system. Previously unknown potassium-neodymium phosphate "K 4Nd 2P 4O 15" has been discovered in the latter isopleth section. This phosphate exists in the solid phase up to a temperature of 890 °C at which it decomposes into the parent phosphates NdPO 4 and K 4P 2O 7. Four invariant points: two quasi-ternary eutectics, E 1 (1057 °C) and E 2 (580 °C) and two quasi-ternary peritectics, P 1 (1078 °C) and P 2 (610 °C), occur in the NdPO 4-K 3PO 4-KPO 3 region.

  1. Improving experimental phases for strong reflections prior to density modification

    SciTech Connect

    Uervirojnangkoorn, Monarin; Hilgenfeld, Rolf; Terwilliger, Thomas C.; Read, Randy J.

    2013-09-20

    Experimental phasing of diffraction data from macromolecular crystals involves deriving phase probability distributions. These distributions are often bimodal, making their weighted average, the centroid phase, improbable, so that electron-density maps computed using centroid phases are often non-interpretable. Density modification brings in information about the characteristics of electron density in protein crystals. In successful cases, this allows a choice between the modes in the phase probability distributions, and the maps can cross the borderline between non-interpretable and interpretable. Based on the suggestions by Vekhter [Vekhter (2005), Acta Cryst. D61, 899–902], the impact of identifying optimized phases for a small number of strong reflections prior to the density-modification process was investigated while using the centroid phase as a starting point for the remaining reflections. A genetic algorithm was developed that optimizes the quality of such phases using the skewness of the density map as a target function. Phases optimized in this way are then used in density modification. In most of the tests, the resulting maps were of higher quality than maps generated from the original centroid phases. In one of the test cases, the new method sufficiently improved a marginal set of experimental SAD phases to enable successful map interpretation. Lastly, a computer program,SISA, has been developed to apply this method for phase improvement in macromolecular crystallography.

  2. Improving experimental phases for strong reflections prior to density modification

    DOE PAGES

    Uervirojnangkoorn, Monarin; Hilgenfeld, Rolf; Terwilliger, Thomas C.; Read, Randy J.

    2013-09-20

    Experimental phasing of diffraction data from macromolecular crystals involves deriving phase probability distributions. These distributions are often bimodal, making their weighted average, the centroid phase, improbable, so that electron-density maps computed using centroid phases are often non-interpretable. Density modification brings in information about the characteristics of electron density in protein crystals. In successful cases, this allows a choice between the modes in the phase probability distributions, and the maps can cross the borderline between non-interpretable and interpretable. Based on the suggestions by Vekhter [Vekhter (2005), Acta Cryst. D61, 899–902], the impact of identifying optimized phases for a small number ofmore » strong reflections prior to the density-modification process was investigated while using the centroid phase as a starting point for the remaining reflections. A genetic algorithm was developed that optimizes the quality of such phases using the skewness of the density map as a target function. Phases optimized in this way are then used in density modification. In most of the tests, the resulting maps were of higher quality than maps generated from the original centroid phases. In one of the test cases, the new method sufficiently improved a marginal set of experimental SAD phases to enable successful map interpretation. Lastly, a computer program,SISA, has been developed to apply this method for phase improvement in macromolecular crystallography.« less

  3. Direct phase coexistence molecular dynamics study of the phase equilibria of the ternary methane-carbon dioxide-water hydrate system.

    PubMed

    Michalis, Vasileios K; Tsimpanogiannis, Ioannis N; Stubos, Athanassios K; Economou, Ioannis G

    2016-09-14

    Molecular dynamics simulation is used to predict the phase equilibrium conditions of a ternary hydrate system. In particular, the direct phase coexistence methodology is implemented for the determination of the three-phase coexistence temperature of the methane-carbon dioxide-water hydrate system at elevated pressures. The TIP4P/ice, TraPPE-UA and OPLS-UA forcefields for water, carbon dioxide and methane respectively are used, in line with our previous studies of the phase equilibria of the corresponding binary hydrate systems. The solubility in the aqueous phase of the guest molecules of the respective binary and ternary systems is examined under hydrate-forming conditions, providing insight into the predictive capability of the methodology as well as the combination of these forcefields to accurately describe the phase behavior of the ternary system. The three-phase coexistence temperature is calculated at 400, 1000 and 2000 bar for two compositions of the methane-carbon dioxide mixture. The predicted values are compared with available calculations with satisfactory agreement. An estimation is also provided for the fraction of the guest molecules in the mixed hydrate phase under the conditions examined. PMID:27507133

  4. Direct phase coexistence molecular dynamics study of the phase equilibria of the ternary methane-carbon dioxide-water hydrate system.

    PubMed

    Michalis, Vasileios K; Tsimpanogiannis, Ioannis N; Stubos, Athanassios K; Economou, Ioannis G

    2016-09-14

    Molecular dynamics simulation is used to predict the phase equilibrium conditions of a ternary hydrate system. In particular, the direct phase coexistence methodology is implemented for the determination of the three-phase coexistence temperature of the methane-carbon dioxide-water hydrate system at elevated pressures. The TIP4P/ice, TraPPE-UA and OPLS-UA forcefields for water, carbon dioxide and methane respectively are used, in line with our previous studies of the phase equilibria of the corresponding binary hydrate systems. The solubility in the aqueous phase of the guest molecules of the respective binary and ternary systems is examined under hydrate-forming conditions, providing insight into the predictive capability of the methodology as well as the combination of these forcefields to accurately describe the phase behavior of the ternary system. The three-phase coexistence temperature is calculated at 400, 1000 and 2000 bar for two compositions of the methane-carbon dioxide mixture. The predicted values are compared with available calculations with satisfactory agreement. An estimation is also provided for the fraction of the guest molecules in the mixed hydrate phase under the conditions examined.

  5. Phase equilibria in the lysozyme-ammonium sulfate-water system.

    PubMed

    Moretti, J J; Sandler, S I; Lenhoff, A M

    2000-12-01

    Ternary phase diagrams were measured for lysozyme in ammonium sulfate solutions at pH values of 4 and 8. Lysozyme, ammonium sulfate, and water mass fractions were assayed independently by UV spectroscopy, barium chloride titration, and lyophilization respectively, with mass balances satisfied to within 1%. Protein crystals, flocs, and gels were obtained in different regions of the phase diagrams, and in some cases growth of crystals from the gel phase or from the supernatant after floc removal was observed. These observations, as well as a discontinuity in protein solubility between amorphous floc precipitate and crystal phases, indicate that the crystal phase is the true equilibrium state. The ammonium sulfate was generally found to partition unequally between the supernatant and the dense phase, in disagreement with an assumption often made in protein phase equilibrium studies. The results demonstrate the potential richness of protein phase diagrams as well as the uncertainties resulting from slow equilibration.

  6. Polarization effects and phase equilibria in high-energy-density polyvinylidene-fluoride-based polymers.

    SciTech Connect

    Ranjan, V.; Yu, L.; Nakhmanson, S.; Bernholc, J.; Nardelli, M. B.; Materials Science Division; North Carolina State Univ.; ORNL

    2010-01-01

    Using first-principles calculations, the phase diagrams of polyvinylidene fluoride (PVDF) and its copolymers under an applied electric field are studied and phase transitions between their nonpolar {alpha} and polar {beta} phases are discussed. The results show that the degree of copolymerization is a crucial parameter controlling the structural phase transition. In particular, for tetrafluoroethylene (TeFE) concentration above 12%, PVDF-TeFE is stabilized in the {beta} phase, whereas the {alpha} phase is stable for lower concentrations. As larger electric fields are applied, domains with smaller concentrations ({le} 12%) undergo a transition from the {alpha} to the {beta} phase until a breakdown field of {approx}600 MV m{sup -1} is reached. These structural phase transitions can be exploited for efficient storage of electrical energy.

  7. Phase equilibria constraints on pre-eruptive magma storage conditions for the 1956 eruption of Bezymianny Volcano, Kamchatka, Russia

    NASA Astrophysics Data System (ADS)

    Shcherbakov, Vasily D.; Neill, Owen K.; Izbekov, Pavel E.; Plechov, Pavel Yu.

    2013-08-01

    Phase equilibria experiments were performed on andesites from the catastrophic 1956 eruption of Bezymianny Volcano, Kamchatka, Russia, to determine pre-eruptive magma storage conditions. Fifteen experiments were conducted under water-saturated conditions, with oxygen fugacity equal to the Ni-NiO oxygen buffer, at temperatures between 775 and 1100 °C and pressures between 50 and 200 MPa. Simultaneous amphibole and plagioclase crystallization is reproduced at ≤ 850 °C and ≥ 200 MPa. The simultaneous crystallization temperature range of the plagioclase-clinopyroxene-orthopyroxene-Fe-Ti oxide assemblage increases with decreasing pressure, from 840 to 940 °C at 150 MPa to 940-1020 °C at 50 MPa. Melt inclusion compositions in plagioclase phenocrysts and matrix glass match experimental melt compositions reproduced at 50-100 MPa and ≤ 50 MPa, respectively. Presence of the silica phase in groundmass and mature amphibole breakdown rims suggests that magma has been stored at ca. 3 km depth prior to the final ascent for at least 40 days. Syn-eruptive ascent led to decompression-driven crystallization, which caused a temperature increase from 850-900 °C to 950-1000 °C.

  8. Transferable potentials for phase equilibria-united atom description of five- and six-membered cyclic alkanes and ethers.

    PubMed

    Keasler, Samuel J; Charan, Sophia M; Wick, Collin D; Economou, Ioannis G; Siepmann, J Ilja

    2012-09-13

    While the transferable potentials for phase equilibria-united atom (TraPPE-UA) force field has generally been successful at providing parameters that are highly transferable between different molecules, the polarity and polarizability of a given functional group can be significantly perturbed in small cyclic structures, which limits the transferability of parameters obtained for linear molecules. This has motivated us to develop a version of the TraPPE-UA force field specifically for five- and six-membered cyclic alkanes and ethers. The Lennard-Jones parameters for the methylene group obtained from cyclic alkanes are transferred to the ethers for each ring size, and those for the oxygen atom are common to all compounds for a given ring size. However, the partial charges are molecule specific and parametrized using liquid-phase dielectric constants. This model yields accurate saturated liquid densities and vapor pressures, critical temperatures and densities, normal boiling points, heat capacities, and isothermal compressibilities for the following molecules: cyclopentane, tetrahydrofuran, 1,3-dioxolane, cyclohexane, oxane, 1,4-dioxane, 1,3-dioxane, and 1,3,5-trioxane. The azeotropic behavior and separation factor for the binary mixtures of 1,3-dioxolane/cyclohexane and ethanol/1,4-dioxane are qualitively reproduced. PMID:22900670

  9. Computation of Phase Equilibria, State Diagrams and Gas/Particle Partitioning of Mixed Organic-Inorganic Aerosols

    NASA Astrophysics Data System (ADS)

    Zuend, A.; Marcolli, C.; Peter, T.

    2009-04-01

    The chemical composition of organic-inorganic aerosols is linked to several processes and specific topics in the field of atmospheric aerosol science. Photochemical oxidation of organics in the gas phase lowers the volatility of semi-volatile compounds and contributes to the particulate matter by gas/particle partitioning. Heterogeneous chemistry and changes in the ambient relative humidity influence the aerosol composition as well. Molecular interactions between condensed phase species show typically non-ideal thermodynamic behavior. Liquid-liquid phase separations into a mainly polar, aqueous and a less polar, organic phase may considerably influence the gas/particle partitioning of semi-volatile organics and inorganics (Erdakos and Pankow, 2004; Chang and Pankow, 2006). Moreover, the phases present in the aerosol particles feed back on the heterogeneous, multi-phase chemistry, influence the scattering and absorption of radiation and affect the CCN ability of the particles. Non-ideal thermodynamic behavior in mixtures is usually described by an expression for the excess Gibbs energy, enabling the calculation of activity coefficients. We use the group-contribution model AIOMFAC (Zuend et al., 2008) to calculate activity coefficients, chemical potentials and the total Gibbs energy of mixed organic-inorganic systems. This thermodynamic model was combined with a robust global optimization module to compute potential liquid-liquid (LLE) and vapor-liquid-liquid equilibria (VLLE) as a function of particle composition at room temperature. And related to that, the gas/particle partitioning of semi-volatile components. Furthermore, we compute the thermodynamic stability (spinodal limits) of single-phase solutions, which provides information on the process type and kinetics of a phase separation. References Chang, E. I. and Pankow, J. F.: Prediction of activity coefficients in liquid aerosol particles containing organic compounds, dissolved inorganic salts, and water - Part

  10. Improving experimental phases for strong reflections prior to density modification

    SciTech Connect

    Uervirojnangkoorn, Monarin; Hilgenfeld, Rolf; Terwilliger, Thomas C.; Read, Randy J.

    2013-10-01

    A genetic algorithm has been developed to optimize the phases of the strongest reflections in SIR/SAD data. This is shown to facilitate density modification and model building in several test cases. Experimental phasing of diffraction data from macromolecular crystals involves deriving phase probability distributions. These distributions are often bimodal, making their weighted average, the centroid phase, improbable, so that electron-density maps computed using centroid phases are often non-interpretable. Density modification brings in information about the characteristics of electron density in protein crystals. In successful cases, this allows a choice between the modes in the phase probability distributions, and the maps can cross the borderline between non-interpretable and interpretable. Based on the suggestions by Vekhter [Vekhter (2005 ▶), Acta Cryst. D61, 899–902], the impact of identifying optimized phases for a small number of strong reflections prior to the density-modification process was investigated while using the centroid phase as a starting point for the remaining reflections. A genetic algorithm was developed that optimizes the quality of such phases using the skewness of the density map as a target function. Phases optimized in this way are then used in density modification. In most of the tests, the resulting maps were of higher quality than maps generated from the original centroid phases. In one of the test cases, the new method sufficiently improved a marginal set of experimental SAD phases to enable successful map interpretation. A computer program, SISA, has been developed to apply this method for phase improvement in macromolecular crystallography.

  11. Phase equilibria and trace element partitioning in a magma ocean to 260 kilobars

    NASA Technical Reports Server (NTRS)

    Herzberg, Claude

    1992-01-01

    A magma ocean can solidify in a way that is intermediate between perfect equilibrium and perfect fractional crystallization. In order to model quantitatively any fractional crystallization scenario, it is necessary to understand the geochemical characteristics of the phases that crystallize from a magma ocean, and how they vary with pressure. The crystallizing phase is called the liquidus phase, and their identities were determined by numerous experiments utilizing the multianvil apparatus. For chondritic compositions the liquidus phases are as follows: olivine at 1 atmosphere to 100 kilobars; garnet from 100 to about 260 kilobars; silicate perovskite from 260 kilobars to possibly the core-mantle boundary in the Earth.

  12. Direct evaluation of multicomponent phase equilibria using flat-histogram methods.

    PubMed

    Errington, Jeffrey R; Shen, Vincent K

    2005-10-22

    We present a method for directly locating density-driven phase transitions in multicomponent systems. Phase coexistence conditions are determined through manipulation of a total density probability distribution evaluated over a density range that includes both coexisting phases. Saturation quantities are determined through appropriate averaging of density-dependent mean values of a given property of interest. We discuss how to implement the method in both the grand-canonical and isothermal-isobaric semigrand ensembles. Calculations can be conducted using any of the recently introduced flat-histogram techniques. Here, we combine the general algorithm with a transition-matrix approach to produce an efficient self-adaptive technique for determining multicomponent phase equilibrium properties. To assess the performance of the new method, we generate phase diagrams for a number of binary and ternary Lennard-Jones mixtures.

  13. Prediction of fluid phase equilibria and interfacial tension of triangle-well fluids using transition matrix Monte Carlo

    NASA Astrophysics Data System (ADS)

    Sengupta, Angan; Adhikari, Jhumpa

    2016-05-01

    The triangle-well (TW) potential is a simple model which is able to capture the essence of the intermolecular attraction in real molecules. Transition matrix Monte Carlo simulations in the grand canonical ensemble (GC-TMMC) are performed to investigate the role of the range of attraction on the features of fluid phase equilibria. As the TW potential range increases, the vapour-liquid coexistence curves shift towards a higher temperature range with the critical temperature and pressure increasing, and the critical density values decreasing. These GC-TMMC results are in excellent agreement with the predictions of Gibbs ensemble Monte Carlo and replica exchange Monte Carlo (REMC) simulations reported in literature. Using the GC-TMMC method, the vapour pressures are also computed directly from the particle number probability distributions (PNPDs). It has been noted in literature that the surface tension values are computationally more expensive and difficult to determine than other coexistence properties using molecular simulations. The PNPDs from GC-TMMC simulations along with Binder's formalism allow for the calculation of the interfacial tension with relative ease. Also, our simulation generated results for the interfacial tension are in good agreement with the literature data obtained using REMC (via the virial route) and the plots of our interfacial tension values as a function of temperature are smooth unlike the literature data.

  14. Protein salting-out: phase equilibria in two-protein systems.

    PubMed

    Coen, C J; Prausnitz, J M; Blanch, H W

    1997-03-20

    The phase behavior of two aqueous binary protein mixtures, lysozyme-chymotrypsin and lysozyme-ovalbumin, was determined in ammonium sulfate solutions. Protein concentrations were determined in both phases as a function of pH and ionic strength. For lysozyme-chymotrypsin mixtures, the observed phase behavior was similar to that for each individual protein; the presence of the second protein had little influence. The phase behavior of lysozyme-ovalbumin mixtures, however, was different from that of the respective single-protein systems. Lysozyme and ovalbumin are found together in egg whites; their association is both pH and ionic-strength dependent. The association of proteins is a key determinant of protein solubility in salt solutions.

  15. Direct molecular dynamics simulation of liquid-solid phase equilibria for two-component plasmas.

    PubMed

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

    2012-06-01

    We determine the liquid-solid phase diagram for carbon-oxygen and oxygen-selenium plasma mixtures using two-phase molecular dynamics simulations. We identify liquid, solid, and interface regions using a bond angle metric. To study finite-size effects, we perform 27,648- and 55,296-ion simulations. To help monitor nonequilibrium effects, we calculate diffusion constants D(i). For the carbon-oxygen system we find that D(O) for oxygen ions in the solid is much smaller than D(C) for carbon ions and that both diffusion constants are 80 or more times smaller than diffusion constants in the liquid phase. There is excellent agreement between our carbon-oxygen phase diagram and that predicted by Medin and Cumming. This suggests that errors from finite-size and nonequilibrium effects are small and that the carbon-oxygen phase diagram is now accurately known. The oxygen-selenium system is a simple two-component model for more complex rapid proton capture nucleosynthesis ash compositions for an accreting neutron star. Diffusion of oxygen, in a predominantly selenium crystal, is remarkably fast, comparable to diffusion in the liquid phase. We find a somewhat lower melting temperature for the oxygen-selenium system than that predicted by Medin and Cumming. This is probably because of electron screening effects. PMID:23005226

  16. Equilibria in Chemical Systems

    1992-01-01

    SOLGASMIX-PV calculates equilibrium relationships in complex chemical systems. Chemical equilibrium calculations involve finding the system composition, within certain constraints, which contains the minimum free energy. The constraints are the preservation of the masses of each element present and either constant pressure or volume. SOLGASMIX-PV can calculate equilibria in systems containing a gaseous phase, condensed phase solutions, and condensed phases of invariant and variable stoichiometry. Either a constant total gas volume or a constant total pressuremore » can be assumed. Unit activities for condensed phases and ideality for solutions are assumed, although nonideal systems can be handled provided activity coefficient relationships are available.« less

  17. Phase Equilibria of Ternary and Quaternary Systems Containing Diethyl Carbonate with Water.

    PubMed

    Chen, Yao; Wen, Caiyu; Zhou, Xiaoming; Zeng, Jun

    2014-01-01

    In this study liquid phase equilibrium compositions were measured at 298.15 K under atmospheric pressure for (water + propan-1-ol + diethyl carbonate (DEC) + benzene or cyclohexane or heptane) quaternary systems and (water + DEC + propan-1-ol or benzene or cyclohexane) ternary systems. Good correlation of the experimental LLE data was seen for the measured systems by both modified and extended UNIQUAC models. The solubility of DEC in aqueous and organic phases is shown by equilibrium distribution coefficients calculated from the LLE data.

  18. Molecular theory for the phase equilibria and cluster distribution of associating fluids with small bond angles.

    PubMed

    Marshall, Bennett D; Chapman, Walter G

    2013-08-01

    We develop a new theory for associating fluids with multiple association sites. The theory accounts for small bond angle effects such as steric hindrance, ring formation, and double bonding. The theory is validated against Monte Carlo simulations for the case of a fluid of patchy colloid particles with three patches and is found to be very accurate. Once validated, the theory is applied to study the phase diagram of a fluid composed of three patch colloids. It is found that bond angle has a significant effect on the phase diagram and the very existence of a liquid-vapor transition.

  19. Transferable potentials for phase equilibria. 10. Explicit-hydrogen description of substituted benzenes and polycyclic aromatic compounds.

    PubMed

    Rai, Neeraj; Siepmann, J Ilja

    2013-01-10

    The explicit-hydrogen version of the transferable potentials for phase equilibria (TraPPE-EH) force field is extended to various substituted benzenes through the parametrization of the exocyclic groups -F, -Cl, -Br, -C≡N, and -OH and to polycyclic aromatic hydrocarbons through the parametrization of the aromatic linker carbon atom for multiple rings. The linker carbon together with the TraPPE-EH parameters for aromatic heterocycles constitutes a force field for fused-ring heterocycles. Configurational-bias Monte Carlo simulations in the Gibbs ensemble were carried out to compute vapor-liquid coexistence curves for fluorobenzene; chlorobenzene; bromobenzene; di-, tri-, and hexachlorobenzene isomers; 2-chlorofuran; 2-chlorothiophene; benzonitrile; phenol; dihydroxybenzene isomers; 1,4-benzoquinone; naphthalene; naphthalene-2-carbonitrile; naphthalen-2-ol; quinoline; benzo[b]thiophene; benzo[c]thiophene; benzoxazole; benzisoxazole; benzimidazole; benzothiazole; indole; isoindole; indazole; purine; anthracene; and phenanthrene. The agreement with the limited experimental data is very satisfactory, with saturated liquid densities and vapor pressures reproduced to within 1.5% and 15%, respectively. The mean unsigned percentage errors in the normal boiling points, critical temperatures, and critical densities are 0.9%, 1.2%, and 1.4%, respectively. Additional simulations were carried out for binary systems of benzene/benzonitrile, benzene/phenol, and naphthalene/methanol to illustrate the transferability of the developed potentials to binary systems containing compounds of different polarity and hydrogen-bonding ability. A detailed analysis of the liquid-phase structures is provided for selected neat systems and binary mixtures. PMID:23205778

  20. A New Approach to Modeling Densities and Equilibria of Ice and Gas Hydrate Phases

    NASA Astrophysics Data System (ADS)

    Zyvoloski, G.; Lucia, A.; Lewis, K. C.

    2011-12-01

    The Gibbs-Helmholtz Constrained (GHC) equation is a new cubic equation of state that was recently derived by Lucia (2010) and Lucia et al. (2011) by constraining the energy parameter in the Soave form of the Redlich-Kwong equation to satisfy the Gibbs-Helmholtz equation. The key attributes of the GHC equation are: 1) It is a multi-scale equation because it uses the internal energy of departure, UD, as a natural bridge between the molecular and bulk phase length scales. 2) It does not require acentric factors, volume translation, regression of parameters to experimental data, binary (kij) interaction parameters, or other forms of empirical correlations. 3) It is a predictive equation of state because it uses a database of values of UD determined from NTP Monte Carlo simulations. 4) It can readily account for differences in molecular size and shape. 5) It has been successfully applied to non-electrolyte mixtures as well as weak and strong aqueous electrolyte mixtures over wide ranges of temperature, pressure and composition to predict liquid density and phase equilibrium with up to four phases. 6) It has been extensively validated with experimental data. 7) The AAD% error between predicted and experimental liquid density is 1% while the AAD% error in phase equilibrium predictions is 2.5%. 8) It has been used successfully within the subsurface flow simulation program FEHM. In this work we describe recent extensions of the multi-scale predictive GHC equation to modeling the phase densities and equilibrium behavior of hexagonal ice and gas hydrates. In particular, we show that radial distribution functions, which can be determined by NTP Monte Carlo simulations, can be used to establish correct standard state fugacities of 1h ice and gas hydrates. From this, it is straightforward to determine both the phase density of ice or gas hydrates as well as any equilibrium involving ice and/or hydrate phases. A number of numerical results for mixtures of N2, O2, CH4, CO2, water

  1. Thermodynamic analysis of phase equilibria in the iron-zirconium system

    SciTech Connect

    Pelton, A.D.; Leibowitz, L.; Blomquist, R.A.

    1992-09-01

    Continuing interest in development of metallic fuels for nuclear reactors has prompted an examination of the phase relations of many of the relevant binary and ternary systems of interest. We performed a thermodynamic analysis and optimization of the Fe-Zr system. Overall reasonably good agreement was found with published diagrams, but some significant changes were required to ensure thermodynamic consistency.

  2. Thermodynamic analysis of phase equilibria in the iron-zirconium system

    SciTech Connect

    Pelton, A.D. ); Leibowitz, L.; Blomquist, R.A. )

    1992-01-01

    Continuing interest in development of metallic fuels for nuclear reactors has prompted an examination of the phase relations of many of the relevant binary and ternary systems of interest. We performed a thermodynamic analysis and optimization of the Fe-Zr system. Overall reasonably good agreement was found with published diagrams, but some significant changes were required to ensure thermodynamic consistency.

  3. A Classroom Experiment on Phase Equilibria Involving Orientational Disordering in Crystals.

    ERIC Educational Resources Information Center

    Mjojo, C. C.

    1985-01-01

    Background information, procedures used, and results obtained are provided for an experiment in which a phase diagram is determined using a differential scanning calorimeter. Commercial samples of D-camphoric anhydride (Eastman Kodak) and D,L-camphoric anhydride (Aldrich) were used in the experiment. (JN)

  4. Transport and Phase Equilibria Properties for Steam Flooding of Heavy Oils

    SciTech Connect

    Gabitto, Jorge; Barrufet, Maria

    2002-11-20

    The objectives of this research included experimental determination and rigorous modeling and computation of phase equilibrium diagrams, volumetric, and transport properties of hydrocarbon/CO2/water mixtures at pressures and temperatures typical of steam injection processes for thermal recovery of heavy oils.

  5. 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.

  6. The system Ta-V-Si: Crystal structure and phase equilibria

    SciTech Connect

    Khan, A.U.; Broz, P.; Bursik, J.; Grytsiv, A.; Chen, X.-Q.; Giester, G.; Rogl, P.

    2012-03-15

    Phase relations have been evaluated for the Ta-V-Si system at 1500 and 1200 Degree-Sign C. Three ternary phases were found: {tau}{sub 1}-(Ta,V){sub 5}Si{sub 3} (Mn{sub 5}Si{sub 3}-type), {tau}{sub 2}-Ta(Ta,V,Si){sub 2} (MgZn{sub 2}-type) and {tau}{sub 3}-Ta(Ta,V,Si){sub 2} (MgCu{sub 2}-type). The crystal structure of {tau}{sub 2}-Ta(Ta,V,Si){sub 2} was solved by X-ray single crystal diffraction (space group P6{sub 3}/mmc). Atom order in the crystal structures of {tau}{sub 1}-(Ta,V){sub 5}Si{sub 3} (Mn{sub 5}Si{sub 3} type) and {tau}{sub 3}-Ta(Ta,V,Si){sub 2} was derived from X-ray powder diffraction data. A large homogeneity range was found for {tau}{sub 1}-(Ta{sub x}V{sub 1-x}){sub 5}Si{sub 3} revealing random exchange of Ta and V at a constant Si content. At 1500 Degree-Sign C, the end points of the {tau}{sub 1}-phase solution (0.082{<=}x{<=}0.624) are in equilibrium with the solutions (Ta{sub 1-x}V{sub x}){sub 5}Si{sub 3} (Cr{sub 5}B{sub 3} type, 0{<=}x{<=}0.128) and (Ta{sub x}V{sub 1-x}){sub 5}Si{sub 3} (W{sub 5}Si{sub 3} type, 0{<=}x{<=}0.048). - Graphical abstract: Phase relations have been evaluated for the Ta-V-Si system at 1500 and 1200 Degree-Sign C. Highlights: Black-Right-Pointing-Pointer Phase relations have been evaluated for the Ta-V-Si system at 1500 and 1200 Degree-Sign C. Black-Right-Pointing-Pointer Three ternary phases were found at 1500 Degree-Sign C. Black-Right-Pointing-Pointer At 1500 Degree-Sign C, {tau}{sub 1}-phase has large homogeneity region (0.064{<=}x{<=}0.624).

  7. TRANSPORT AND PHASE EQUILIBRIA PROPERITIES FOR STEAM FLOODING OF HEAVY OILS

    SciTech Connect

    Jorge Gabitto; Maria Barrufet

    2002-09-01

    Hydrocarbon/water and CO{sub 2} systems are frequently found in petroleum recovery processes, petroleum refining, and gasification of coals, lignites and tar sands. Techniques to estimate the phase volume and phase composition are indispensable to design and improve oil recovery processes such as steam, hot water, or CO{sub 2}/steam combinations of flooding techniques typically used for heavy oils. An interdisciplinary research program to quantify transport, PVT, and equilibrium properties of selected oil/CO{sub 2}/water mixtures at pressures up to 10,000 psia and at temperatures up to 500 F has been put in place. The objectives of this research include experimental determination and rigorous modeling and computation of phase equilibrium diagrams, and volumetric properties of hydrocarbon/CO{sub 2}/water mixtures at pressures and temperatures typical of steam injection processes for thermal recovery of heavy oils. Highlighting the importance of phase behavior, researchers ([1], and [2]) insist on obtaining truly representative reservoir fluids samples for experimental analysis. The prevailing sampling techniques used for compositional analysis of the fluids have potential for a large source of error. These techniques bring the sample to atmospheric conditions and collect the liquid and vapor portion of the samples for further analysis. We developed a new experimental technique to determine phase volumes, compositions and equilibrium K-values at reservoir conditions. The new methodology is able to measure phase volume and composition at reservoir like temperatures and pressures. We use a mercury free PVT system in conjunction with a Hewlett Packard gas chromatograph capable of measuring compositions on line at high pressures and temperatures. This is made possible by an essentially negligible disturbance of the temperature and pressure equilibrium during phase volume and composition measurements. In addition, not many samples are withdrawn for compositional analysis

  8. Calculations of phase equilibria for mixtures of triglycerides, fatty acids, and their esters in lower alcohols

    NASA Astrophysics Data System (ADS)

    Stepanov, D. A.; Ermakova, A.; Anikeev, V. I.

    2011-01-01

    The objects of study were mixtures containing triglycerides and lower alcohols and also the products of the transesterification of triglycerides, glycerol and fatty acid esters. The Redlich-Kwong-Soave equation of state was used as a thermodynamic model for the phase state of the selected mixtures over wide temperature, pressure, and composition ranges. Group methods were applied to determine the critical parameters of pure substances and their acentric factors. The parameters obtained were used to calculate the phase diagrams and critical parameters of mixtures containing triglycerides and lower alcohols and the products of the transesterification of triglycerides, glycerol and fatty acid esters, at various alcohol/oil ratios. The conditions of triglyceride transesterification in various lower alcohols providing the supercritical state of reaction mixtures were selected.

  9. Ceria in an oxygen environment: Surface phase equilibria and its descriptors

    NASA Astrophysics Data System (ADS)

    Botu, Venkatesh; Ramprasad, Rampi; Mhadeshwar, Ashish B.

    2014-01-01

    Ceria offers great promise in catalysis, due to its facile switchable oxidation state manifested from its oxygen buffering capability. This work presents the first equilibrium surface phase diagram of ceria exposed to various oxygen providing reservoirs (e.g., a pure O2 reservoir as well as NO/NO2, H2/H2O, or CO/CO2 redox environments) using first principles thermodynamics. For a pure O2 environment, the stoichiometric ceria (111) surface is favored at ambient conditions. Any appreciable surface reduction is observed only at ultra-low oxygen partial pressures (< 10- 30 atm) and room temperature or at temperatures > 2000 K and ambient pressures. On the other hand, a redox environment promotes surface reduction at temperatures as low as 300 K. Semi-local, Hubbard modified semi-local, and hybrid electronic exchange-correlation functionals are used to capture the energetics and phase transitions. We observe no difference between the three theories in the energetics governing ceria surface reduction in the dilute limit. The predicted phase transitions by all levels of theory are in agreement with each other and in excellent agreement with literature experimental data. Creation of oxygen vacancies in the sub-surface is energetically favored over surface vacancies, and is pivotal in determining the key features of the surface phase diagram. Consequently, we identify the oxygen vacancy formation energy as a descriptor for the surface reactivity of ceria in various oxygen environments. This single governing factor could be used in future studies to probe the surface reactivity of ceria and also to design improved ceria-based materials for redox reactions.

  10. Volumetric Properties and Fluid Phase Equilibria of CO2 + H2O

    SciTech Connect

    Capobianco, Ryan; Gruszkiewicz, Miroslaw {Mirek} S; Wesolowski, David J; Cole, David R; Bodnar, Robert

    2013-01-01

    The need for accurate modeling of fluid-mineral processes over wide ranges of temperature, pressure and composition highlighted considerable uncertainties of available property data and equations of state, even for the CO2 + H2O binary system. In particular, the solubility, activity, and ionic dissociation equilibrium data for the CO2-rich phase, which are essential for understanding dissolution/precipitation, fluid-matrix reactions, and solute transport, are uncertain or missing. In this paper we report the results of a new experimental study of volumetric and phase equilibrium properties of CO2 + H2O, to be followed by measurements for bulk and confined multicomponent fluid mixtures. Mixture densities were measured by vibrating tube densimetry (VTD) over the entire composition range at T = 200 and 250 C and P = 20, 40, 60, and 80 MPa. Initial analysis of the mutual solubilities, determined from volumetric data, shows good agreement with earlier results for the aqueous phase, but finds that the data of Takenouchi and Kennedy (1964) significantly overestimated the solubility of water in supercritical CO2 (by a factor of more than two at 200 C). Resolving this well-known discrepancy will have a direct impact on the accuracy of predictive modeling of CO2 injection in geothermal reservoirs and geological carbon sequestration through improved equations of state, needed for calibration of predictive molecular-scale models and large-scale reactive transport simulations.

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

    PubMed

    Ioniţă, Simona; Feroiu, Viorel; Geană, Dan

    2013-11-14

    In this work experimental vapor-liquid equilibrium (VLE) data and three-phase vapor-liquid-liquid equilibrium (VLLE) data are presented for the carbon dioxide + 1-decanol system. The VLE data were measured at five temperatures, (303.2, 308.2, 323.2, 333.2, and 343.2) K, and pressures up to 16 MPa. The VLLE data cover pressure-temperature (P-T) values from 289 K and 5 MPa to the upper critical end point (UCEP). We have used two models to represent the complex fluid phase behavior (P-T critical curve, VLLE line, and VLE isotherms) of the carbon dioxide + 1-decanol system: the cubic general equation of state (GEOS) and Peng-Robinson (PR) equation in conjunction with van der Waals two parameters conventional mixing rules (2PCMR). A correlation method involving temperature-dependent interaction parameters and a semipredictive approach with independent temperature interaction parameters have been used. Comparisons with experimental data reported in this work and available in the literature indicate that the topology of fluid phase behavior is satisfactorily given by the semipredictive procedure both for the critical line and in subcritical region, considering the relative simple used cubic equations of state. PMID:24249919

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

    PubMed

    Ioniţă, Simona; Feroiu, Viorel; Geană, Dan

    2013-11-14

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

  13. Reentrant radio-frequency resonator for automated phase-equilibria and dielectric measurements in fluids

    SciTech Connect

    Goodwin, A.R.; Mehl, J.B.; Moldover, M.R.

    1996-12-01

    A reentrant rf cavity resonator has been developed for automated detection of phase separation of fluid mixtures contained within the cavity. Successful operation was demonstrated by redetermining the phase boundaries of a CO{sub 2}+C{sub 2}H{sub 6} mixture in the vicinity of its critical point. We developed an accurate electrical model for the resonator and used helium to determine the deformation of the resonator under pressure. With the model and pressure compensation, the resonator was capable of very accurate dielectric measurements. We confirmed this by remeasuring the molar dielectric polarizability {ital A}{sub {epsilon}} of argon and obtained the result {ital A}{sub {epsilon}}=(4.140{plus_minus}0.006) cm{sup 3}/mol (standard uncertainty) in excellent agreement with published values. We exploited the capability for accurate dielectric measurements to determine the densities of the CO{sub 2}+C{sub 2}H{sub 6} mixture at the phase boundaries and to determine the dipole moment of 1,1,1,2,3,3-hexafluoropropane, a candidate replacement refrigerant. Near the operating frequency of 375 MHz the capacitor in the resonator has an impedance near 14 {Omega}. This low impedance is more tolerant of electrical conductivity within the test fluid and in parallel paths in the support structures than comparable capacitors operating at audio frequencies. This will be an advantage for operation at high temperatures where some conductivity must be expected in all fluids. Of further value for high-temperature applications, the present rf resonator has only two metal{endash}insulator joints. These joints seal coaxial cables; neither joint is subjected to large mechanical stresses and neither joint is required to maintain precise dimensional tolerances. The resonator is rugged and may be operated with inexpensive electronics.

  14. Phase equilibria of Fe-C binary alloys in a magnetic field

    NASA Astrophysics Data System (ADS)

    England, Roger Dale

    The deployment of high flux magnetic processing in industry requires the ability to model the expected results of a proposed processing, and the current assumptions in the literature did not reflect the actual outcome in measurements of ductile iron. Simple binary iron-carbon alloys of less than one weight percent carbon were thermo-magnetically processed and then compared with Gibbs free energy phase transformation predictions. The data was used to quantify the change in the Gibbs free energy associated with the addition of a static high flux magnetic field, which is complicated by the change in magnetic response as the iron carbon alloys pass through the Curie point. A current common practice is to modify Gibbs free energy by -12J per mole per Tesla applied, as has been reported in the literature. This current prediction practice was employed in initial experiments for this work and the experimental data did not agree with these predicted values. This work suggests two specific influences that affect the model, chemistry and magnetic dipole changes. First, that the influence of alloying elements in the original chemistry, as the samples in the literature were a manganese alloy with 0.45 weight percent carbon, as well as not being precisely controlled for tramp elements that commonly occur in recycled material, created a change that was not predicted and therefore the temperatures were incorrect. Also, the phase transformation in a high flux magnetic field was measured to have a different response under warming versus cooling than the normal hysteresis under ambient magnetism. The change in Gibbs free energy for the binary alloys was calculated as -3J per mole per Tesla in warming, and -8J per mole per tesla in cooling. The change from these values to the -12J per mole per Tesla previously reported is attributed to the change in chemistry. This work attributes the published increase in physical properties to the Hall-Petch relation as a result of the finer product

  15. Phase equilibria and stability characteristics of chlorpropamide-urea solid dispersions.

    PubMed

    Ford, J L; Rubinstein, M H

    1977-04-01

    Physical mixtures and melts of various compositions of chlorpropamide and urea have been prepared. The phase diagrams and the effects of ageing of the systems have been measured by differential scanning calorimetry. The eutectic composition was found to contain 89% w/w chlorpropamide. Greater concentrations of chlorpropamide produced solid solutions of urea in chlorpropamide, whereas solid solution formation did not occur at compositions less than 89%. Melts in the range 50-100% chlorpropamide, which included the eutectic, existed as glass solids. The effect of ageing produced generally an increase in the liquidus peak temperature which was considered to be due to a gradual increase in crystal size. PMID:17669

  16. Phase equilibria in a system of aqueous arginine with an octane solution of sulfonic acid

    NASA Astrophysics Data System (ADS)

    Kuvaeva, Z. I.; Koval'chuk, I. V.; Vodop'yanova, L. A.; Soldatov, V. S.

    2013-05-01

    The extraction of arginine (Arg) from aqueous salt (0.1 M NaCl) solutions with a sulfo extractant in a wide range of pH values and amino acid concentrations was studied. The 0.1 M solution of dinonylnaphthalenesulfonic acid (HD) in octane was used as an extractant. The degree of extraction was found to be high at pH 0.8-9.0. This can be explained by the effect of additional intermolecular interactions in the extractant phase involving the guanidine group of Arg.

  17. The high-temperature phase equilibria of the Ni–Sn–Zn system: Isothermal sections

    PubMed Central

    Schmetterer, Clemens; Rajamohan, Divakar; Ipser, Herbert; Flandorfer, Hans

    2011-01-01

    In this work three complete isothermal sections of the Ni–Sn–Zn system at 700, 800 and 900 °C are presented. They were constructed based on experimental investigation of more than 60 alloy samples. Powder XRD, single crystal XRD, EPMA, and DTA measurements on selected samples were carried out. Two new ternary compounds, designated as τ2 (Ni5Sn4Zn) and τ3 (Ni7Sn9Zn5), were identified and their homogeneity ranges and crystal structures could be described. Whereas τ3 is only present at 700 °C, the τ2-phase was found at both 700 and 800 °C. No truly ternary compound could be found in the isothermal section at 900 °C. A seemingly ternary compound at 20 at% Sn in the Ni-rich part of Ni–Sn–Zn was found at 800 and 900 °C. Our XRD results, however, indicate that this phase is a ternary solid solution of Ni3Sn-HT from constituent binary Ni–Sn. It is stabilized to lower temperatures by additions of Zn. These new experimental results will provide valuable information to the thermodynamic description of alloy systems relevant for high-temperature lead-free soldering. PMID:27087750

  18. Phase equilibria and thermal expansion of CaTiO 3 doped with neptunium

    NASA Astrophysics Data System (ADS)

    Sato, Tsuyoshi; Yamashita, Toshiyuki; Matsui, Tsuneo

    2005-09-01

    Phase relationships between NpO 2 and CaTiO 3 or Ca(Ti,Al)O 3 were investigated by X-ray diffraction (XRD) analysis at room temperature, using specimens prepared at 1773 K in Ar-8%H 2 atmosphere. Single phase solid solutions were formed for 0-7.5 mol% Np doped CaTiO 3 and 1-10 mol% Np doped Ca(Ti,Al)O 3. By substituting Al for Ti in CaTiO 3, Np solubility in Ca(Ti,Al)O 3 increased. Thermal expansions of (Ca 1- xNp x)TiO 3 ( x = 0.03, 0.05 and 0.075) were measured for temperatures between room temperature and 1273 K in Ar-8%H 2 atmosphere using high-temperature XRD technique. Volumetric thermal expansion coefficients of these three specimens were nearly the same value, suggesting that the incorporation of tetravalent Np into CaTiO 3 had practically no effect on stabilization of the crystal lattice.

  19. Development of a force field for molecular simulation of the phase equilibria of perfluoromethylpropyl ether

    NASA Astrophysics Data System (ADS)

    Li, H.-C.; McCabe, C.; Cui, S. T.; Cummings, P. T.; Cochran, H. D.

    A first step towards the development of a general, realistic potential model for perfluoroether compounds has been to parameterize a united atom model for a short chain perfluoroether perfluoromethylpropyl ether (CF 3 CF 2 CF 2 OCF 3 ). The potential model takes the usual form in which separate bond bending and torsional terms describe the intramolecular interactions with the addition of van der Waals and electrostatic terms to describe the non-bonded interactions. Ab initio quantum calculations have been carried out to obtain the partial charges and intramolecular torsional and bending potentials. Phase equilibrium data were then used to optimize the van der Waals interaction parameters through Gibbs ensemble Monte Carlo simulations. The resulting model reproduces vapour-liquid equilibrium densities, the critical temperature and the critical density of perfluoromethylpropyl ether, in good agreement with those from experiment.

  20. Phase equilibria of charge-, size-, and shape-asymmetric model electrolytes.

    PubMed

    Yan, Qiliang; de Pablo, Juan J

    2002-03-01

    The low-temperature phase behavior of two 2:1 hard-core electrolyte models has been investigated by Monte Carlo simulations. In the first model, both bivalent cations and monovalent anions are spherical, and the charges are located at the ion's centers; in the second model, bivalent cations are modeled as rigid dimers composed of two tangent hard spheres, each carrying a positive charge at the center. It is found that the critical temperature and the critical density are strongly affected by the size asymmetry and the shape of the ions. The results presented in this work provide insights into the behavior of charged colloidal suspensions and polyelectrolytes, where large, symmetric or asymmetric ionic species carrying like charges can attract each other and give rise to thermodynamically unstable conditions.

  1. Thermal analysis, phase equilibria, and superconducting properties in magnesium boride and carbon doped magnesium boride

    NASA Astrophysics Data System (ADS)

    Bohnenstiehl, Scot David

    In this work, the low temperature synthesis of MgB2 from Mg/B and MgH2/B powder mixtures was studied using Differential Scanning Calorimetry (DSC). For the Mg/B powder mixture, two exothermic reaction events were observed and the first reaction event was initiated by the decomposition of Mg(OH)2 on the surface of the magnesium powder. For the MgH 2/B powder mixture, there was an endothermic event at ˜375 °C (the decomposition of MgH2 into H2 and Mg) and an exothermic event ˜600 °C (the reaction of Mg and B). The Kissinger analysis method was used to estimate the apparent activation energy of the Mg and B reaction using DSC data with different furnace ramp rates. The limitations of MgB2 low temperature synthesis led to the development of a high pressure induction furnace that was constructed using a pressure vessel and an induction heating power supply. The purpose was to not only synthesize more homogeneous MgB2 samples, but also to determine whether MgB2 melts congruently or incongruently. A custom implementation of the Smith Thermal Analysis method was developed and tested on aluminum and AlB2, the closest analogue to MgB2. Measurements on MgB2 powder and a high purity Mg/B elemental mixture confirmed that MgB2 melts incongruently and decomposes into a liquid and MgB4 at ˜1445 °C at 10 MPa via peritectic decomposition. Another measurement using a Mg/B elemental mixture with impure boron suggested that ˜0.7 wt% carbon impurity in the boron raised the incongruent melting temperature to ˜1490-1500 °C. Lastly, the solubility limit for carbon in MgB2 was studied by making samples from B4C and Mg at 1530 °C, 1600 °C and 1700 °C in the high pressure furnace. All three samples had three phases: Mg, MgB2C2, and carbon doped MgB2. The MgB 2C2 and carbon doped MgB2 grain size increased with temperature and the 1700 °C sample had needle-like grains for both phases. The presence of the ternary phase, MgB2C2, suggested that the maximum doping limit for carbon in

  2. Application of the cell potential method to predict phase equilibria of multicomponent gas hydrate systems.

    PubMed

    Anderson, Brian J; Bazant, Martin Z; Tester, Jefferson W; Trout, Bernhardt L

    2005-04-28

    We present the application of a mathematical method reported earlier by which the van der Waals-Platteeuw statistical mechanical model with the Lennard-Jones and Devonshire approximation can be posed as an integral equation with the unknown function being the intermolecular potential between the guest molecules and the host molecules. This method allows us to solve for the potential directly for hydrates for which the Langmuir constants are computed, either from experimental data or from ab initio data. Given the assumptions made in the van der Waals-Platteeuw model with the spherical-cell approximation, there are an infinite number of solutions; however, the only solution without cusps is a unique central-well solution in which the potential is at a finite minimum at the center to the cage. From this central-well solution, we have found the potential well depths and volumes of negative energy for 16 single-component hydrate systems: ethane (C2H6), cyclopropane (C3H6), methane (CH4), argon (Ar), and chlorodifluoromethane (R-22) in structure I; and ethane (C2H6), cyclopropane (C3H6), propane (C3H8), isobutane (C4H10), methane (CH4), argon (Ar), trichlorofluoromethane (R-11), dichlorodifluoromethane (R-12), bromotrifluoromethane (R-13B1), chloroform (CHCl3), and 1,1,1,2-tetrafluoroethane (R-134a) in structure II. This method and the calculated cell potentials were validated by predicting existing mixed hydrate phase equilibrium data without any fitting parameters and calculating mixture phase diagrams for methane, ethane, isobutane, and cyclopropane mixtures. Several structural transitions that have been determined experimentally as well as some structural transitions that have not been examined experimentally were also predicted. In the methane-cyclopropane hydrate system, a structural transition from structure I to structure II and back to structure I is predicted to occur outside of the known structure II range for the cyclopropane hydrate. Quintuple (L

  3. Experimental constraints on the Qitianling granite in south China: phase equilibria and petrogenetic implications

    NASA Astrophysics Data System (ADS)

    Huang, Fangfang; Scaillet, Bruno; Wang, Rucheng; Erdmann, Saskia; Chen, Yan; Faure, Michel; Liu, Hongsheng; Xie, Lei; Wang, Bo; Zhu, Jinchu

    2016-04-01

    In South China, the huge distribution of the Mesozoic metallogenic province reflects the abundant magmatism and associated mineralizations which occurred during that period. Building up the phase equilibrium diagrams of representative Mesozoic granites allows us to better understand Mesozoic magmatic events, an approach so far little applied to granites of South China. The Qitianling ganite is a representative Jurassic A-type metaluminous pluton which is associated with tin mineralization in South China. The dominant rock-types are hornblende-biotite monzonitic granites, biotite±hornblende bearing granites and fine-grained biotite-bearing granites. Three metaluminous granite samples (QTL38C, QTL14A and QTL13), of varying mafic character but all bearing hornblende, were chosen for constraining crystallization and magma generation conditions of the Qitianling composite batholith. Crystallization experiments were performed in the 100-700 MPa range, albeit mainly at 200 MPa, at an fO2 at NNO-1 or NNO +2.5, in a temperature range 700°C to 900°C. At 200 MPa, the water content in melt varies between 3 wt% and 6.5 wt% (water-saturated). Experimental results show that under H2O-saturated conditions and at NNO-1, ilmenite, magnetite and pyroxene are the liquidus phases, followed by hornblende, biotite and plagioclase. Hornblende is present only in the most mafic sample (QTL38C), below 900°C and above 5 wt% H2O. In contrast, for H2O-saturated conditions and at NNO+2.5, magnetite, pyroxene crystallize first, followed by biotite while ilmenite is rarely observed. Petrographic observations of natural samples show that magnetite and ilmenite coexist, whereas pyroxene is never observed. The Fe# value (Fe/Mg+Fe) of natural amphibole goes up to 0.69, being on average at 0.67. Experiments indicate that the crystallization of pyroxene occurs at early magmatic stages, but it breaks down to hornblende and biotite at low temperatures, explaining its absence in natural assemblages

  4. Phase equilibria of NdC1 3NaClKCl

    NASA Astrophysics Data System (ADS)

    Hosoya, Yuji; Terai, Takayuki; Tanaka, Satoru; Takahashi, Yoichi

    1997-08-01

    Molten chloride is considered to be applied to a fast-breeder-reactor fuel and a solvent in the pyrochemical reprocessing of spent nuclear fuel. In this work, phase diagrams for molten chloride systems were constructed, using NdCl 3 as an imitative substance in place of UCl 3 or PuCl 3. A compound of 3NdC1 3 · NaCl, which melts incongruently at 540°C to NdCl 3 and liquid and a eutectic at 437°C were found in the NdC1 3NaCl system. In the NdCl 3KCl system, many invariant reactions were observed: the decomposition of NdCl 3 · 2KCl and 2NdCl 3 · KCl at 444 and 474°C, respectively; a eutectic at 489°C; a peritectic at 506°C and a monotectic at 624°C. It is thought that there should be a peritectic compound of 6NdCl 3 · KCl above 474°C. A compound of 2NdC1 3 · NaCl · KCl was considered to exist in the ternary system of NdCl 3NaClKCl, to which attention should be paid in determining the composition of the fuel of the molten-salt fast breeder reactor.

  5. Phase equilibria in the U-Si system from first-principles calculations

    NASA Astrophysics Data System (ADS)

    Noordhoek, Mark J.; Besmann, Theodore M.; Andersson, David; Middleburgh, Simon C.; Chernatynskiy, Aleksandr

    2016-10-01

    Density functional theory calculations have been used with spin-orbit coupling and on-site Coulomb correction (GGA + U) methods to investigate the U-Si system. Structural prediction methods were employed to identify alternate stable structures. Convex hulls of the U-Si system were constructed for each of the methods to highlight the competing energetics of various phases. For GGA calculations, new structures are predicted to be dynamically stable, but these have not been experimentally observed. When the GGA + U (Ueff > 1.3 eV) method is considered, the experimentally observed structures are predicted to be energetically preferred. Phonon calculations were used to investigate the energy predictions and showed that the use of the GGA + U method removes the significant imaginary frequencies observed for U3Si2 when the correction is not considered. Total and partial electron density of states calculations were also performed to understand the role of GGA + U methods and orbitals on the bonding and stability of U-Si compounds.

  6. Phase equilibria in the UO 2-austenitic steel system up to 3000°C

    NASA Astrophysics Data System (ADS)

    Kleykamp, Heiko

    1997-08-01

    The pseudobinary UO 2-austenitic steel system was investigated by DTA up to 1500°C, by isothermal annealing up to 2000°C, by induction heating up to 2850°C and by arc melting up to about 3000°C. The system is characterized by a degenerate eutectic at 1433°C on the steel side and a monotectic at 2830°C and about 1 mol% steel. The maximum solubility of steel in solid U0 2 is 0.6 mol%, that in liquid U0 2 at 3000°C is about 4 mol%. U0 2 and steel form (Fe, Mn, Cr) 2O 3 precipitates between 1300 and 2600°C as U02 becomes hypostoichiometric. Liquid steel is stabilized to higher temperatures above its boiling point at 2790°C by dissolution of uranium and decomposes peritectically to liquid UO 2-χ and gas at estimated 3200°C. The critical data of the single-phase U0 2-steel melt based on the application of the Redlich-Kister model are Tc = 4900°C, Pc = 300 bar and χ c, steel = 0.41.

  7. Phase Equilibria of a S- and C-Poor Lunar Core

    NASA Technical Reports Server (NTRS)

    Righter, K.; Pando, K.; Go, B. M.; Danielson, L. R.; Habermann, M.

    2016-01-01

    The composition of the lunar core can have a large impact on its thermal evolution, possible early dynamo creation, and physical state. Geochemical measurements have placed better constraints on the S and C content of the lunar mantle. In this study we have carried out phase equilibrium studies of geochemically plausible S- and C-poor lunar core compositions in the Fe-Ni-S-C system, and apply them to the early history of the Moon. We chose two bulk core compositions, with differing S and C content based on geochemical analyses of S and C trapped melts in Apollo samples, and on the partitioning of S and C between metal and silicate. This approach allowed calculation of core S and C contents - 90% Fe, 9% Ni, 0.5% C, and 0.375% S by weight; a second composition contained 1% each of S and C. Experiments were carried out from 1473K to 1973K and 1 GPa to 5 GPa, in piston cylinder and multi- anvil apparatuses. Combination of the thermal model of with our results, shows that a solid inner core (and therefore initiation of a dynamo) may have been possible in the earliest history of the Moon (approximately 4.2 Ga ago), in agreement with. Thus a volatile poor lunar core may explain the thermal and magnetic history of the Moon.

  8. Ternary clathrates Ba Cd Ge: phase equilibria, crystal chemistry and physical properties

    NASA Astrophysics Data System (ADS)

    Melnychenko-Koblyuk, N.; Grytsiv, A.; Berger, St.; Kaldarar, H.; Michor, H.; Röhrbacher, F.; Royanian, E.; Bauer, E.; Rogl, P.; Schmid, H.; Giester, G.

    2007-01-01

    The present paper describes the formation, phase relations at subsolidus temperatures and at 800 °C, crystal chemistry and physical properties of a series of ternary clathrates as part of the solid solution {\\mathrm {Ba_{8}Cd}}_{x}\\mathrm {Ge}_{43-5x/8}\\square _{3-3x/8} , derived from binary {\\mathrm {Ba_{8}Ge_{43}}}\\square_{3} with a solubility limit of 8 Cd per formula unit at 800 °C. Structural investigations in all cases confirm cubic primitive symmetry with a lattice parameter aap1.1 nm, consistent with the space group type Pm{\\bar {3}}n . Both the temperature dependent x-ray spectra and the heat capacity define a low-lying, almost localized, phonon branch. Studies of transport properties show electrons to be the majority charge carriers in the systems. As the Cd content increases, the system is driven towards a metal-to-insulator transition, causing \\mathrm {Ba_{8}Cd_{4.7}Ge_{40.3}}\\square_{1.0} , for example, to show metallic behaviour at low temperatures while at high temperatures semiconducting features become obvious. A model based on a gap of the electronic density of states slightly above the Fermi energy perfectly explains such a scenario. Thermal conductivity exhibits a pronounced low temperature maximum, dominated by the lattice contribution, while at higher temperatures the electronic part becomes more important.

  9. Experimental Determinations of the Activity-Composition Relations and Phase Equilibria of H{sub 2}O-CO{sub 2}-NaCl Fluids

    SciTech Connect

    Anovitz, L.M.; Labotka, T.C.; Blencoe, J.G.; Singh, J.; Horita, J.

    1999-09-12

    An understanding of activity-composition (a/X) relations and phase equilibria for halite-bearing, mixed-species supercritical fluids is critically important in many geological and industrial applications. The authors have performed experiments on the a/X relations and phase equilibria of H{sub 2}O-CO{sub 2}-NaCl fluids at 5OO C, 500 bars, to obtain highly accurate and precise data for this ternary system. H{sub 2}O-CO{sub 2}-NaCl samples were reacted at a (H{sub 2}O) = 0.350, 0.425, 0.437, 0.448, 0.560, 0.606, 0.678, 0.798, and 0.841. Results indicate that fluids with these activities lie in the vapor-NaCl two-phase region, and that a fluid with the last value has a composition close to the three-phase (vapor + brine + halite) field. Data from these experiments and NaCl solubility runs also suggest that the vapor comer of the three-phase field lies near X(H{sub 2}O) = 0.760, X(NaCl) = 0.065, which is a significantly more water-rich composition than suggested by the model of [1].

  10. Experiments on phase equilibria in hydrous tholeiitic systems: implications for the genesis of oceanic plagiogranites

    NASA Astrophysics Data System (ADS)

    Koepke, J.; Berndt, J.; Feig, S. T.

    2003-04-01

    For the genesis of oceanic plagiogranites at mid-ocean spreading systems, two models are under discussion: (1) Late-stage differentiation of a MORB-type melt and (2) partial melting of pre-existing gabbros within high-temperature shear zones. In this study, we have applied recent experimental data of the experimental lab in Hannover to the plagiogranite petrogenesis in order to test both models. The role of water during the genesis of these rocks (presence of amphibole as mafic phase in natural plagiogranites) was assessed by including water to the systems. Crystallization experiments were performed in a MORB system doped with different water contents at different redox conditions at 200 MPa (Berndt, 2002), and hydrous partial melting experiments were performed at 200 MPa on typical oceanic gabbros (Feig et al., this volume). For the experiments we have used an internally heated pressure vessel for high temperatures (up to 1250°C) equipped with a rapid-quench system and a hydrogen membrane for controlling the oxygen fugacity. Liquid lines of descent obtained via crystallization experiments are mainly controlled by oxygen fugacity and only to a little extent by water activity. SiO2-rich residual melts can be obtained under both oxidizing and reducing redox condition at low temperatures, but at least one fractionation step is required to reach high-silicic plagiogranites (SiO2 > 70 wt%). The partial melting of typical oceanic gabbro leads at low temperatures also to plagiogranitic melts. At 940°C, the normalized SiO2 contents of the experimental melts of the three investigated systems range between 60 and 61 wt%, and at 900°C from 63 and 68 wt%. These melts coexist with orthopyroxene, amphibole, plagioclase and in one sample also with olivine. The experimental melt compositions are compared with those of natural plagiogranites of different tectonic settings and show in general a broad compositional overlap with those. Our experiments imply, in concordance with the

  11. Re-investigation of phase equilibria in the system Al–Cu and structural analysis of the high-temperature phase η1-Al1−δCu

    PubMed Central

    Ponweiser, Norbert; Lengauer, Christian L.; Richter, Klaus W.

    2011-01-01

    The phase equilibria and reaction temperatures in the system Al–Cu were re-investigated by a combination of optical microscopy, powder X-ray diffraction (XRD) at ambient and elevated temperature, differential thermal analysis (DTA) and scanning electron microscopy (SEM). A full description of the phase diagram is given. The phase equilibria and invariant reactions in the Cu-poor part of the phase diagram could be confirmed. The Cu-rich part shows some differences in phase equilibria and invariant reactions compared to the known phase diagram. A two phase field was found between the high temperature phase η1 and the low temperature phase η2 thus indicating a first order transition. In the ζ1/ζ2 region of the phase diagram recent findings on the thermal stability could be widely confirmed. Contrary to previous results, the two phase field between δ and γ1 is very narrow. The results of the current work indicate the absence of the high temperature β0 phase as well as the absence of a two phase field between γ1 and γ0 suggesting a higher order transition between γ1 and γ0. The structure of γ0 (I-43m, Cu5Zn8-type) was confirmed by means of high-temperature XRD. Powder XRD was also used to determine the structure of the high temperature phase η1-Al1−δCu. The phase is orthorhombic (space group Cmmm) and the lattice parameters are a = 4.1450(1) Å, b = 12.3004(4) Å and c = 8.720(1) Å; atomic coordinates are given. PMID:27103761

  12. 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.

  13. A practical application of Driscoll's equation for predicting the acid-neutralizing capacity in acidic natural waters equilibria with the mineral phase gibbsite.

    PubMed

    Bi, S P; An, S Q; Liu, F

    2001-05-01

    A practical application of Driscoll's equation for predicting the acid-neutralizing capacity (ANC) in acidic waters equilibria with the mineral phase gibbsite is reported in this paper. Theoretical predication values of ANC are compared with the experimental data obtained from different literatures. The effect of aluminum (Al) on the value of ANC is investigated. It indicates that Al plays an important role in regulating the buffering effects in acidic natural waters. Failure to consider Al in acidic waters may bias assessment results in certain situations so as to overestimate the ANC values in response to increase in atmospheric deposition.

  14. Priming Silicic Giant Magma Bodies: Finding Evidence for Internal Forcing Versus External Triggering of Supereruptions by Phase Equilibria Modeling.

    NASA Astrophysics Data System (ADS)

    Tramontano, S.; Gualda, G. A. R.; Ghiorso, M. S.; Kennedy, B.

    2015-12-01

    It is important to understand what triggers silicic eruptions because of the implications for modern-day systems. The goal of this project is to use phase equilibria modeling (i.e. rhyolite-MELTS) to determine to what extent magmas within the crust are induced to erupt due to external triggers (e.g. earthquakes; new magma injection; neighboring eruptions) and to what extent they naturally evolve to a point where eruption is inevitable (e.g. by fluid exsolution and decrease in magma strength and density). Whole-rock compositions from four rhyolite tuffs across the globe associated with large or supereruptions (Mamaku Tuff, New Zealand; Peach Spring Tuff, SW USA; early and late-erupted Bishop Tuff, California; and Toba Tuff, Indonesia) are studied using rhyolite-MELTS modeling. Key physical properties of magma are strongly affected by the initial volatile content due to fluid exsolution. By running simulations with varying water contents, we can track the evolution of fluid exsolution during crystallization. Isobaric (constrained temperature change at constant pressure) and isochoric (constrained temperature change at constant volume) models were run for the four compositions. In constrained-pressure scenarios, fluid is free to exsolve as crystallization proceeds, and the total system volume can increase or decrease accordingly; this would require deformation of the surrounding crust to accommodate the magma volume change. In constrained-volume scenarios, bubble exsolution is limited to the volume change due to crystallization; in this case, pressure can decrease or increase (if bubbles are absent or present). For fixed-pressure scenarios, fluid exsolution is more extensive and leads to internal triggering, at least for fluid-saturated conditions; external triggering is more likely in fluid-undersaturated conditions. For fixed-volume scenarios, none of the systems cross a fragmentation threshold for the crystal contents typically observed in natural pumice. If

  15. 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

  16. Experimental determination and prediction of (solid+liquid) phase equilibria for binary mixtures of heavy alkanes and fatty acids

    NASA Astrophysics Data System (ADS)

    Benziane, Mokhtar; Khimeche, Kamel; Dahmani, Abdellah; Nezar, Sawsen; Trache, Djalal

    2012-06-01

    Solid-liquid equilibria for three binary mixtures, n-Eicosane (1) + Lauric acid (2), n-Tetracosane (1) + Stearic acid (2), and n-Octacosane (1) + Palmitic acid (2), were measured using a differential scanning calorimeter. Simple eutectic behaviour was observed for these systems. The experimental results were correlated by means of the modified UNIFAC (Larsen and Gmehling versions), UNIQUAC and ideal models. The root-mean-square deviations of the solubility temperatures for all measured data vary from 0.26 to 3.15 K and depend on the particular model used. The best solubility correlation was obtained with the UNIQUAC model.

  17. An analytical equation of state for describing isotropic-nematic phase equilibria of Lennard-Jones chain fluids with variable degree of molecular flexibility

    NASA Astrophysics Data System (ADS)

    van Westen, Thijs; Oyarzún, Bernardo; Vlugt, Thijs J. H.; Gross, Joachim

    2015-06-01

    We develop an equation of state (EoS) for describing isotropic-nematic (IN) phase equilibria of Lennard-Jones (LJ) chain fluids. The EoS is developed by applying a second order Barker-Henderson perturbation theory to a reference fluid of hard chain molecules. The chain molecules consist of tangentially bonded spherical segments and are allowed to be fully flexible, partially flexible (rod-coil), or rigid linear. The hard-chain reference contribution to the EoS is obtained from a Vega-Lago rescaled Onsager theory. For the description of the (attractive) dispersion interactions between molecules, we adopt a segment-segment approach. We show that the perturbation contribution for describing these interactions can be divided into an "isotropic" part, which depends only implicitly on orientational ordering of molecules (through density), and an "anisotropic" part, for which an explicit dependence on orientational ordering is included (through an expansion in the nematic order parameter). The perturbation theory is used to study the effect of chain length, molecular flexibility, and attractive interactions on IN phase equilibria of pure LJ chain fluids. Theoretical results for the IN phase equilibrium of rigid linear LJ 10-mers are compared to results obtained from Monte Carlo simulations in the isobaric-isothermal (NPT) ensemble, and an expanded formulation of the Gibbs-ensemble. Our results show that the anisotropic contribution to the dispersion attractions is irrelevant for LJ chain fluids. Using the isotropic (density-dependent) contribution only (i.e., using a zeroth order expansion of the attractive Helmholtz energy contribution in the nematic order parameter), excellent agreement between theory and simulations is observed. These results suggest that an EoS contribution for describing the attractive part of the dispersion interactions in real LCs can be obtained from conventional theoretical approaches designed for isotropic fluids, such as a Perturbed

  18. Phase modifications in polysilicon films with fibrous and dendritic structure

    NASA Astrophysics Data System (ADS)

    Nakhodkin, N. G.; Kulish, N. P.; Rodionova, T. V.; Strutinsky, A. M.

    2000-01-01

    X-ray and electron diffraction have been used to study structure modifications in polysilicon films produced by low-pressure chemical vapour deposition. It was shown that additional diffraction reflections are observed in polysilicon films with fibrous and dendritic structure. These additional reflections may be considered as relative to close-packed hexagonal structure with the following lattice parameters: a=3.808 Å, b=6.186 Å. The orientation relationship between the cubic diamond and hexagonal phases is [1 1 1] cub‖[0 0 1] and ( 1¯ 1 0) ∗cub‖(1 0 0) ∗. The suggested hexagonal structure formation mechanism is based upon the existence of planar faults in {1 1 1} planes.

  19. Optimized Mie potentials for phase equilibria: Application to noble gases and their mixtures with n-alkanes

    NASA Astrophysics Data System (ADS)

    Mick, Jason R.; Soroush Barhaghi, Mohammad; Jackman, Brock; Rushaidat, Kamel; Schwiebert, Loren; Potoff, Jeffrey J.

    2015-09-01

    Transferrable force fields, based on n-6 Mie potentials, are presented for noble gases. By tuning the repulsive exponent, ni, it is possible to simultaneously reproduce experimental saturated liquid densities and vapor pressures with high accuracy, from the normal boiling point to the critical point. Vapor-liquid coexistence curves for pure fluids are calculated using histogram reweighting Monte Carlo simulations in the grand canonical ensemble. For all noble gases, saturated liquid densities and vapor pressures are reproduced to within 1% and 4% of experiment, respectively. Radial distribution functions, extracted from NVT and NPT Monte Carlo simulations, are in similarly excellent agreement with experimental data. The transferability of the optimized force fields is assessed through calculations of binary mixture vapor-liquid equilibria. These mixtures include argon + krypton, krypton + xenon, methane + krypton, methane + xenon, krypton + ethane, and xenon + ethane. For all mixtures, excellent agreement with experiment is achieved without the introduction of any binary interaction parameters or multi-body interactions.

  20. Optimized Mie potentials for phase equilibria: Application to noble gases and their mixtures with n-alkanes.

    PubMed

    Mick, Jason R; Soroush Barhaghi, Mohammad; Jackman, Brock; Rushaidat, Kamel; Schwiebert, Loren; Potoff, Jeffrey J

    2015-09-21

    Transferrable force fields, based on n-6 Mie potentials, are presented for noble gases. By tuning the repulsive exponent, ni, it is possible to simultaneously reproduce experimental saturated liquid densities and vapor pressures with high accuracy, from the normal boiling point to the critical point. Vapor-liquid coexistence curves for pure fluids are calculated using histogram reweighting Monte Carlo simulations in the grand canonical ensemble. For all noble gases, saturated liquid densities and vapor pressures are reproduced to within 1% and 4% of experiment, respectively. Radial distribution functions, extracted from NVT and NPT Monte Carlo simulations, are in similarly excellent agreement with experimental data. The transferability of the optimized force fields is assessed through calculations of binary mixture vapor-liquid equilibria. These mixtures include argon + krypton, krypton + xenon, methane + krypton, methane + xenon, krypton + ethane, and xenon + ethane. For all mixtures, excellent agreement with experiment is achieved without the introduction of any binary interaction parameters or multi-body interactions. PMID:26395716

  1. Optimized Mie potentials for phase equilibria: Application to noble gases and their mixtures with n-alkanes.

    PubMed

    Mick, Jason R; Soroush Barhaghi, Mohammad; Jackman, Brock; Rushaidat, Kamel; Schwiebert, Loren; Potoff, Jeffrey J

    2015-09-21

    Transferrable force fields, based on n-6 Mie potentials, are presented for noble gases. By tuning the repulsive exponent, ni, it is possible to simultaneously reproduce experimental saturated liquid densities and vapor pressures with high accuracy, from the normal boiling point to the critical point. Vapor-liquid coexistence curves for pure fluids are calculated using histogram reweighting Monte Carlo simulations in the grand canonical ensemble. For all noble gases, saturated liquid densities and vapor pressures are reproduced to within 1% and 4% of experiment, respectively. Radial distribution functions, extracted from NVT and NPT Monte Carlo simulations, are in similarly excellent agreement with experimental data. The transferability of the optimized force fields is assessed through calculations of binary mixture vapor-liquid equilibria. These mixtures include argon + krypton, krypton + xenon, methane + krypton, methane + xenon, krypton + ethane, and xenon + ethane. For all mixtures, excellent agreement with experiment is achieved without the introduction of any binary interaction parameters or multi-body interactions.

  2. Chemical synthesis and modification of target phases of chalcogenide nanomaterials

    NASA Astrophysics Data System (ADS)

    Sines, Ian T.

    Inorganic nanoparticles have been at the forefront of materials research in recent years due to their utility in modern technological processes. Chalcogenide nanomaterials are of particular interest because of their wide range of desirable properties for semiconductors, magnetic devices, and energy industries. Primary factors that dictate the properties of the material are the elemental composition, crystal structure, stoichiometry, crystallite size, and particle morphology. One of the most common approaches to synthesize these materials is through solution mediated routes. This approach offers unique advantages in controlling the morphology and particle size that other methods lack. This dissertation describes our recent work on exploiting solution chemical routes to control the crystal structure and composition of chalcogenide nanomaterials. We will start by discussing solution chemistry routes to synthesize non-equilibrium phases of chaclogenide nanomaterials. By using low-temperature bottom-up techniques it is possible to trap kinetically stable phases that cannot be accessed using traditional high-temperature techniques. We used solution chemistry to synthesize and characterize, for the first time, wurtzite-type MnSe. Wurtzite-type MnSe is the end-member of the highly investigated ZnxMn1-xSe solid solution, a classic magnetic semiconductor system. We will then discuss PbO-type FeS, another non-equilibrium phase that is isostructural with the superconducting phase of FeSe. We synthesized phase-pure PbO-type FeS using a low-temperature solvothermal route. We will then discuss the post-synthetic modification of chalcogenides nanomaterials. By exploiting the solubility of Se and S in tri-n-octylphosphine we can selectively extract the chalcogen from preformed chalcogenide nanomaterials. This gives chemists a technique for purification and phase-targeting of particular chalcogenide phases. This method can be modified to facilitate anion exchange. When Te is

  3. Tales from supereruptions: Combining pumice and mineral textures with phase equilibria to constrain the evolution of giant silicic magma bodies in the crust

    NASA Astrophysics Data System (ADS)

    Gualda, G. A. R.; Pamukcu, A. S.; Wright, K. A.; Ghiorso, M. S.; Miller, C. F.

    2014-12-01

    Supereruption deposits demonstrate that giant magma bodies sporadically exist within the Earth's crust. We rely on study of such deposits to better understand the underlying magma bodies and their eruptions. We are studying several deposits: Bishop Tuff (BT, CA USA), Peach Spring Tuff (PST, SW USA), and Oruanui Tuff (OT, NZ). We combine quantitative textural characterization in 3D via x-ray tomography (XRT), focusing particularly on CSDs of major and accessory minerals; characterization of mineral zoning, particularly of Ti and CL in quartz, including inferences from diffusion chronometry; documentation of glass inclusion textures in 3D via XRT, with implications to crystallization timescales; and phase equilibria modeling (rhyolite-MELTS), including glass (inclusion and matrix) composition geobarometry, to constrain crystallization conditions. CSDs ubiquitously record a growth-dominated regime, characterized by limited nucleation, consistent with pre-eruptive crystallization under low supersaturation. Phenocryst interiors are largely unzoned, consistent with phase equilibria predictions of nearly invariant, effectively isothermal crystallization. Glass compositions record storage over a large spread of depths (~125-250 MPa) for early and late-erupted BT, while the OT represents multiple magma batches evacuated from different depths. Diffusion chronometry and melt inclusion faceting suggest pre-eruptive crystallization over centennial timescales. CSDs and mineral textures also record syn-eruptive crystallization, which results in huge numbers of small crystals, revealing extensive nucleation prior to eruption. Crystal rims develop on pre-existing phenocrysts, and they can be obvious if compositionally distinct from interiors (BT and PST). In PST, evidence for rim crystallization from hotter magma is very strong. BT contrasts with PST in many ways; evidence for heating is ambiguous, and pumice properties are difficult to reconcile with magma mixing, while the

  4. Turbulent transition modification in dispersed two-phase pipe flow

    NASA Astrophysics Data System (ADS)

    Winters, Kyle; Longmire, Ellen

    2014-11-01

    In a pipe flow, transition to turbulence occurs at some critical Reynolds number, Rec , and transition is associated with intermittent swirling structures extending over the pipe cross section. Depending on the magnitude of Rec , these structures are known either as puffs or slugs. When a dispersed second liquid phase is added to a liquid pipe flow, Rec can be modified. To explore the mechanism for this modification, an experiment was designed to track and measure these transitional structures. The facility is a pump-driven circuit with a 9m development and test section of diameter 44mm. Static mixers are placed upstream to generate an even dispersion of silicone oil in a water-glycerine flow. Pressure signals were used to identify transitional structures and trigger a high repetition rate stereo-PIV system downstream. Stereo-PIV measurements were obtained in planes normal to the flow, and Taylor's Hypothesis was employed to infer details of the volumetric flow structure. The presentation will describe the sensing and imaging methods along with preliminary results for the single and two-phase flows. Supported by Nanodispersions Technology.

  5. Alkali exchange equilibria between a silicate melt and coexisting magmatic volatile phase: an experimental study at 800°C and 100 MPa

    NASA Astrophysics Data System (ADS)

    Frank, Mark R.; Candela, Philip A.; Piccoli, Philip M.

    2003-04-01

    complex. fH 2Osys and the ASI are the main controls on model NaOH m/ΣNa m in the system, with model NaOH m/ΣNa m increasing with increasing fH 2Osys. This relationship can be used to estimate the C HClb in subaluminous systems, an improvement over previous models. Data for metal partitioning between a volatile phase and melt are commonly presented in the literature as metal-sodium exchange equilibria (i.e., K Cu,Na for the exchange of copper and sodium). However, the variation in K' meas (K, Na) observed in this study implies that the treatment of metal partitioning between a volatile phase and melt as metal-alkali exchange equilibria is complex because alkali partitioning is not constant and suggests that experimental partitioning studies need to carefully control the HCl/NaCl in experimental vapors and brines. This effect may explain discrepancies in metal-alkali exchange equilibria presented in the literature. Therefore, metal-alkali exchange cannot be described fully by a single metal-alkali equilibrium but must be examined by multiple equilibria.

  6. On the topological stability of magnetostatic equilibria

    NASA Technical Reports Server (NTRS)

    Tsinganos, K. C.; Rosner, R.; Distler, J.

    1984-01-01

    The topological stability of MHD equilibria is investigated by exploring the formal analogy, in the ideal MHD limit, between the topology of magnetic lines of force in coordinate space and the topology of integral surfaces of one- and two-dimensional Hamiltonian systems in phase space. It is demonstrated that in an astrophysical setting, symmetric magnetostatic equilibria satisfying the ideal MHD equations are exceptional. The principal result of the study is that previous infinitesimal perturbation theory calculations can be generalized to include finite-amplitude and symmetry-breaking effects. The effect of the ergodicity of perturbed symmetric equilibria on heat dispersal in magnetically dominated plasmas is discussed.

  7. Investigation of the Phase Equilibria of Sn-Cu-Au Ternary and Ag-Sn-Cu-Au Quaternary Systems and Interfacial Reactions in Sn-Cu/Au Couples

    NASA Astrophysics Data System (ADS)

    Yen, Yee-Wen; Jao, Chien-Chung; Hsiao, Hsien-Ming; Lin, Chung-Yung; Lee, Chiapyng

    2007-02-01

    The phase equilibria of the Sn-Cu-Au ternary, Ag-Sn-Cu-Au quaternary systems and interfacial reactions between Sn-Cu alloys and Au were experimentally investigated at specific temperatures in this study. The experimental results indicated that there existed three ternary intermetallic compounds (IMCs) and a complete solid solubility between AuSn and Cu6Sn5 phases in the Sn-Cu-Au ternary system at 200°C. No quaternary IMC was found in the isoplethal section of the Ag-Sn-Cu-Au quaternary system. Three IMCs, AuSn, AuSn2, and AuSn4, were found in all couples. The same three IMCs and (Au,Cu)Sn/(Cu,Au)6Sn5 phases were found in all Sn-Cu/Au couples. The thickness of these reaction layers increased with increasing temperature and time. The mechanism of IMC growth can be described by using the parabolic law. In addition, when the reaction time was extended and the Cu content of the alloy was increased, the AuSn4 phase disappeared gradually. The (Au, Cu)Sn and (Cu,Au)6Sn5 layers played roles as diffusion barriers against Sn in Sn-Cu/Au reaction couple systems.

  8. Micelle-monomer equilibria in solutions of ionic surfactants and in ionic-nonionic mixtures: a generalized phase separation model.

    PubMed

    Danov, Krassimir D; Kralchevsky, Peter A; Ananthapadmanabhan, Kavssery P

    2014-04-01

    On the basis of a detailed physicochemical model, a complete system of equations is formulated that describes the equilibrium between micelles and monomers in solutions of ionic surfactants and their mixtures with nonionic surfactants. The equations of the system express mass balances, chemical and mechanical equilibria. Each nonionic surfactant is characterized by a single thermodynamic parameter--its micellization constant. Each ionic surfactant is characterized by three parameters, including the Stern constant that quantifies the counterion binding. In the case of mixed micelles, each pair of surfactants is characterized with an interaction parameter, β, in terms of the regular solution theory. The comparison of the model with experimental data for surfactant binary mixtures shows that β is constant--independent of the micelle composition and electrolyte concentration. The solution of the system of equations gives the concentrations of all monomeric species, the micelle composition, ionization degree, surface potential and mean area per head group. Upon additional assumptions for the micelle shape, the mean aggregation number can be also estimated. The model gives quantitative theoretical interpretation of the dependence of the critical micellization concentration (CMC) of ionic surfactants on the ionic strength; of the CMC of mixed surfactant solutions, and of the electrolytic conductivity of micellar solutions. It turns out, that in the absence of added salt the conductivity is completely dominated by the contribution of the small ions: monomers and counterions. The theoretical predictions are in good agreement with experimental data.

  9. The heat capacity of a natural monticellite and phase equilibria in the system CaO-MgO-SiO2-CO2

    USGS Publications Warehouse

    Sharp, Z.D.; Essene, E.J.; Anovitz, Lawrence M.; Metz, G.W.; Westrum, E.F.; Hemingway, B.S.; Valley, J.W.

    1986-01-01

    The heat capacity of a natural monticellite (Ca1.00Mg.09Fe.91Mn.01Si0.99O3.99) measured between 9.6 and 343 K using intermittent-heating, adiabatic calorimetry yields Cp0(298) and S2980 of 123.64 ?? 0.18 and 109.44 ?? 0.16 J ?? mol-1 K-1 respectively. Extrapolation of this entropy value to end-member monticellite results in an S0298 = 108.1 ?? 0.2 J ?? mol-1 K-1. High-temperature heat-capacity data were measured between 340-1000 K with a differential scanning calorimeter. The high-temperature data were combined with the 290-350 K adiabatic values, extrapolated to 1700 K, and integrated to yield the following entropy equation for end-member monticellite (298-1700 K): ST0(J ?? mol-1 K-1) = S2980 + 164.79 In T + 15.337 ?? 10-3 T + 22.791 ?? 105 T-2 - 968.94. Phase equilibria in the CaO-MgO-SiO2 system were calculated from 973 to 1673 K and 0 to 12 kbar with these new data combined with existing data for akermanite (Ak), diopside (Di), forsterite (Fo), merwinite (Me) and wollastonite (Wo). The location of the calculated reactions involving the phases Mo and Fo is affected by their mutual solid solution. A best fit of the thermodynamically generated curves to all experiments is made when the S0298 of Me is 250.2 J ?? mol-1 K-1 less than the measured value of 253.2 J ?? mol-1 K-1. A best fit to the reversals for the solid-solid and decarbonation reactions in the CaO-MgO-SiO2-CO2 system was obtained with the ??G0298 (kJ ?? mole-1) for the phases Ak(-3667), Di(-3025), Fo(-2051), Me(-4317) and Mo(-2133). The two invariant points - Wo and -Fo for the solid-solid reactions are located at 1008 ?? 5 K and 6.3 ?? 0.1 kbar, and 1361 ?? 10 K and 10.2 ?? 0.2 kbar respectively. The location of the thermodynamically generated curves is in excellent agreement with most experimental data on decarbonation equilibria involving these phases. ?? 1986.

  10. Extension of Toth function from gas-solid to liquid-solid equilibria and application to reversed-phase liquid chromatography systems

    SciTech Connect

    Gritti, Fabrice; Guiochon, Georges A

    2006-03-01

    The extension of the {Psi} function developed by Toth from equilibria taking place at gas-solid interfaces to those taking place at liquid-solid interfaces was investigated. The results were applied to conventional liquid-solid systems used in reversed-phase liquid chromatography (RPLC). The adsorbents in these systems are made of porous silica having a hydrophobic solid surface obtained by chemically bonding C{sub 18} alkyl chains to a porous silica gel then endcapping the surface with trimethylsilyl groups. The liquid is an aqueous solution of an organic solvent, most often methanol or acetonitrile. The probe compound used here is phenol. Adsorption data of phenol were measured using the dynamic frontal analysis (FA) method. The excess adsorption of the organic solvent was measured using the minor disturbance (MD) method. Activity coefficients in the bulk were estimated through the UNIFAC group contributions. The results show that the {Psi} function predicts 90% of the total free energy of immersion, {Delta}F, of the solid when the concentration of phenol is moderate (typically less than 10 g/L). At higher concentrations, the nonideal behavior of the bulk liquid phase becomes significant and it may contribute up to about 30% of {Delta}F. The high concentration of adsorbed molecules of phenol at the interface decreases the interfacial tension, {sigma}, by about 18 mN/m, independently of the structure of the adsorbed phase and of the nature of the organic solvent.

  11. Thermodynamic analysis of the cubic-tetragonal phase equilibria in the system ZrO{sub 2}-YO{sub 1.5}

    SciTech Connect

    Katamura, Junji; Sakuma, Taketo

    1997-10-01

    The cubic-tetragonal (c-t) phase equilibria in the system ZrO{sub 2}-YO{sub 1.5} are thermodynamically analyzed from Landau`s phenomenological theory. The calculated c-t two-phase field is depicted as a miscibility gap with a sharp maximum and the spinodal region as originally predicted by Hillert and Sakuma. However, the observed c-t two-phase field and the spinodal region are better described by the present model. In addition, this model can be used to discuss the nature of the c-t diffusionless transformation from the order parameter in contrast with the original model. The predicted change in the tetragonality of t-ZrO{sub 2} with YO{sub 1.5} content is slightly different from that in the cla axial ratio estimated from X-ray diffraction analysis. The displacement of cations and anions may not take place simultaneously during the c-t transformation.

  12. Phase Equilibria of the Ternary Sn-Pb-Co System at 250°C and Interfacial Reactions of Co with Sn-Pb Alloys

    NASA Astrophysics Data System (ADS)

    Wang, Chao-hong; Kuo, Chun-yi; Yang, Nian-cih

    2015-11-01

    The isothermal section of the ternary Sn-Pb-Co system at 250°C was experimentally determined through a series of the equilibrated Sn-Pb-Co alloys of various compositions. The equilibrium phases were identified on the basis of compositional analysis. For the Sn-Co intermetallic compounds (IMCs), CoSn3, CoSn2, CoSn and Co3Sn2, the Pb solubility was very limited. There exist five tie-triangle regions. The Co-Pb system involves one monotectic reaction, so the phase separation of liquid alloys near the Co-Pb side occurred prior to solidification. The immiscibility field was also determined. Additionally, interfacial reactions between Co and Sn-Pb alloys were conducted. The reaction phase for the Sn-48 at.%Pb and Sn-58 at.%Pb at 250°C was CoSn3 and CoSn2, respectively. Both of them were simultaneously formed in the Sn-53 at.%Pb/Co. The formed IMCs were closely associated to the phase equilibria relationship of the liquid-CoSn3-CoSn2 tie-triangle. Furthermore, with increasing temperatures, the phase formed in equilibrium with Sn-37 wt.%Pb was found to transit from CoSn3 to CoSn2 at 275°C. We propose a simple method of examining the phase transition temperature in the interfacial reactions to determine the boundaries of the liquid-CoSn3-CoSn2 tie-triangles at different temperatures.

  13. Computational Thermodynamic Study to Predict Complex Phase Equilibria in the Nickel-Base Superalloy Rene N6

    NASA Technical Reports Server (NTRS)

    Copland, Evan H.; Jacobson, Nathan S.; Ritzert, Frank J.

    2001-01-01

    A previous study by Ritzert et al. on the formation and prediction of topologically closed packed (TCP) phases in the nickel-base superalloy Rene' N6 is re-examined with computational thermodynamics. The experimental data on phase distribution in forty-four alloys with a composition within the patent limits of the nickel-base superalloy Rene' N6 provide a good basis for comparison to and validation of a commercial nickel superalloy database used with ThermoCalc. Volume fraction of the phases and partitioning of the elements are determined for the forty-four alloys in this dataset. The baseline heat treatment of 400 h at 1366 K was used. This composition set is particularly interesting since small composition differences lead to dramatic changes in phase composition. In general the calculated values follow the experimental trends. However, the calculations indicated no TCP phase formation when the experimental measurements gave a volume percent of TCP phase less than 2 percent. When TCP phases were predicted, the calculations under-predict the volume percent of TCP phases by a factor of 2 to 8. The calculated compositions of the gamma and gamma' phases show fair agreement with the measurements. However, the calculated compositions of the P Phase do not agree with those measured. This may be due to inaccuracies in the model parameters for P phase and/or issues with the microprobe analyses of these phases. In addition, phase fraction diagrams and sigma and P phase solvus temperatures are calculated for each of the alloys. These calculations indicate that P phase is the primary TCP phase formed for the alloys considered here at 1366 K. Finally, a series of isopleths are calculated for each of the seven alloying elements. These show the effect of each alloying element on creating TCP phases.

  14. Petrology, phase equilibria and monazite geochronology of granulite-facies metapelites from deep drill cores in the Ordos Block of the North China Craton

    NASA Astrophysics Data System (ADS)

    He, Xiao-Fang; Santosh, M.; Bockmann, Kiara; Kelsey, David E.; Hand, Martin; Hu, Jianmin; Wan, Yusheng

    2016-10-01

    Among the various Precambrian crustal blocks in the North China Craton (NCC), the geology and evolution of the Ordos Block remain largely enigmatic due to paucity of outcrop. Here we investigate granulite-facies metapelites obtained from deep-penetrating drill holes in the Ordos Block and report petrology, calculated phase equilibria and in-situ monazite LA-ICP-MS geochronology. The rocks we studied are two samples of cordierite-bearing garnet-sillimanite-biotite metapelitic gneisses and one graphite-bearing, two-mica granitic gneiss. The peak metamorphic age from LA-ICP-MS dating of monazite in all three samples is in the range of 1930-1940 Ma. The (U + Pb)-Th chemical ages through EPMA dating reveals that monazite occurring as inclusions in garnet are older than those in the matrix. Calculated metamorphic phase diagrams for the cordierite-bearing metapelite suggest peak P-T conditions ca. 7-9 kbar and 775-825 °C, followed by decompression and evolution along a clockwise P-T path. Our petrologic and age data are consistent with those reported from the Khondalite Belt in the Inner Mongolia Suture Zone in the northern part of the Ordos Block, suggesting that these granulite-facies metasediments represent the largest Paleoproterozoic accretionary belt in the NCC.

  15. Using nanogranitoids and phase equilibria modeling to unravel anatexis in the crustal footwall of the Ronda peridotites (Betic Cordillera, S Spain)

    NASA Astrophysics Data System (ADS)

    Bartoli, Omar; Acosta-Vigil, Antonio; Tajčmanová, Lucie; Cesare, Bernardo; Bodnar, Robert J.

    2016-07-01

    Anatexis in the crustal footwall of Ronda peridotites (Betic Cordillera, S Spain) is apparently related to the hot emplacement of this mantle slab over metasedimentary rocks. In this study, we combine the analysis of melt inclusions (MI) and phase equilibria calculations on quartzo-feldspathic mylonites (former migmatites) occurring at the contact with the mantle rocks, in the region of Sierra Alpujata (Ojén unit). The goal is to better characterize anatexis in these rocks and to provide new constraints on the geodynamic evolution of the crustal footwall. Such data are important for understanding the mechanisms of crustal emplacement of the mantle slice. The quartzo-feldspathic mylonites are characterized by the mineral assemblage Qtz + Pl + Kfs + Sil + Grt + Ilm + Bt ± Ap ± Gr. Clusters of MI are observed both at the core and toward the rim of peritectic garnet. In each cluster, MI range from totally glassy to nanogranitoids, consisting of Qtz + Kfs + Bt + Ms + Pl aggregates. The trapped melt is leucogranitic and peraluminous with variable Na2O/K2O values and low H2O contents (≈ 2-4 wt%). Phase equilibria modeling in the MnO-Na2O-CaO-K2O-FeO-MgO-Al2O3-SiO2-H2-TiO2-O2-C (MnNCaKFMASHTOC) system with graphite-saturated fluid constrains the P-T conditions of melting at ≈ 6 kbar, ≈ 820 °C. MI data support the fluid-absent character of melting. The investigated MI represent the primary anatectic melts produced during prograde anatexis of the host rocks via biotite dehydration melting. Field, compositional, and textural observations indicate that mylonitic migmatites represent strongly deformed former diatexites. The comparison between the new data and some recently published information on migmatites located further from the contact with the peridotites and toward the bottom of the crustal footwall, raises some important issues which question the previously proposed geodynamic models for this region. Among them, (i) the crustal footwall at Sierra Alpujata

  16. Three-phase liquid-liquid-vapor equilibria behavior of certain binary CO/sub 2/-n-paraffin systems

    SciTech Connect

    Hottovy, J.D.; Kohn, J.P.; Luks, K.D.

    1981-07-01

    The 3-phase liquid-liquid-vapor loci of 4 binary CO/sub 2/-n-paraffin systems (n-dodecane, n-tridecane, n-tetradecane, n-pentadecane) are studied, and temperature, pressure, and molar volumes and composition of both liquid phases are reported. It is within this group of n-paraffins that the nature of the upper critical end point for the CO/sub 2/-containing binary systems changes with increasing carbon number from an upper critical solution (temperature) point where L/sub 1/ and L/sub 2/ phases become critical in presence of vapor phase to a K point, where L/sub 2/ and vapor phases become critical in the presence of L/sub 1/ phase. These 4 loci are compared with earlier obtained loci on CO/sub 2/-n-decane and CO/sub 2/-n-elcosane.

  17. Extrathermodynamic interpretation of retention equilibria in reversed-phase liquid chromatography using octadecylsilyl-silica gels bonded to C1 and C18 ligands of different densities.

    PubMed

    Miyabe, Kanji; Guiochon, Georges

    2005-12-16

    The retention behavior on silica gels bonded to C18 and C1 alkyl ligands of different densities was studied in reversed-phase liquid chromatography (RPLC) from the viewpoints of two extrathermodynamic relationships, enthalpy-entropy compensation (EEC) and linear free energy relationship (LFER). First, the four tests proposed by Krug et al. were applied to the values of the retention equilibrium constants (K) normalized by the alkyl ligand density. These tests showed that a real EEC of the retention equilibrium originates from substantial physico-chemical effects. Second, we derived a new model based on the EEC to explain the LFER between the retention equilibria under different RPLC conditions. The new model indicates how the slope and intercept of the LFER are correlated to the compensation temperatures derived from the EEC analyses and to several parameters characterizing the molecular contributions to the changes in enthalpy and entropy. Finally, we calculated K under various RPLC conditions from only one original experimental K datum by assuming that the contributions of the C18 and C1 ligands to K are additive and that their contributions are proportional to the density of each ligand. The estimated K values are in agreement with the corresponding experimental data, demonstrating that our model is useful to explain the variations of K due to changes in the RPLC conditions.

  18. Phase equilibria in the system H{sub 2}O-NaCl-KCl-MgCl{sub 2} relevant to salt cake processing

    SciTech Connect

    Bodnar, R.J.; Vityk, M.O.; Hryn, J.N.; Mavrogenes, J.

    1997-02-01

    One waste product in recycling of Al is salt cake, a mixture of Al, salts, and residue oxides. Several methods have been proposed to recycle salt cake, one involving high-temperature leaching of salts from the salt cake. The salt composition can be approximated as a mixture predominantly of NaCl and KCl salts, with lesser amounts of Mg chloride. In order to better assess the feasibility of recycling salt cake, an experimental study was conducted of phase equilibria in the system H{sub 2}O-NaCl-KCl-MgCl{sub 2} at pressure (P), temperature (T), and composition conditions appropriate for high- temperature salt cake recycling. These experiments were designed to evaluate the effect of small amounts (2-10 wt%) of MgCl{sub 2} on solubilities of halite (NaCl) and sylvite (KCl) in saturated solutions (30-50 wt% NaCl+KCl; NaCl:KCl = 1:1 and 3:1) at elevated P and T.

  19. Comparison of polyethylene glycol and polyoxyethylene stearate as excipients for solid dispersion systems of griseofulvin and tolbutamide I: phase equilibria.

    PubMed

    Kaur, R; Grant, D J; Eaves, T

    1980-11-01

    Phase equilibrium diagrams were constructed based on hot-stage microscopy and differential scanning calorimetry of solid dispersions of griseofulvin or tolbutamide in polyethylene glycol 2000 or polyoxyethylene 40 stearate. The solid dispersions were prepared by physical mixing, fusion, and coprecipitation from ethanol. The phase diagrams were largely independent of the method of preparation of the dispersion systems. The diagrams were of the monotectic type for polyethylene glycol 2000 with each drug and for griseofulvin with each excipient, with the monotectic species being the pure drug. Polyoxyethylene 40 stearate with tolbutamide gave eutectic systems in which liquid polyoxyethylene 40 stearate dissolved up to 20% of the tolbutamide. The phase diagrams showed greater solubility of tolbutamide in liquid polyoxyethylene 40 stearate than in polyethylene glycol 2000 but showed a similar solubility of griseofulvin in each experiment. Solid solution formation was not detected. PMID:7452463

  20. Chemical potentials and phase equilibria of Lennard-Jones mixtures: a self-consistent integral equation approach.

    PubMed

    Wilson, D Scott; Lee, Lloyd L

    2005-07-22

    We explore the vapor-liquid phase behavior of binary mixtures of Lennard-Jones-type molecules where one component is supercritical, given the system temperature. We apply the self-consistency approach to the Ornstein-Zernike integral equations to obtain the correlation functions. The consistency checks include not only thermodynamic consistencies (pressure consistency and Gibbs-Duhem consistency), but also pointwise consistencies, such as the zero-separation theorems on the cavity functions. The consistencies are enforced via the bridge functions in the closure which contain adjustable parameters. The full solution requires the values of not only the monomer chemical potentials, but also the dimer chemical potentials present in the zero-separation theorems. These are evaluated by the direct chemical-potential formula [L. L. Lee, J. Chem. Phys. 97, 8606 (1992)] that does not require temperature nor density integration. In order to assess the integral equation accuracy, molecular-dynamics simulations are carried out alongside the states studied. The integral equation results compare well with simulation data. In phase calculations, it is important to have pressure consistency and valid chemical potentials, since the matching of phase boundaries requires the equality of the pressures and chemical potentials of both the liquid and vapor phases. The mixtures studied are methane-type and pentane-type molecules, both characterized by effective Lennard-Jones potentials. Calculations on one isotherm show that the integral equation approach yields valid answers as compared with the experimental data of Sage and Lacey. To study vapor-liquid phase behavior, it is necessary to use consistent theories; any inconsistencies, especially in pressure, will vitiate the phase boundary calculations.

  1. Phase equilibria and distribution constants of metal ions in diantipyryl alkane-organic acid-hydrochloric acid-water systems

    NASA Astrophysics Data System (ADS)

    Degtev, M. I.; Popova, O. N.; Yuminova, A. A.

    2014-08-01

    The ability of antipyrine and its derivatives (diantipyryl alkanes) to form separating systems in the presence of salicylic (sulfosalicylic) acid and hydrochloric acid and water is studied. The optimum volume of the organic phase, the composition of complexes, and the mechanism for the distribution of metal ions are determined, depending on the concentrations of the main components and the salting-out agent. The complex distribution and extraction constants are calculated.

  2. Phase equilibria and elements partitioning in zirconolite-rich region of Ca-Zr-Ti-Al-Gd-Si-O system

    SciTech Connect

    Knyazev, O.A.; Stefanovsky, S.V.; Ioudintsev, S.V.; Nikonov, B.S.; Omelianenko, B.I.; Mokhov, A.V.; Yakushev, A.I.

    1997-12-31

    Zirconolite-rich ceramics were produced by the cold crucible melting technique in an air atmosphere, at 1550 {+-} 50 C and 1 atm. Four samples with overall composition (in wt.%): 4.9-14.3 CaO; 19.0-41.3 ZrO{sub 2}; 24.1-42.6 TiO{sub 2}; 1.3-11.3 Al{sub 2}O{sub 3}; 6.8-30.0 Gd{sub 2}O{sub 3}; and 1.1-8.5 SiO{sub 2} have been studied. Total phases in the ceramics consist of major zirconolite and minor rutile, perovskite, zirconia, aluminium titanate, and glass. The Gd{sub 2}O{sub 3} content in zirconolite reaches up to 31.4 wt.% corresponding to the formula: (Ca{sub 0.4},Gd{sub 0.7})Zr{sub 1.0}(Ti{sub 1.4},Al{sub 0.5})O{sub 7.0}. The data on the phase composition agree well with coupled Gd incorporation into the mineral structure: Ca(II) + Ti(IV) = Gd(III) + Al(III), and 2Gd(III) = Ca(II) + Zr(IV). The highest Gd contents observed in the other phases are 25.4% for zirconia, 12.6% in glass, 8.8% in perovskite, and 1.4% for rutile. The rest of the elements` distribution in the samples are analyzed.

  3. Tubing modifications for countercurrent chromatography (CCC): Stationary phase retention and separation efficiency.

    PubMed

    Englert, Michael; Vetter, Walter

    2015-07-16

    Countercurrent chromatography (CCC) is a separation technique in which two immiscible liquid phases are used for the preparative purification of synthetic and natural products. In CCC the number of repetitive mixing and de-mixing processes, the retention of the stationary phase and the mass transfer between the liquid phases are significant parameters that influence the resolution and separation efficiency. Limited mass transfer is the main reason for peak broadening and a low number of theoretical plates along with impaired peak resolution in CCC. Hence, technical improvements with regard to column design and tubing modifications is an important aspect to enhance mixing and mass transfer. In this study we constructed a crimping tool which allowed us to make reproducible, semi-automated modifications of conventional round-shaped tubing. Six crimped tubing modifications were prepared, mounted onto multilayer coils which were subsequently installed in the CCC system. The stationary phase retention of the tubing modifications were compared to the conventional system with unmodified tubing in a hydrophobic, an intermediate and a hydrophilic two-phase solvent system. Generally, the tubing modifications provided higher capabilities to retain the stationary phase depending on the solvent system and flow rates. In the intermediate solvent system the separation efficiency was evaluated with a mixture of six alkyl p-hydroxybenzoates. The peak resolution could be increased up to 50% with one of the tubing modifications compared to the unmodified tubing. Using the most convincing tubing modification at fixed values for the stationary phase retention, a reasonable comparison to the unmodified tubing was achieved. The peak width could be reduced up to 49% and a strong positive impact at increased flow rates regarding peak resolution and theoretical plate number was observed compared to unmodified tubing. It could be concluded that the tubing modification enhanced the interphase

  4. Tubing modifications for countercurrent chromatography (CCC): Stationary phase retention and separation efficiency.

    PubMed

    Englert, Michael; Vetter, Walter

    2015-07-16

    Countercurrent chromatography (CCC) is a separation technique in which two immiscible liquid phases are used for the preparative purification of synthetic and natural products. In CCC the number of repetitive mixing and de-mixing processes, the retention of the stationary phase and the mass transfer between the liquid phases are significant parameters that influence the resolution and separation efficiency. Limited mass transfer is the main reason for peak broadening and a low number of theoretical plates along with impaired peak resolution in CCC. Hence, technical improvements with regard to column design and tubing modifications is an important aspect to enhance mixing and mass transfer. In this study we constructed a crimping tool which allowed us to make reproducible, semi-automated modifications of conventional round-shaped tubing. Six crimped tubing modifications were prepared, mounted onto multilayer coils which were subsequently installed in the CCC system. The stationary phase retention of the tubing modifications were compared to the conventional system with unmodified tubing in a hydrophobic, an intermediate and a hydrophilic two-phase solvent system. Generally, the tubing modifications provided higher capabilities to retain the stationary phase depending on the solvent system and flow rates. In the intermediate solvent system the separation efficiency was evaluated with a mixture of six alkyl p-hydroxybenzoates. The peak resolution could be increased up to 50% with one of the tubing modifications compared to the unmodified tubing. Using the most convincing tubing modification at fixed values for the stationary phase retention, a reasonable comparison to the unmodified tubing was achieved. The peak width could be reduced up to 49% and a strong positive impact at increased flow rates regarding peak resolution and theoretical plate number was observed compared to unmodified tubing. It could be concluded that the tubing modification enhanced the interphase

  5. High and low pressure phase equilibria of a mildly alkalic lava from the 1965 Surtsey eruption: Experimental results

    NASA Astrophysics Data System (ADS)

    Thy, P.

    1991-01-01

    Melting experiments have been performed on a primitive, mildly alkalic glassy lava (10 wt.% MgO) from the 1965 eruption of the Surtsey volcano located at the tip of the south-eastern propagating rift zone of Iceland. At atmospheric pressure, approximately on the FMQ oxygen buffer, olivine (Fo 81) crystallizes from 1240°C, followed by plagioclase (An 70) from 1180°C and augite from 1140°C. The experimental glasses coexisting with olivine, plagioclase and augite are ferrobasaltic enriched in FeO (13.6-14.2 wt.%) and TiO 2 (4.0-4.4 wt.%). In high pressure, piston-cylinder, graphite-controlled runs, olivine occurs as the liquidus phase until 14 kbar, above which augite is the liquidus phase. Low-Ca pyroxene is not a liquidus phase at any pressure. The high pressure liquids are, relative to the one atmosphere liquids, significantly enriched in Al 2O 3 and Na 2O and depleted in CaO as a result of changes in the crystallizing assemblages. Furthermore, liquidus augite is dominantly subcalcic and shows significant enrichment in Al and depletion in Ti. Subliquidus plagioclase is enriched in sodium relative to low pressure phase compositions. Evaluated in normative projections, contrasting liquid lines of descent are revealed as a function of pressure. At one atmosphere, the multisaturated liquids are located close to the thermal divide defined by the plane olivine-plagioclase-augite, but appear, with advanced degrees of crystallization, to be moving away from the thermal divide toward normative quartz. The augites crystallizing in the one atmosphere experiments are calcic and slightly nepheline normative. In the 10 and 12.5 kbar experiments, the augites become subcalcic and dominantly hypersthene normative. Because of this shift in augite compositions, transitional basaltic liquids may at high pressure evolve from the tholeiitic side of the olivine-plagioclase-diopside normative divide onto the alkalic side. With increasing pressure above 15 kbar, the liquidus augite

  6. A controller resetting strategy for the stabilization of DC-to-DC power converters towards non-minimum phase equilibria

    SciTech Connect

    Llanes-Santiago, O.; Sira-Ramirez, H.

    1994-12-31

    A feedback resetting strategy, exercised on the output of a purposely designed unstable dynamical feedback controller, is shown to yield a robust, and efficient, output voltage stabilization of nonlinear average models of DC-to-DC Power Converters around any non-minimum phase equilibrium point of the system. The technique guarantees, in an average sense, an asymptotically stable behavior of the controlled converter state variables towards their required equilibrium values, while the unstable dynamical compensator output is forcefully kept bounded within an arbitrarily small neighborhood of the required controller operating point.

  7. Phase equilibria in the P(2)O(5)-CaO-CaF(2)-NaF-H(2)O quinary system and the formation of apatite

    NASA Astrophysics Data System (ADS)

    Martin, Roger Isaac

    Phase equilibria among calcium phosphates in the Hsb3POsb4-Ca(OH)sb2-Hsb2O ternary system were determined as a basis for research in the formation of hydroxyapatite, a biomaterial. The acidic portion of the ternary diagram was established. Ca(Hsb2POsb4)sb2 was not stable for temperatures below 100sp°C. The experimental and theoretical dissolution paths of Ca(Hsb2POsb4)sb2{*}Hsb2O were compared. It is possible for the initial dissolution of Ca(Hsb2POsb4)sb2{*}Hsb2O to supersaturate the system with respect to hydroxyapatite because Ca(Hsb2POsb4)sb2{*}Hsb2O is "twice" incongruently soluble. Hydroxyapatite composition is variable with a Ca/P ratio ranging from 1.5 to 1.67. Hydroxyapatite formation from acid-base reactions of CaHPOsb4 and Casb4(POsb4)sb2O was investigated for composition at the terminal limits. The total heats-of-reaction (Delta Hsb{r}) were determined to be 261.3 and 320 kJ/mol for the formation of calcium deficient and stoichiometric hydroxyapatite, respectively. Activation energies of 84.7 and 87.4 kJ/mol were calculated for the formation of calcium deficient and stoichiometric hydroxyapatite, respectively. Heats-of-formation (Delta Hsb{f}) for Casb4(POsb4)sb2O and Casb9HPOsb4(POsb4)sb5OH were calculated to be -4764.1 and -1207.7 kJ/mol, respectively. The effects of magnesium on hydroxyapatite formation in vitro from CaHPOsb4 and Casb4(POsb4)sb2O at 37.4sp°C were investigated. Magnesium is a biological agent with 0.78 mM concentrations in blood. Magnesium inhibited nucleation for 1 mM concentrations and above for a 5 liquid-to-solids ratio. However, a 5 mM concentration of MgClsb2 slightly accelerated the growth rate. The activity of magnesium is approximately 6% of its concentration. Therefore the inorganic chemical activity of magnesium may not significantly inhibit the formation of bioapatites. Phase equilibria in the Psb2Osb5-CaO-CaFsb2-Hsb2O system at 37.4sp°C was determined and dental fluorosis explained. Fluoroapatite dissolves

  8. Density functional models of the interfacial tensions near the critical endpoints and tricritical point of three-phase equilibria

    NASA Astrophysics Data System (ADS)

    Koga, K.; Widom, B.

    2016-06-01

    We treat two different density-functional models of the structures and tensions of the interfaces between phases on approach to the tricritical point of three-phase equilibrium. The major objective is to account for some of the results of earlier experimental measurements of these tensions. The thermodynamic background is first reviewed, including representations of the properties near the critical endpoints and tricritical point and of the wetting transitions that may occur on approach to those critical points. The first of the models treated is analytically soluble. Its properties are illuminating but at the price of some artificiality paid for its analytical solubility. The second model, called model T, is in a class of those treated in the past and analyzed numerically. Some of its properties are obtained with sufficient precision to allow one to conclude with near certainty what the analytically exact results would be. This model, too, illuminates the experimental measurements. It is noted where its properties are in accord with those of the analytically soluble model and where the two differ.

  9. Programmable phase plate for tool modification in laser machining applications

    DOEpatents

    Thompson Jr., Charles A.; Kartz, Michael W.; Brase, James M.; Pennington, Deanna; Perry, Michael D.

    2004-04-06

    A system for laser machining includes a laser source for propagating a laser beam toward a target location, and a spatial light modulator having individual controllable elements capable of modifying a phase profile of the laser beam to produce a corresponding irradiance pattern on the target location. The system also includes a controller operably connected to the spatial light modulator for controlling the individual controllable elements. By controlling the individual controllable elements, the phase profile of the laser beam may be modified into a desired phase profile so as to produce a corresponding desired irradiance pattern on the target location capable of performing a machining operation on the target location.

  10. Sorption equilibria of vapor-phase organic pollutants on unsaturated soils and soil minerals. Final report, Mar 85-Mar 89

    SciTech Connect

    Lion, L.W.; Ong, S.K.; Linder, S.R.; Swager, J.L.; Schwager, S.J.

    1990-04-01

    Most groundwater pollutants are volatile organic compounds; however, there is relatively little understanding of the sorption reactions that control the transport and fate of organic vapors in the vadose zone. This investigation identified the physical/chemical properties of the soil matrix and organic vapors which control vapor-solid phase distribution. The dominant property which regulates vapor sorption in the unsaturated zone is the moisture content of the soil. Under very dry conditions, soil mineral/vapor interactions are regulated by specific surface area, indicating the dominance of a relatively non-specific physical adsorption process. However, at moisture contents exceeding an average surface coverage of four to eight layers of water, vapor uptake is controlled by partitioning reactions into soil moisture and soil organic matter.

  11. Phase Equilibria, Crystal Structure and Hydriding/Dehydriding Mechanism of Nd4Mg80Ni8 Compound

    NASA Astrophysics Data System (ADS)

    Luo, Qun; Gu, Qin-Fen; Zhang, Jie-Yu; Chen, Shuang-Lin; Chou, Kuo-Chih; Li, Qian

    2015-10-01

    In order to find out the optimal composition of novel Nd-Mg-Ni alloys for hydrogen storage, the isothermal section of Nd-Mg-Ni system at 400 °C is established by examining the equilibrated alloys. A new ternary compound Nd4Mg80Ni8 is discovered in the Mg-rich corner. It has the crystal structure of space group I41/amd with lattice parameters of a = b = 11.2743(1) Å and c = 15.9170(2) Å, characterized by the synchrotron powder X-ray diffraction (SR-PXRD). High-resolution transmission electron microscopy (HR-TEM) is used to investigate the microstructure of Nd4Mg80Ni8 and its hydrogen-induced microstructure evolution. The hydrogenation leads to Nd4Mg80Ni8 decomposing into NdH2.61-MgH2-Mg2NiH0.3 nanocomposites, where the high density phase boundaries provide a great deal of hydrogen atoms diffusion channels and nucleation sites of hydrides, which greatly enhances the hydriding/dehydriding (H/D) properties. The Nd4Mg80Ni8 exhibits a good cycle ability. The kinetic mechanisms of H/D reactions are studied by Real Physical Picture (RPP) model. The rate controlling steps are diffusion for hydriding reaction in the temperature range of 100 ~ 350 °C and surface penetration for dehydriding reaction at 291 ~ 347 °C. In-situ SR-PXRD results reveal the phase transformations of Mg to MgH2 and Mg2Ni to Mg2NiH4 as functions of hydrogen pressure and hydriding time.

  12. Phase Equilibria, Crystal Structure and Hydriding/Dehydriding Mechanism of Nd4Mg80Ni8 Compound

    PubMed Central

    Luo, Qun; Gu, Qin-Fen; Zhang, Jie-Yu; Chen, Shuang-Lin; Chou, Kuo-Chih; Li, Qian

    2015-01-01

    In order to find out the optimal composition of novel Nd-Mg-Ni alloys for hydrogen storage, the isothermal section of Nd-Mg-Ni system at 400 °C is established by examining the equilibrated alloys. A new ternary compound Nd4Mg80Ni8 is discovered in the Mg-rich corner. It has the crystal structure of space group I41/amd with lattice parameters of a = b = 11.2743(1) Å and c = 15.9170(2) Å, characterized by the synchrotron powder X-ray diffraction (SR-PXRD). High-resolution transmission electron microscopy (HR-TEM) is used to investigate the microstructure of Nd4Mg80Ni8 and its hydrogen-induced microstructure evolution. The hydrogenation leads to Nd4Mg80Ni8 decomposing into NdH2.61-MgH2-Mg2NiH0.3 nanocomposites, where the high density phase boundaries provide a great deal of hydrogen atoms diffusion channels and nucleation sites of hydrides, which greatly enhances the hydriding/dehydriding (H/D) properties. The Nd4Mg80Ni8 exhibits a good cycle ability. The kinetic mechanisms of H/D reactions are studied by Real Physical Picture (RPP) model. The rate controlling steps are diffusion for hydriding reaction in the temperature range of 100 ~ 350 °C and surface penetration for dehydriding reaction at 291 ~ 347 °C. In-situ SR-PXRD results reveal the phase transformations of Mg to MgH2 and Mg2Ni to Mg2NiH4 as functions of hydrogen pressure and hydriding time. PMID:26471964

  13. Phase equilibria, formation, crystal and electronic structure of ternary compounds in Ti-Ni-Sn and Ti-Ni-Sb ternary systems

    SciTech Connect

    Romaka, V.V.; Rogl, P.; Romaka, L.; Stadnyk, Yu.; Melnychenko, N.; Grytsiv, A.; Falmbigl, M.; Skryabina, N.

    2013-01-15

    The phase equilibria of the Ti-Ni-Sn and Ti-Ni-Sb ternary systems have been studied in the whole concentration range by means of X-ray and EPM analyses at 1073 K and 873 K, respectively. Four ternary intermetallic compounds TiNiSn (MgAgAs-type), TiNi{sub 2-x}Sn (MnCu{sub 2}Al-type), Ti{sub 2}Ni{sub 2}Sn (U{sub 2}Pt{sub 2}Sn-type), and Ti{sub 5}NiSn{sub 3} (Hf{sub 5}CuSn{sub 3}-type) are formed in Ti-Ni-Sn system at 1073 K. The TiNi{sub 2}Sn stannide is characterized by homogeneity in the range of 50-47 at% of Ni. The Ti-Ni-Sb ternary system at 873 K is characterized by formation of three ternary intermetallic compounds, Ti{sub 0.8}NiSb (MgAgAs-type), Ti{sub 5}Ni{sub 0.45}Sb{sub 2.55} (W{sub 5}Si{sub 3}-type), and Ti{sub 5}NiSb{sub 3} (Hf{sub 5}CuSn{sub 3}-type). The solubility of Ni in Ti{sub 0.8}NiSb decreases number of vacancies in Ti site up to Ti{sub 0.91}Ni{sub 1.1}Sb composition. - Graphical abstract: Isothermal section of the Ti-Ni-Sn phase diagram and DOS distribution in hypothetical TiNi{sub 1+x}Sn solid solution. Highlights: Black-Right-Pointing-Pointer Ti-Ni-Sn phase diagram was constructed at 1073 K. Black-Right-Pointing-Pointer Four ternary compounds are formed: TiNiSn, TiNi{sub 2-x}Sn, Ti{sub 2}Ni{sub 2}Sn, and Ti{sub 5}NiSn{sub 3}. Black-Right-Pointing-Pointer Three ternary compounds exist in Ti-Ni-Sb system at 873 K. Black-Right-Pointing-Pointer The TiNi{sub 2}Sb compound is absent.

  14. Effect of chlorine on near-liquidus phase equilibria of an Fe-Mg-rich tholeiitic basalt

    NASA Astrophysics Data System (ADS)

    Filiberto, Justin; Dasgupta, Rajdeep; Gross, Juliane; Treiman, Allan H.

    2014-07-01

    The importance of Cl in basalt petrogenesis has been recognized, yet constraints on its effect on liquidus crystallization of basalts are scarce. In order to quantify the role of Cl in basaltic systems, we have experimentally determined near-liquidus phase relations of a synthetic Fe-Mg-rich basalt, doped with 0.0-2.5 wt% dissolved Cl, at 0.7, 1.1, and 1.5 GPa. Results have been parameterized and compared with previous data from literature. The effect of Cl on mineral chemistry and liquidus depression is dependent on the starting basaltic composition. The liquidus depression measured for a SiO2-rich, Al2O3-poor basalt is smaller than that observed for a basaltic melt depleted in silica and enriched in FeOT and Al2O3. The effect of Cl on depression of the olivine-orthopyroxene-liquid multiple saturation pressure does not seem to vary with the starting composition of the basaltic liquid. This suggests that Cl may significantly promote the generation of silica-poor, Fe-Al-rich magmas in the Earth, Mars, and the Moon.

  15. Modeling of the phase equilibria of polystyrene in methylcyclohexane with semi-empirical quantum mechanical methods I.

    PubMed

    Wilczura-Wachnik, Hanna; Jónsdóttir, Svava Osk

    2003-04-01

    A method for calculating interaction parameters traditionally used in phase-equilibrium computations in low-molecular systems has been extended for the prediction of solvent activities of aromatic polymer solutions (polystyrene+methylcyclohexane). Using ethylbenzene as a model compound for the repeating unit of the polymer, the intermolecular interaction energies between the solvent molecule and the polymer were simulated. The semiempirical quantum chemical method AM1, and a method for sampling relevant internal orientations for a pair of molecules developed previously were used. Interaction energies are determined for three molecular pairs, the solvent and the model molecule, two solvent molecules and two model molecules, and used to calculated UNIQUAC interaction parameters, a(ij) and a(ji). Using these parameters, the solvent activities of the polystyrene 90,000 amu+methylcyclohexane system, and the total vapor pressures of the methylcyclohexane+ethylbenzene system were calculated. The latter system was compared to experimental data, giving qualitative agreement. Figure Solvent activities for the methylcylcohexane(1)+polystyrene(2) system at 316 K. Parameters aij (blue line) obtained with the AM1 method; parameters aij (pink line) from VLE data for the ethylbenzene+methylcyclohexane system. The abscissa is the polymer weight fraction defined as y2(x1)=(1mx1)M2/[x1M1+(1mx1)M2], where x1 is the solvent mole fraction and Mi are the molecular weights of the components.

  16. Phase equilibria investigations and thermodynamic modeling of the system Bi2O3-Al2O3

    NASA Astrophysics Data System (ADS)

    Oudich, F.; David, N.; Mathieu, S.; Vilasi, M.

    2015-02-01

    The system Bi2O3-Al2O3 has been experimentally investigated above 600 °C by DTA, XRD and EPMA under air and low oxygen pressure. Only two compounds were found to exist in equilibrium, which are Bi2Al4O9(1Bi2O3:2Al2O3) and Bi25AlO39(25:1). The latter exhibits a sillenite structure and does not contain pentavalent bismuth. A peritectoid decomposition of (25:1) and a peritectic melting of (1:2) occur at 775 °C and 1075 °C respectively, while an eutectic transformation was observed at 815 °C for 97 mol% Bi2O3. On the basis of the results obtained within the present work as well as experimental data provided from literature, a thermodynamic modeling where the liquid phase is described by the two-sublattice ionic liquid model was performed according to the Calphad approach. The resulting thermodynamic optimization yielded good agreement with experimental results in the investigated region.

  17. Phase-space transport in cuspy triaxial potentials: can they be used to construct self-consistent equilibria?

    NASA Astrophysics Data System (ADS)

    Siopis, Christos; Kandrup, Henry E.

    2000-11-01

    This paper focuses on the statistical properties of chaotic orbit ensembles evolved in triaxial generalizations of the Dehnen potential which have been proposed recently to model realistic ellipticals that have a strong density cusp and manifest significant deviations from axisymmetry. Allowance is made for a possible supermassive black hole, as well as low-amplitude friction, noise, and periodic driving which can mimic irregularities associated with discreteness effects and/or an external environment. The chaos exhibited by these potentials is quantified by determining (1) how the relative number of chaotic orbits depends on the steepness of the cusp, as probed by γ, the power-law exponent with which density diverges, and MBH, the black hole mass, (2) how the size of the largest Lyapunov exponent varies with γ and MBH, and (3) the extent to which Arnold webs significantly impede phase-space transport, both with and without perturbations. The most important conclusions dynamically are (1) that, in the absence of irregularities, chaotic orbits tend to be extremely `sticky', so that different pieces of the same chaotic orbit can behave very differently for times ~10000tD or more, but (2) that even very low-amplitude perturbations can prove efficient in erasing many - albeit not all - of these differences. The implications of these facts are discussed both for the structure and evolution of real galaxies and for the possibility of constructing approximate near-equilibrium models using Schwarzschild's method. For example, when trying to use Schwarzschild's method to construct model galaxies containing significant numbers of chaotic orbits, it seems advantageous to build libraries with chaotic orbits evolved in the presence of low-amplitude friction and noise, since such noisy orbits are more likely to represent reasonable approximations to time-independent building blocks. Much of the observed qualitative behaviour can be reproduced with a toy potential given as the

  18. Vapor Pressure Plus: An Experiment for Studying Phase Equilibria in Water, with Observation of Supercooling, Spontaneous Freezing, and the Triple Point

    ERIC Educational Resources Information Center

    Tellinghuisen, Joel

    2010-01-01

    Liquid-vapor, solid-vapor, and solid-liquid-vapor equilibria are studied for the pure substance water, using modern equipment that includes specially fabricated glass cells. Samples are evaporatively frozen initially, during which they typically supercool to -5 to -10 [degrees]C before spontaneously freezing. Vacuum pumping lowers the temperature…

  19. Determination of Epsomite-Hexahydrite Equilibria by the Humidity-Buffer Technique at 0.1 MPa with Implications for Phase Equilibria in the System MgSO4-H2O

    NASA Astrophysics Data System (ADS)

    Chou, I.-Ming; Seal, Robert R.

    2003-11-01

    Epsomite (MgSO4.7H2O) and hexahydrite (MgSO4.6H2O) are common minerals found in marine evaporite deposits, in saline lakes as precipitates, in weathering zones of coal and metallic deposits, in some soils and their efflorescences, and possibly on the surface of Europa as evaporite deposits. Thermodynamic properties of these two minerals reported in the literature are in poor agreement. In this study, epsomite-hexahydrite equilibria were determined along four humidity-buffer curves at 0.1 MPa and between 25 and 45°C. Results obtained for the reaction epsomite = hexahydrite + H2O, as demonstrated by very tight reversals along each humidity buffer, can be represented by ln K(+/- 0.012) = 20.001 - 7182.07/T, where K is the equilibrium constant, and T is temperature in Kelvin. The derived standard Gibbs free energy of reaction is 10.13 +/- 0.07 kJ/mol, which is essentially the same value as that calculated from vapor pressure measurements reported in the literature. However, this value is at least 0.8 kJ/mol lower than those calculated from the data derived mostly from calorimetric measurements.

  20. Determination of epsomite-hexahydrite equilibria by the humidity-buffer technique at 0.1 MPa with implications for phase equilibria in the system MgSO4-H2O.

    USGS Publications Warehouse

    Chou, I.-Ming; Seal, R.R.

    2003-01-01

    Epsomite (MgSO(4).7H(2)O) and hexahydrite (MgSO(4).6H(2)O) are common minerals found in marine evaporite deposits, in saline lakes as precipitates, in weathering zones of coal and metallic deposits, in some soils and their efflorescences, and possibly on the surface of Europa as evaporite deposits. Thermodynamic properties of these two minerals reported in the literature are in poor agreement. In this study, epsomite-hexahydrite equilibria were determined along four humidity-buffer curves at 0.1 MPa and between 25 and 45 degrees C. Results obtained for the reaction epsomite = hexahydrite + H(2)O, as demonstrated by very tight reversals along each humidity buffer, can be represented by ln K(+/- 0.012) = 20.001 - 7182.07/T, where K is the equilibrium constant, and T is temperature in Kelvin. The derived standard Gibbs free energy of reaction is 10.13 +/- 0.07 kJ/mol, which is essentially the same value as that calculated from vapor pressure measurements reported in the literature. However, this value is at least 0.8 kJ/mol lower than those calculated from the data derived mostly from calorimetric measurements.

  1. Bifurcations of relative equilibria

    NASA Technical Reports Server (NTRS)

    Krupa, Martin

    1990-01-01

    The characteristics of equivariant dynamical systems near relative equilibria (RE: group orbits which are invariant in the flow of an equivariant vector field) are investigated analytically, with a focus on the dynamics and bifurcation (B) behavior. The principles of Lie-group theory are reviewed; the decomposition of the vector field is explained; and particular attention is given to the Bs of RE occurring when an eigenvalue passes through zero, Hopf Bs of RE, the classification of generic secondary steady-state and Hopf Bs with symmetry group O(2), Bs of the zero solution of the Kuramoto-Shivashinsky equation, and possible generic steady-state Bs in the two-dimensional Benard problem. In the latter case, it is shown that the primary generic Bs are to two types of equilibria (hexagons and rolls), while the secondary Bs result in trajectories which are either equilibria or rotating waves.

  2. Phase Equilibria Study in the TeO2-Na2O-SiO2 System in Air Between 723 K (500 °C) and 1473 K (1200 °C)

    NASA Astrophysics Data System (ADS)

    Santoso, Imam; Taskinen, Pekka

    2016-08-01

    Knowledge of phase equilibria in the TeO2-Na2O-SiO2 system at elevated temperatures is important for ceramic and glass industries and for improving the operation of the smelting process of tellurium-containing materials. A review of previous investigations has indicated, however, that there are omissions in the available datasets on the liquidus temperatures of the molten TeO2-Na2O-SiO2 mixtures. The employed experimental method included equilibration of mixtures made from high purity oxides, rapid quenching of the equilibrated samples in water and followed by compositional analysis of the phases using an electron probe X-ray microanalyzer. The liquidus and phase equilibria in the TeO2-SiO2, TeO2-Na2O, and SiO2-TeO2-Na2O systems have been studied for a wide range of compositions between 723 K (500 °C) and 1473 K (1200 °C) at TeO2, SiO2, and Na2SiO3 saturations. New data have been generated in the SiO2-TeO2-Na2O system at SiO2 saturation. The liquidus compositions in the TeO2-Na2O system at TeO2 saturation have been compared with the previous data and an assessed phase diagram.

  3. Effect of trans-cis photoisomerization on phase equilibria and phase transition of liquid-crystalline azobenzene chromophore and its blends with reactive mesogenic diacrylate

    NASA Astrophysics Data System (ADS)

    Kim, Namil; Li, Quan; Kyu, Thein

    2011-03-01

    Photoisomerization-induced phase transition of neat liquid-crystalline azobenzene chromophore (LCAC) and its effect on phase diagrams of its mixtures with reactive mesogenic diacrylate monomer (RM257) have been investigated experimentally and theoretically. Upon irradiation with ultraviolet light, the nematic phase of LCAC transformed to isotropic, while the crystal phase showed corrugated textures on the surface (i.e., ripples). The phase-transition temperatures and corresponding morphologies of the blends have been investigated by means of differential scanning calorimetry and optical microscopy. A theoretical phase diagram of a binary nematic and crystalline system was constructed by self-consistently solving the combined free energies of Flory-Huggins, Maier-Saupe, and phase-field theory. The calculation revealed various coexistence regions such as nematic + liquid (N1 + L2), crystal + liquid (Cr1 + L2), crystal + nematic (Cr1 + N2), and crystal + crystal (Cr1 + Cr2) over a broad range of compositions including the single-phase nematic (N1, N2) of the corresponding constituents. The calculated liquidus lines were in good accord with the depressed mesophase-isotropic transition points. The present paper demonstrates the effect of trans-cis photoisomerization on the mesophase transitions of neat LCAC and the phase diagram of LCAC-RM257 as well as on the ripple formation (i.e., periodic undulation) on the azobenzene crystals.

  4. Phase Equilibria of the Cu-Ti-Er System at 773 K (500 °C) and Stability of the CuTi3 Phase

    NASA Astrophysics Data System (ADS)

    Zhan, Yongzhong; Peng, Dan; She, Jia

    2012-11-01

    The phase relationships of the Cu-Ti-Er ternary phase diagram at 773 K (500 °C) were investigated mainly by means of X-ray powder diffraction (XRD), scanning electron microscopy (SEM) with energy dispersive spectroscopy (EDS), and differential thermal analysis (DTA). It is confirmed in this work that the binary compounds Cu9Er2 and Cu7Er2 exist in the Cu-Er binary system at 773 K (500 °C). The stability of the CuTi3 phase is confirmed in the Cu-Ti system. After heat treatment at 1023 K (750 °C) for 90 hours, the phase CuTi3 is observed in the microstructure of the alloy 25Cu75Ti. The temperature of the eutectoid transformation, namely, β-Ti ↔ α-Ti + CuTi3, is determined to be 1078 K (805 °C) in this work. The 773 K (500 °C) isothermal section consists of 14 single-phase regions, 25 two-phase regions, and 12 three-phase regions. None of the phases in this system reveals a remarkable homogeneity range at 773 K (500 °C).

  5. High-grade metamorphism during Archean-Paleoproterozoic transition associated with microblock amalgamation in the North China Craton: Mineral phase equilibria and zircon geochronology

    NASA Astrophysics Data System (ADS)

    Yang, Qiong-Yan; Santosh, M.; Tsunogae, Toshiaki

    2016-10-01

    Metamorphic regimes in Archean terranes provide important keys to the plate tectonic processes in early Earth. The North China Craton (NCC) is one of the ancient continental nuclei in Asia and recent models propose that the cratonic architecture was built through the assembly of several Archean microcontinental blocks into larger crustal blocks. Here we investigate garnet- and pyroxene-bearing granulite facies rocks along the periphery of the Jiaoliao microcontinental block in the NCC. The garnet-bearing granulites contain peak mineral assemblage of garnet + clinopyroxene + orthopyroxene + magnetite + plagioclase + quartz ± biotite ± ilmenite. Mineral phase equilibria computations using pseudosection and geothermobarometry suggest peak P-T condition of 800-830 °C and 7-8 kbar for metamorphism. Isopleths using XMg of orthopyroxene and XCa of garnet in another sample containing the peak mineral assemblage of garnet + orthopyroxene + quartz + magnetite ± fluid yield peak P-T conditions of 860-920 °C and 11-14 kbar. Geochemical data show tonalitic to granodioritic composition and arc-related tectonic setting for the magmatic protoliths of these rocks. Zircon LA-ICP-MS analyses yield well-defined discordia with upper intercept ages of 2562 ± 20 Ma (MSWD = 0.94) and 2539 ± 21 Ma (MSWD = 0.59) which is correlated with the timing of emplacement of the magmatic protolith. A younger group of zircons with upper intercept ages of 2449 ± 41 Ma (MSWD = 0.83); N = 6 as 2449 ± 41 Ma (MSWD = 0.83; N = 6) and 2480 ± 44 Ma (MSWD = 1.2; N = 9) constrains the timing of metamorphism. Zircon Lu-Hf data show dominantly positive εHf(t) values (up to 8.5), and yield crustal residence ages (TDMC) in the range of 2529 to 2884 Ma, suggesting magma sources from Meso-Neoarchean juvenile components. The high temperature and medium to high pressure metamorphism is considered to have resulted from the subduction-collision tectonics associated with microblock amalgamation in the NCC at

  6. Geometric phases causing lifetime modifications of metastable states of hydrogen

    NASA Astrophysics Data System (ADS)

    Trappe, Martin-Isbjörn; Augenstein, Peter; DeKieviet, Maarten; Gasenzer, Thomas; Nachtmann, Otto

    2016-04-01

    Externally applied electromagnetic fields in general have an influence on the width of atomic spectral lines. The decay rates of atomic states can also be affected by the geometry of an applied field configuration giving rise to an imaginary geometric phase. A specific chiral electromagnetic field configuration is presented which geometrically modifies the lifetimes of metastable states of hydrogen. We propose to extract the relevant observables in a realistic longitudinal atomic beam spin-echo apparatus which allows the initial and final fluxes of the metastable atoms to be compared with each other interferometrically. A geometry-induced change in lifetimes at the 5%-level is found, an effect large enough to be observed in an available experiment.

  7. The system AgI-AgBr: Energetic consequences of defect equilibria in single-phase and two-phase regions

    SciTech Connect

    Khandkar, A.; Navrotsky, A.; Tare, V.B.; Wagner, J.B.

    1984-11-01

    The enthalpy of solution of various single- and two-phase AgI-AgBr compositions in AgNO/sub 3/ at 518 K has been determined using a Calvet-type twin microcalorimeter. The enthalpy (H/sub 518/ - H/sub 298/) of melted and unmelted mixtures of AgI and AgBr of various compositions within two-phase regions of the phase diagram has also been obtained using the same calorimeter. The effect of AgBr on the temperature and enthalpy of transformation of ..beta..-AgI to ..cap alpha..AgI has been investigated using a Perkin Elmer Differential Scanning Calorimeter. The terminal compositions at 518 K of the two-phase region of AgI-AgBr system has been found to be AgI /SUB 0.85/ Br /SUB 0.15/ and AgI /SUB 0.3/ Br /SUB 0.7/ . The excess enthalpy, the difference in (H/sub 518/ - H/sub 298/) values of the unmelted and melted mixtures in the two-phase region of the AgI-AgBr system, has been found to be maximum at the equivolume concentration of the two terminal phases and is suggested to be due to the generation of silver ion vacancies at the interfaces due to a space-charge layer.

  8. Gaseous phase coal surface modification. Final technical report

    SciTech Connect

    Okoh, J.M.; Pinion, J.; Thiensatit, S.

    1992-05-07

    In this report, we present an improved, feasible and potentially cost effective method of cleaning and beneficiating ultrafine coal. Increased mechanization of mining methods and the need towards depyritization, and demineralization have led to an increase in the quantity of coal fines generated in recent times. For example, the amount of {minus}100 mesh coal occurring in coal preparation plant feeds now typically varies from 5 to 25% of the total feed. Environmental constraints coupled with the greatly increased cost of coal have made it increasingly important to recover more of these fines. Our method chemically modifies the surface of such coals by a series of gaseous phase treatments employing Friedel-Crafts reactions. By using olefins (ethene, propene and butene) and hydrogen chloride catalyst at elevated temperature, the surface hydrophobicity of coal is enhanced. This increased hydrophobicity is manifest in surface phenomena which reflect conditions at the solid/liquid interphase (zeta potential) and those which reflect conditions at the solid/liquid/gas interphases (contact angle, wettability and floatability).

  9. Liquid phase methanol LaPorte process development unit: Modification, operation, and support studies

    SciTech Connect

    Not Available

    1991-02-02

    This report consists of Detailed Data Acquisition Sheets for Runs E-6 and E-7 for Task 2.2 of the Modification, Operation, and Support Studies of the Liquid Phase Methanol Laporte Process Development Unit. (Task 2.2: Alternate Catalyst Run E-6 and Catalyst Activity Maintenance Run E-7).

  10. Synthesis and solution-phase conformation of the RG-I fragment of the plant polysaccharide pectin reveals a modification-modulated assembly mechanism.

    PubMed

    Scanlan, Eoin M; Mackeen, Mukram M; Wormald, Mark R; Davis, Benjamin G

    2010-06-01

    The syntheses of pure RG-I fragments of key plant matrix biomolecule pectin using a counterintuitive late-stage convergent cis-glycosylation has allowed detailed analyses of their solution-phase conformations, metal binding affinities, pK(a) values, self-assembly equilibria, and diffusional kinetics. These reveal a striking, right-handed 3(1)-helix that provides an effective and repeating lateral display of putative liganding carboxylates. Moreover, these heteropolymeric structures allow units as short as tetrasaccharides to self-assemble through carbohydrate-carbohydrate interactions that are induced by the presence of Ca(II), a known dynamic trigger in planta. These self-assembly properties can be switched simply by the addition or removal of a single methyl group in this repeating unit through methyl (de)esterification, another known dynamic trigger in planta. Together, the combined effect of Ca(II) and methylation revealed here suggests a concerted molecular basis for these two major dynamic modifications in planta.

  11. Calculation of complex equilibria involving vaporization into vacuum

    NASA Technical Reports Server (NTRS)

    Paule, R. C.

    1974-01-01

    A simplified, direct approach is presented to the description of complex equilibria involving vaporization into vacuum. Emphasis is on the basic problem-solving process and on modification of existing techniques. Sequential solutions are presented to problems involving purification of a melt by vaporization into vacuum. The effects of concentration of melt and oxygen partial pressures on vaporization rates are demonstrated.

  12. Phase variable type III restriction-modification systems of host-adapted bacterial pathogens.

    PubMed

    Fox, Kate L; Srikhanta, Yogitha N; Jennings, Michael P

    2007-09-01

    Phase variation, the high-frequency on/off switching of gene expression, is a common feature of host-adapted bacterial pathogens. Restriction-modification (R-M) systems, which are ubiquitous among bacteria, are classically assigned the role of cellular defence against invasion of foreign DNA. These enzymes are not obvious candidates for phase variable expression, a characteristic usually associated with surface-expressed molecules subject to host immune selection. Despite this, numerous type III R-M systems in bacterial pathogens contain repetitive DNA motifs that suggest the potential for phase variation. Several roles have been proposed for phase variable R-M systems based on DNA restriction function. However, there is now evidence in several important human pathogens, including Haemophilus influenzae, Neisseria meningitidis and Neisseria gonorrhoeae, that these systems are 'phasevarions' (phase variable regulons) controlling expression of multiple genes via a novel epigenetic mechanism. PMID:17714447

  13. Solution Versus Gas-Phase Modification of Peptide Cations with NHS-Ester Reagents

    NASA Astrophysics Data System (ADS)

    Mentinova, Marija; Barefoot, Nathan Z.; McLuckey, Scott A.

    2012-02-01

    A comparison between solution and gas phase modification of primary amine sites in model peptide cations with N-hydroxysuccinimide (NHS) ester reagents is presented. In all peptides, the site of modification in solution was directed to the N-terminus by conducting reactions at pH = 5, whereas for the same peptides, a lysine residue was preferentially modified in the gas phase. The difference in pKa values of the N-terminus and ɛ-amino group of the lysine allows for a degree of control over sites of protonation of the peptides in aqueous solution. With removal of the dielectric and multiple charging of the peptide ions in the gas phase, the accommodation of excess charge can affect the preferred sites of reaction. Interaction of the lone pair of the primary nitrogen with a proton reduces its nucleophilicity and, as a result, its reactivity towards NHS-esters. While no evidence for reaction of the N-terminus with sulfo-NHS-acetate was noted in the model peptide cations, a charge inversion experiment using bis[sulfosuccinimidyl] suberate, a cross-linking reagent with two sulfo-NHS-ester functionalities, showed modification of the N-terminus. Hence, an unprotonated N-terminus can serve as a nucleophile to displace NHS, which suggests that its lack of reactivity with the peptide cations is likely due to the participation of the N-terminus in solvating excess charge.

  14. Reagent Cluster Anions for Multiple Gas-Phase Covalent Modifications of Peptide and Protein Cations

    NASA Astrophysics Data System (ADS)

    Prentice, Boone M.; Stutzman, John R.; McLuckey, Scott A.

    2013-07-01

    Multiple gas phase ion/ion covalent modifications of peptide and protein ions are demonstrated using cluster-type reagent anions of N-hydroxysulfosuccinimide acetate (sulfo-NHS acetate) and 2-formyl-benzenesulfonic acid (FBMSA). These reagents are used to selectively modify unprotonated primary amine functionalities of peptides and proteins. Multiple reactive reagent molecules can be present in a single cluster ion, which allows for multiple covalent modifications to be achieved in a single ion/ion encounter and at the `cost' of only a single analyte charge. Multiple derivatizations are demonstrated when the number of available reactive sites on the analyte cation exceeds the number of reagent molecules in the anionic cluster (e.g., data shown here for reactions between the polypeptide [K10 + 3H]3+ and the reagent cluster [5R5Na - Na]-). This type of gas-phase ion chemistry is also applicable to whole protein ions. Here, ubiquitin was successfully modified using an FBMSA cluster anion which, upon collisional activation, produced fragment ions with various numbers of modifications. Data for the pentamer cluster are included as illustrative of the results obtained for the clusters comprised of two to six reagent molecules.

  15. Reversed-phase ion-pair liquid chromatographic method for determination of reaction equilibria involving ionic species: exemplification of the method using ligand substitution reactions of ethylenediaminetetraacetatochromium(III) ion with acetate and phosphate ions.

    PubMed

    Sato, Emiko; Miya, Seiko; Saitoh, Kazunori; Saito, Shingo; Shibukawa, Masami

    2011-02-18

    A reversed-phase ion-pair liquid chromatographic method is presented for the determination of reaction equilibria involving ionic species of the same charge sign as reactant and product compounds. It has been demonstrated that ion-exchange chromatography or reversed-phase ion-pair chromatography is a useful tool for the determination of equilibrium constants of chemical reactions involving ionic species such as metal complexation reactions. Previous work with these methods has been based on the assumption that the limiting retention factors of the reactant and product species are constant independent of concentration of the chemical species (X) in the mobile phase, which reacts with the analyte compound. However, when all the reactant and product species are ions of the same charge sign as that of the species X, it is virtually impossible to apply these methods to the equilibrium constant determination because the retention factors of both the reactant and product species may depend on the concentration of X. In this study, an alternative approach was developed that estimates the limiting retention factors of ionic species from the dependence of the retention factor on the ionic strength of the mobile phase. Ligand substitution reactions of ethylenediaminetetraacetatochromium(III) ion with acetate and phosphate ions were used as model reactions to test this method. The equilibrium constants determined by this method are in good agreement with those obtained by a UV-visible spectrophotometric method.

  16. Modifications in the glycerophospholipid composition between the Coxiella burnetii phase I and phase II cells suggest an association with phase variation of the bacterium.

    PubMed

    Frimmelová, M; Toman, R; Pompach, P; Škultéty, L

    2016-03-01

    Glycerophospholipids (GP) extracted from the Coxiella burnetii strain Nine Mile in virulent phase I (NM I) and low virulent phase II (NM II) were analyzed by Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometry (MS) that gave a superior mass resolution and mass accuracy allowing unambiguous peak recognition and precise assignment of ions. We showed that GP present in the pathogen's outer membrane underwent considerable modifications during the phase variation that might be related to impact of various environmental factors. It was found that GP from phase I cells were much more complex than those from phase II cells. While glycerophosphoethanolamines (PE), glycerophosphocholines (PC) and glycerophosphoglycerols (PG) were present in both phases of C. burnetii, major differences were observed in the presence of glycerophosphates (PA) and glycerophosphoserines (PS). Thus, PA but no PS were detected in NM I variant in contrast with NM II cells where PS but no PA were identified. It is suggested that enzymes for PA head group modifications to form PS, PE, and PG become active during the phase variation of the bacterium. PMID:26982464

  17. Reduction of erosion in elbows due to flow modifications: Final report, Phase 1. [Elbows

    SciTech Connect

    Johnson, E.K.; Means, K.H.; Eyler, R.L.; Holtzworth, J.D.

    1987-11-01

    The objective of this project is to investigate the concept of flow-field modification as a method for reducing erosion in bends (elbows) used in pneumatic transport systems. Flow field modifications were primarily accomplished by injecting air at selected locations within the bends. Part I of this project shows the feasibility of the concept. Part II of this project will include further experiments and analysis, leading to a design methodology for incorporating this concept into piping systems. This report represents the final report for Part I of this project. This report contains a survey of the literature dealing with the erosion in bends (elbows) and the fundamental subjects of erosion and two-phase, gas-solids, flow. Based on this literature survey, a pneumatic transport test loop was constructed. Several bend designs were tested, using sand, under a variety of operating conditions. The results of this exploratory effort indicate that modifying the flow field in a bend with jets may: (1) decrease erosion; (2) change the erosion pattern with the same amount of erosion; or (3) significantly increase the erosion process. Data indicate that the erosion rate may be reduced by low-velocity jets for high phase-density flow. Apparently the interaction of jets with dilute phase-density flow tends to accelerate the erosion process. It is recommended that the project be continued in order to more fully understand the process and its capabilities to solve the difficult technical problem of erosion in bends (elbows).

  18. Chemometric investigation of complex equilibria in solution phase II: Sensitivity of chemical models for the interaction of AADH and FAH with Ni(II) in aqueous medium.

    PubMed

    Babu, A R; Krishna, D M; Rao, R S

    1993-12-01

    A detailed study of the species formed in the complex equilibria involving adipic acid dihydrazide (AADH)/2-furoic acid hydrazide (FAH) with Ni(II) using pH titration with glass electrode is performed. The results of modeling studies and effect of errors on the equilibrium constants of AADH/FAH with Ni(II) refined by the non-linear least squares program MINIQUAD75 are reported. Based on the expert system approach developed in our laboratory for the species formed from secondary formation data (n and n (H)), several preliminary chemical models were tested. For the four species identified (MLH, ML, ML(2)H, ML(2)), an exhaustive search of a different combination of models (15) was performed. Then other suspected minor species (ML(2)H(2), ML(3) and ML(3)H) were tested. The final best fit chemical model was found to contain ML(3)H to an extent of 3% along with the other four major species. In order to ascertain the accuracy of the stability constants and consequently distribution of the species, a detailed error analysis is attempted. As the existing least squares procedures cannot suppress the systematic errors, three-dimensional plots of the simultaneous effects of pH and TLO:TMO (1.5:1 to 5:1) on the percentage of species are drawn which are of immense use in arriving at optimum conditions for the preparation of a complex of definite stoichiometry. PMID:18965865

  19. Transferable SAFT-VR models for the calculation of the fluid phase equilibria in reactive mixtures of carbon dioxide, water, and n-alkylamines in the context of carbon capture.

    PubMed

    Mac Dowell, N; Pereira, F E; Llovell, F; Blas, F J; Adjiman, C S; Jackson, G; Galindo, A

    2011-06-30

    The amine functional groups are fundamental building blocks of many molecules that are central to life, such as the amino acids, and to industrial processes, such as the alkanolamines, which are used extensively for gas absorption. The modeling of amines and of mixtures of amines with water (H(2)O) and carbon dioxide (CO(2)) is thus relevant to a number of applications. In this contribution, we use the statistical associating fluid theory for potentials of variable range (SAFT-VR) to describe the fluid phase behavior of ammonia + H(2)O + CO(2) and n-alkyl-1-amine + H(2)O + CO(2) mixtures. Models are developed for ammonia (NH(3)) and n-alkyl-1-amines up to n-hexyl-1-amine (CH(3)NH(2) to C(6)H(13)NH(2)). The amines are modeled as homonuclear chain molecules formed from spherical segments with additional association sites incorporated to mediate the effect of hydrogen-bonding interactions. The SAFT-VR approach provides a representation of the pure component fluid phase equilibria, on average, to within 1.48% of the experimental data in relative terms for the saturated liquid densities and vapor pressures. A simple empirical correlation is derived for the SAFT-VR parameters of the n -alkylamine series as a function of molecular weight. Aqueous mixtures of the amines are modeled using a model of water taken from previous work. The models developed for the mixtures are of high fidelity and can be used to calculate the binary fluid phase equilibrium of these systems to within 2.28% in relative terms for the temperature or pressure and 0.027 in absolute terms for the mole fraction. Regions of both vapor-liquid and liquid-liquid equilibria are considered. We also consider the reactive mixtures of amines and CO(2) in aqueous solution. To model the reaction of CO(2) with the amine, an additional site is included on the otherwise nonassociating CO(2) model. The unlike interaction parameters for the NH(3) + H(2)O + CO(2) ternary mixture are obtained by comparison to the

  20. Altering the interfacial activation mechanism of a lipase by solid-phase selective chemical modification.

    PubMed

    López-Gallego, Fernando; Abian, Olga; Guisán, Jose Manuel

    2012-09-01

    This study presents a combined protein immobilization, directed mutagenesis, and site-selective chemical modification approach, which was used to create a hyperactivated semisynthetic variant of BTL2. Various alkane chains were tethered at three different positions in order to mimic the lipase interfacial activation exogenously triggered by detergents. Optimum results were obtained when a dodecane chain was introduced at position 320 by solid-phase site-selective chemical modification. The resulting semisynthetic variant showed a 2.5-fold higher activity than the wild-type nonmodified variant in aqueous conditions. Remarkably, this is the maximum hyperactivation ever observed for BTL2 in the presence of detergents such as Triton X-100. We present evidence to suggest that the endogenous dodecane chain hyperactivates the enzyme in a similar fashion as an exogenous detergent molecule. In this way, we also observe a faster irreversible enzyme inhibition and an altered detergent sensitivity profile promoted by the site-selective chemical modification. These findings are also supported by fluorescence studies, which reveal that the structural conformation changes of the semisynthetic variant are different to those of the wild type, an effect that is more pronounced in the presence of detergent. Finally, the optimal immobilized semisynthetic variant was successfully applied to the selective synthesis of oxiran-2-yl butyrate. Significantly, this biocatalyst is 12-fold more efficient than the immobilized wild-type enzyme, producing the S-enantiomer with higher enantiospecificity (ee = 92%). PMID:22876885

  1. Liquid phase methanol LaPorte process development unit: Modification, operation, and support studies

    SciTech Connect

    Not Available

    1990-10-23

    The objectives of this program are to implement and test the process improvements identified through the engineering studies of the current program to demonstrate the capability of long-term catalyst activity maintenance, and to perform process and design engineering work that can be applied to a scaled-up Liquid Phase Methanol (LPMEOH) facility. An optional series of PDU runs is offered to extend the testing of the process improvements. A parallel research program will be performed to enhance the LPMEOH technical data base to improve the likelihood of commercialization of the LPMEOH process. Activities this quarter include: Flow sheet development for La Porte PDU modifications continues. A preliminary P ID review was completed and flow sheet modifications were identified and are being incorporated. A preliminary hazards review was completed on 22 May. Some minor flow sheet modifications resulted and a number of action items were identified. The most significant action item is to develop a materials reactivity and compatibility grid for the different alcohols, ethers, and esters which will be produced at the PDU. Heat and material balances were completed for the maximum production case of the mixed DME/MEOH synthesis campaign. An improved rate expression was developed. 1 fig.

  2. Toroidal equilibria in spherical coordinates

    SciTech Connect

    Tsui, K. H.

    2008-11-15

    The standard Grad-Shafranov equation for axisymmetric toroidal plasma equilibrium is customary expressed in cylindrical coordinates with toroidal contours, and through which benchmark equilibria are solved. An alternative approach to cast the Grad-Shafranov equation in spherical coordinates is presented. This equation, in spherical coordinates, is examined for toroidal solutions to describe low {beta} Solovev and high {beta} plasma equilibria in terms of elementary functions.

  3. Code System to Model Aqueous Geochemical Equilibria.

    2001-08-23

    Version: 00 MINTEQ is a geochemical program to model aqueous solutions and the interactions of aqueous solutions with hypothesized assemblages of solid phases. It was developed for the Environmental Protection Agency to perform the calculations necessary to simulate the contact of waste solutions with heterogeneous sediments or the interaction of ground water with solidified wastes. MINTEQ can calculate ion speciation/solubility, adsorption, oxidation-reduction, gas phase equilibria, and precipitation/dissolution ofsolid phases. MINTEQ can accept a finite massmore » for any solid considered for dissolution and will dissolve the specified solid phase only until its initial mass is exhausted. This ability enables MINTEQ to model flow-through systems. In these systems the masses of solid phases that precipitate at earlier pore volumes can be dissolved at later pore volumes according to thermodynamic constraints imposed by the solution composition and solid phases present. The ability to model these systems permits evaluation of the geochemistry of dissolved traced metals, such as low-level waste in shallow land burial sites. MINTEQ was designed to solve geochemical equilibria for systems composed of one kilogram of water, various amounts of material dissolved in solution, and any solid materials that are present. Systems modeled using MINTEQ can exchange energy and material (open systems) or just energy (closed systems) with the surrounding environment. Each system is composed of a number of phases. Every phase is a region with distinct composition and physically definable boundaries. All of the material in the aqueous solution forms one phase. The gas phase is composed of any gaseous material present, and each compositionally and structurally distinct solid forms a separate phase.« less

  4. Structural phase modification in Cu incorporated nanostructured zinc sulfide thin films

    NASA Astrophysics Data System (ADS)

    Chalana, S. R.; Jolly Bose, R.; Reshmi Krishnan, R.; Kavitha, V. S.; Sreeja Sreedharan, R.; Mahadevan Pillai, V. P.

    2016-08-01

    Cu incorporated zinc sulfide (ZnS) films are prepared by a RF magnetron sputtering technique and the influence of Cu doping concentration on the structural, morphological and optical properties is systematically analyzed using techniques like grazing incidence X-Ray diffraction (GIXRD), micro-Raman spectroscopy, atomic force microscopy (AFM), field emission scanning electron microscopy (FESEM), energy dispersive X-ray spectroscopy (EDS) and UV-vis spectroscopy. XRD examination of the as-prepared films revealed the presence of polycrystalline structure with co-existence of cubic and hexagonal phases in the pure and lower Cu incorporated films. Increase in Cu doping concentration causes a gradual phase transformation from mixed phase to cubic phase. Micro-Raman spectra further confirms the structural phase modifications with the addition of Cu in ZnS. Morphological analysis shows compact distribution of elongated grain geometry with good connectivity and detectable grain boundary in the pure and Cu incorporated films. Increase in Cu incorporation results in the systematic reduction of RMS surface roughness. EDS analysis confirms the incorporation of Cu and surface vacancy defects in the doped films. All the films are transparent in the visible region and band gap calculation by Tauc plot shows that increase in Cu incorporation results in band gap renormalization.

  5. Phase modification and surface plasmon resonance of Au/WO3 system

    NASA Astrophysics Data System (ADS)

    Bose, R. Jolly; Kavitha, V. S.; Sudarsanakumar, C.; Pillai, V. P. Mahadevan

    2016-08-01

    We report the action of gold as catalyst for the modification of phase from triclinic WO3 to monoclinic W18O49 and nucleation centre for the formation of W18O49 phase, in gold incorporated tungsten oxide films prepared by RF magnetron sputtering technique. A new band is observed near 925 cm-1 in the Raman spectra of gold incorporated tungsten oxide films which is not observed in the pure tungsten oxide film. The intensity of this band enhances with gold content. A localized surface plasmon resonance (LSPR) band is observed near the wavelength 604 nm in gold incorporated tungsten oxide films. The integrated intensities of LSPR band and Raman band (∼925 cm-1) can be used for sensing the quantity of gold in the Au/WO3 matrix.

  6. Modification of the aluminium rich portion of the Nd-Al phase diagram

    SciTech Connect

    Kale, G.B.; Biswas, A.; Sharma, I.G.

    1997-10-01

    The phase diagrams of neodymium-aluminum binary systems have been studied extensively during the last three decades. Most common methods of preparation of Nd-Al alloy is by melting the component species according to the desired ratios followed by homogenization. However, these alloys can be prepared by other methods such as aluminothermic reduction of neodymium oxide or fused salt electrowinning. In the present work aluminothermic reduction of neodymium oxide with excess of aluminum was used to make the alloys. The melted alloys were characterized with the help of optical microscope, Electron Probe Micro Analyzer (EPMA) and by X-ray Diffractometer (XRD). Based on the results obtained, few modifications pertaining to aluminum rich side of neodymium-aluminum phase diagram are suggested.

  7. Genetically engineered charge modifications to enhance protein separation in aqueous two-phase systems: Electrochemical partitioning

    SciTech Connect

    Luther, J.R.; Glatz, C.E. . Dept. of Chemical Engineering)

    1994-06-20

    The authors examined the effect of genetically engineered charge modifications on the partitioning behavior of proteins in dextran/polyethylene glycol two-phase systems containing potassium phosphate. By genetically altering a protein's charge, the role of charge on partitioning can be assessed directly without the need to modify the phase system. The charge modifications used are of two types: charged tails of polyaspartic acid fused to [beta]-galactosidase and charge-change point mutations of T4 lysozyme which replace positive lysine residues with negative glutamic acids. The partition coefficient K[sub p] for these proteins was related to measured interfacial potential differences [Delta][phi] using the simple thermodynamic model, In K[sub p] = In K, + (FIRT)Z[sub p] [Delta][phi]. The protein net charge Z[sub p] was determined using the Henderson-Hasselbalch relationship with modifications based on experimentally determined titration and isoelectric point data. It was found that when the electropartitioning term Z[sub p] [Delta][phi] was varied by changing the pH, the partitioning of T4 lysozyme was quantitatively described by the thermodynamic model. The [beta]-galactosidase fusions displayed qualitative agreement, and although less than predicted, the partitioning increased more than two orders of magnitude for the pH range examined. Changes in the partitioning of lysozyme due to the various mutations agreed qualitatively with the thermodynamic model, but with a smaller than expected dependence on the estimated charge differences. The [beta]-galactosidase fusions, on the other hand, did not display a consistent charge based trend, which is likely due either to the enzyme's large size and complexity or to nonelectrostatic contributions from the tails. The lack of quantitative fit with the model described above suggests that the assumptions made in developing this model are oversimplified.

  8. An Extensive Study of Protein Phase Diagram Modification: Increasing Macromolecular Crystallizability by Temperature Screening

    SciTech Connect

    Lin, Yi-Bin; Zhu, Dao-Wei; Wang, Tao; Song, Jian; Zou, Yong-Shui; Zhang, Yong-Lian; Lin, Sheng-Xiang

    2009-02-23

    A new parameter 'relative crystallizability' for protein crystallization has been proposed, and its relationship with protein solubility and crystallization success has been studied (Zhu et al. J. Struct. Biol. 2006, 154, 297). Here we further construct the phase diagrams of a larger number of proteins, study the phase modification as a function of temperature, and establish the relationship between the nucleation zone area (S{sub N}) and crystallization success. The phase diagrams of 10 proteins were constructed and their S{sub N} were compared, demonstrating that temperature modifies the protein nucleation zone. Such modification can significantly enlarge the S{sub N} and increase protein crystallizability. For example, the S{sub N} of ribonuclease S and trypsin increases by 2.4- and 1.6-fold when the temperature moves to 277 K from 295 K, while at the same time the crystallization hits increase from 20.8% to 42.9% and 12.5% to 25%, respectively. S{sub N} of chymotrypsinogen A and concanavalin A increases by 1.6- and 1.7-fold (277 to 295 K), while the hits increase from 37.5% to 54.2% and 43.3% to 73.4%, respectively. Such an excellent agreement strongly supports the validity of protein 'relative crystallizability', and crystallization screening at several temperatures can significantly increase the success for most proteins. A new protein epididymal-specific lipocalin was crystallized by varying temperature, yielding quickly the first crystals, and complete data sets have been collected at 1.97 {angstrom}.

  9. Wavelength resolved specific optical rotations and homochiral equilibria.

    PubMed

    Polavarapu, P L; Covington, C L

    2015-09-01

    The fundamental expressions governing specific optical rotations (SORs) of homochiral systems exhibiting monomer-dimer equilibria are presented. These equations are then utilized with the experimental measurements of wavelength resolved circular birefringence for (R)-(-)-α-hydroxy-β,β-dimethyl-γ-butyrolactone, to determine the wavelength resolved SORs of monomer and dimer components for the first time. Density functional theory predictions on the corresponding dispersion properties of monomer and dimer are found to match with experimentally determined quantities within a factor of ∼2. The wavelength resolved circular birefringence in the liquid solution phase thus provides a powerful means to investigate the molecular properties involved in homochiral equilibria. PMID:26227210

  10. Engineering study TWRS privatization phase I roads and rail system modifications

    SciTech Connect

    Ackerman, R.L.

    1996-09-30

    The DOE-RL is pursuing a new business strategy of hiring private contractors for treatment of Hanford Site tank wastes. This strategy is called privatization and includes design, permitting , construction, operation and deactivation of facilities for tank waste treatment. The TWRS Privatization Infrastructure Project is part of the first phase of the initiative. It consists of several sub-projects which will provide key physical interfaces and services needed to support the privatization mission. One sub-project is to establish transport system changes needed to support the privatization initiative. Specifically, this study identifies the road and rail system modifications needed to service the privatization site in 2OOE; an area previously developed and characterized for Grout Disposal.

  11. Phase Equilibria of ``Cu2O''-``FeO''-CaO-MgO-Al2O3 Slags at PO2 of 10-8.5 atm in Equilibrium with Metallic Copper for a Copper Slag Cleaning Production

    NASA Astrophysics Data System (ADS)

    Henao, Hector M.; Pizarro, Claudio; Font, Jonkion; Moyano, Alex; Hayes, Peter C.; Jak, Evgueni

    2010-12-01

    Limited data are available on phase equilibria of the multicomponent slag system at the oxygen partial pressures used in the copper smelting, converting, and slag-cleaning processes. Recently, experimental procedures have been developed and have been applied successfully to characterize several complex industrial slags. The experimental procedures involve high-temperature equilibration on a substrate and quenching followed by electron probe X-ray microanalysis. This technique has been used to construct the liquidus for the “Cu2O”-“FeO”-SiO2-based slags with 2 wt pct of CaO, 0.5 wt pct of MgO, and 4.0 wt pct of Al2O3 at controlled oxygen partial pressures in equilibrium with metallic copper. The selected ranges of compositions and temperatures are directly relevant to the copper slag-cleaning processes. The new experimental equilibrium results are presented in the form of ternary sections and as a liquidus temperature vs Fe/SiO2 weight ratio diagram. The experimental results are compared with the FactSage thermodynamic model calculations.

  12. Vent fluid chemistry of the Rainbow hydrothermal system (36°N, MAR): Phase equilibria and in situ pH controls on subseafloor alteration processes

    NASA Astrophysics Data System (ADS)

    Seyfried, W. E., Jr.; Pester, Nicholas J.; Ding, Kang; Rough, Mikaella

    2011-03-01

    -fluid equilibria. Indeed, the predicted correlation between dissolved silica and H 2 defines a trend that is in good agreement with vent fluid data from Rainbow and other high-temperature ultramafic-hosted hydrothermal systems. We speculate that the moderate concentrations of dissolved silica in vent fluids from these systems result from hydrothermal alteration of plagioclase and olivine in the form of subsurface gabbroic intrusions, which, in turn are variably replaced by chlorite + magnetite + talc ± tremolite, with important implications for pH lowering, dissolved sulfide concentrations, and metal mobility.

  13. Stable and Metastable Equilibria in the Pb-Cd System

    NASA Astrophysics Data System (ADS)

    Chuang, Ying-Yu; Paik, J.-S.; Zhang, C.; Perepezko, J. H.; Chang, Y. A.

    2013-07-01

    Thermodynamic and phase diagram data in the Pb-Cd system are reevaluated. A substitutional solution model is used for the liquid and fcc and hcp phases. The stable and metastable equilibria of this system are calculated using the thermodynamic equations derived from equilibrium data. Besides the well-established eutectic reaction at 521 K (248 °C), one stable monotectic reaction at 548 K (275 °C) is found due to the existence of a stable liquid miscibility gap. The stable monotectic reaction has been missed in all previous evaluations. Experimental verifications of the stable and metastable phase equilibria are provided using droplet samples and undercooled liquid alloys. A differential thermal analysis (DTA) method is applied to determine the phase reaction temperatures using both traditional heating and cooling processes and a specially designed cycling process. Additional microstructural evidence is used to elucidate the nature of the phase reactions. The refined thermodynamic descriptions are based upon both the thermochemical and phase diagram stable and metastable data. The agreement between the calculated and experimental data is good. All experimental stable and metastable results are well explained by the new Pb-Cd phase diagram calculations within the experimental accuracy limits. Combined experimental and thermodynamic modeling procedures developed for determining the stable and metastable phase equilibria yield a highly reliable overall phase diagram assessment and a quantitative basis for the interpretation of non-equilibrium solidification processing.

  14. Sulfate Mineral Phase Equilibria as a Function of Relative Humidity. Intermediate Compositions in the (Mg,Fe,Cu)SO4-H2O System at 1 atm

    NASA Astrophysics Data System (ADS)

    Anderson, J. L.; Peterson, R. C.

    2007-07-01

    Careful characterization of minerals present at the martian surface requires a detailed understanding of hydrous sulfate phase relationships. This study explores the effect of metal substitution on the hydration behaviour of hydrous metal sulfates.

  15. K-feldspar-muscovite-andalusite-quartz-brine phase equilibria: An experimental study at 25 to 60 MPa and 400 to 550 C

    SciTech Connect

    Frank, M.R.; Candela, P.A.; Piccoli, P.M.

    1998-12-01

    Felsic magmas may evolve one or more water or chlorine-rich fluid phases which can transport heat and solutes into associated hydrothermal systems and can contribute to alteration and ore deposition. To understand the role of a high-salinity aqueous phase in the magmatic hydrothermal environment, the composition of a subcritical, vapor-undersaturated high-salinity liquid phase (brine) in equilibrium with K-feldspar-muscovite-quartz and muscovite-andalusite-quartz was determined for pressures and temperatures ranging from 25 MPa and 400 C to 60 MPa and 550 C, with total Cl (NaCl + KCl + HCl) concentrations ranging from 3.42 to 8.56 (moles of solute/kg solution). Comparison of results with previous studies conducted at higher pressures and lower-salinity aqueous phases show that the mineral stability fields in the K-feldspar-muscovite-andalusite-quartz system shift to lower KCl/KCl values with increasing salinity and decreasing pressure.

  16. Experimental Investigation and Thermodynamic Assessment of Phase Equilibria in the PLLA/Dioxane/Water Ternary System for Applications in the Biomedical Field.

    PubMed

    Ruggiero, Flavia; Netti, Paolo Antonio; Torino, Enza

    2015-12-01

    Fundamental understanding of thermodynamic of phase separation plays a key role in tuning the desired features of biomedical devices. In particular, phase separation of ternary solution is of remarkable interest in processes to obtain biodegradable and biocompatible architectures applied as artificial devices to repair, replace, or support damaged tissues or organs. In these perspectives, thermally induced phase separation (TIPS) is the most widely used technique to obtained porous morphologies and, in addition, among different ternary systems, polylactic acid (PLLA)/dioxane/water has given promising results and has been largely studied. However, to increase the control of TIPS-based processes and architectures, an investigation of the basic energetic phenomena occurring during phase separation is still required. Here we propose an experimental investigation of the selected ternary system by using isothermal titration calorimetric approach at different solvent/antisolvent ratio and a thermodynamic explanation related to the polymer-solvents interactions in terms of energetic contribution to the phase separation process. Furthermore, relevant information about the phase diagrams and interaction parameters of the studied systems are furnished in terms of liquid-liquid miscibility gap. Indeed, polymer-solvents interactions are responsible for the mechanism of the phase separation process and, therefore, of the final features of the morphologies; the knowledge of such data is fundamental to control processes for the production of membranes, scaffolds and several nanostructures. The behavior of the polymer at different solvent/nonsolvent ratios is discussed in terms of solvation mechanism and a preliminary contribution to the understanding of the role of the hydrogen bonding in the interface phenomena is also reported. It is the first time that thermodynamic data of a ternary system are collected by mean of nano-isothermal titration calorimetry (nano-ITC). Supporting

  17. Microstructural study of phase equilibria in the Fe-Ca-O system involving CaFe/sub 5/O/sub 7/

    SciTech Connect

    Bergman, B.; Song, C. )

    1989-08-01

    By microscopic studies it is found that CaFe/sub 5/O/sub 7/ (often represented by CW/sub 3/F) does not disappear by decomposition to three solid phases at about 1050{sup 0}C, as suggested by previous phase diagrams. Instead it disappears by melting at about 1100{sup 0}C. On cooling, part of the liquid solidifies to a eutectic structure, wustite + Ca/sub 2/Fe/sub 2/O/sub 5/ (often represented by C/sub 2/F). A revision of Turkdogan's oxygen potential-temperature diagram is proposed in order to account for the new information.

  18. Effects of energetic particle phase space modifications by instabilities on integrated modeling

    NASA Astrophysics Data System (ADS)

    Podestà, M.; Gorelenkova, M.; Fredrickson, E. D.; Gorelenkov, N. N.; White, R. B.

    2016-11-01

    Tokamak plasmas can feature a large population of energetic particles (EP) from neutral beam injection or fusion reactions. In turn, energetic particles can drive instabilities, which affect the driving EP population leading to a distortion of the original EP distribution function and of quantities that depend on it. The latter include, for example, neutral beam (NB) current drive and plasma heating through EP thermalization. Those effects must be taken into account to enable reliable and quantitative simulations of discharges for present devices as well as predictions for future burning plasmas. Reduced models for EP transport are emerging as an effective tool for long time-scale integrated simulations of tokamak plasmas, possibly including the effects of instabilities on EP dynamics. Available models differ in how EP distribution properties are modified by instabilities, e.g. in terms of gradients in real or phase space. It is therefore crucial to assess to what extent different assumptions in the transport models affect predicted quantities such as EP profile, energy distribution, NB driven current and energy/momentum transfer to the thermal populations. A newly developed kick model, which includes modifications of the EP distribution by instabilities in both real and velocity space, is used in this work to investigate these issues. Coupled to TRANSP simulations, the kick model is used to analyze NB-heated NSTX and DIII-D discharges featuring unstable Alfvén eigenmodes (AEs). Results show that instabilities can strongly affect the EP distribution function, and modifications propagate to macroscopic quantities such as NB-driven current profile and NB power transferred to the thermal plasma species. Those important aspects are only qualitatively captured by simpler fast ion transport models that are based on radial diffusion of energetic ions only.

  19. Nucleophilic substitution in preparation and surface modification of hypercrosslinked stationary phases.

    PubMed

    Janků, Simona; Škeříková, Veronika; Urban, Jiří

    2015-04-01

    Four linear diaminoalkanes (1,2-diaminoethane, 1,4-diaminobutane, 1,6-diaminohexane, and 1,8-diaminooctane) have been used to hypercrosslink poly(styrene-co-vinylbenzyl chloride-co-divinylbenzene) monolithic stationary phases by nucleophilic substitution reaction. The column efficiency of polymer monoliths improved with longer diaminoalkane with 1,8-diaminoctane providing the highest efficiency. The concentration of 1,8-diaminoctane, together with hypercrosslinking time and temperature has been optimized. To improve the permeability of prepared columns, the hypercrosslinking modification has been combined with an early termination of polymerization reaction and decrease in polymerization temperature. The optimal column has been prepared by a polymerization reaction for 2h at 65°C and hypercrosslinked in the presence of 3% 1,8-diaminooctane for 2h at 95°C. The repeatability study of the presented protocol provided relative standard deviation for nine columns prepared independently out of three individual polymerization mixtures in between 2.0-12.0% for retention factors and 1.5-6.5% for plate heights, respectively. Further, we have modified residual chloromethyl groups with 2-aminoethanesulfonic acid (taurine) to prepare monolithic columns suitable for separation of small polar molecules in hydrophilic interaction chromatography. The highest retention of polar thiourea showed the column modified at 70°C for 20 h. Taurine-modified hypercrosslinked column showed the minimum of van Deemter curve of 20 μm. The prepared column provided dual-retention mechanism, including hydrophilic interaction and reversed-phase liquid chromatography that can be controlled by the composition of the mobile phase. The prepared column has been successfully used for an isocratic separation of low-molecular phenolic acids. PMID:25728663

  20. Equilibria in Quantitative Reachability Games

    NASA Astrophysics Data System (ADS)

    Brihaye, Thomas; Bruyère, Véronique; de Pril, Julie

    In this paper, we study turn-based quantitative multiplayer non zero-sum games played on finite graphs with reachability objectives. In this framework each player aims at reaching his own goal as soon as possible. We prove existence of finite-memory Nash (resp. secure) equilibria in multiplayer (resp. two-player) games.

  1. A new equation of state of a flexible-chain polyelectrolyte solution: Phase equilibria and osmotic pressure in the salt-free case

    NASA Astrophysics Data System (ADS)

    Budkov, Yu. A.; Kolesnikov, A. L.; Georgi, N.; Nogovitsyn, E. A.; Kiselev, M. G.

    2015-05-01

    We develop a first-principle equation of state of salt-free polyelectrolyte solution in the limit of infinitely long flexible polymer chains in the framework of a field-theoretical formalism beyond the linear Debye-Hueckel theory and predict a liquid-liquid phase separation induced by a strong correlation attraction. As a reference system, we choose a set of two subsystems—charged macromolecules immersed in a structureless oppositely charged background created by counterions (polymer one component plasma) and counterions immersed in oppositely charged background created by polymer chains (hard-core one component plasma). We calculate the excess free energy of polymer one component plasma in the framework of modified random phase approximation, whereas a contribution of charge densities' fluctuations of neutralizing backgrounds we evaluate at the level of Gaussian approximation. We show that our theory is in a very good agreement with the results of Monte Carlo and MD simulations for critical parameters of liquid-liquid phase separation and osmotic pressure in a wide range of monomer concentration above the critical point, respectively.

  2. Investigations on the phase equilibria of some hydride ion conducting electrolyte systems and their application for hydrogen monitoring in sodium coolant

    NASA Astrophysics Data System (ADS)

    Joseph, Kitheri; Sujatha, K.; Nagaraj, S.; Mahendran, K. H.; Sridharan, R.; Periaswami, G.; Gnanasekaran, T.

    2005-09-01

    Electrochemical meters for measuring hydrogen levels in liquid sodium need thermodynamically stable hydride ion conducting electrolytes. In order to identify electrolytes that have high hydride ion conductivity, phase diagram of systems consisting of low melting compounds such as CaCl 2-LiCl, SrBr 2-LiBr, SrBr 2-SrHBr and CaBr 2-CaHBr were investigated by differential scanning calorimetry and their phase diagrams established. Using these information and supplementary information on effects of addition of alkaline earth hydride to these systems, potential electrolytes were tested for their use in electrochemical meters. Meters were constructed using electrolytes with (i) 22mol%SrCl 2-12.2mol%CaCl 2-54.5mol%LiCl-11.3mol%CaHCl, (ii) 70mol%LiCl-16mol%CaHCl-14mol%CaCl 2 and (iii) 40mol%CaHBr-60mol%CaBr 2 compositions. Output of meters that had Li ions in liquid phase electrolyte showed non-linearity at low hydrogen levels. Output of meters using CaBr 2-40mol%CaHBr solid showed linearity in the concentration range of 50-250 ppb in sodium.

  3. Study of improved methods for predicting chemical equilibria. Final technical report, April 1, 1993--August 31, 1997

    SciTech Connect

    Lenz, T.G.; Vaughan, J.D.

    1997-10-01

    A long-standing goal of chemical engineers and chemists has been the development of techniques for accurate prediction of the thermodynamic properties of isolated molecules. The thermochemical functions for an ideal gas then provide a means of computing chemical equilibria, and such computations can be extended to condensed phase chemical equilibria with appropriate physical property data. Such capability for predicting diverse chemical equilibria is important in today`s competitive international economic environment, where bringing new products to market rapidly and efficiently is crucial. The purpose of this project has been to develop such computational methods for predicting chemical equilibria.

  4. Spontaneous Decay of Periodic Magnetostatic Equilibria.

    PubMed

    East, William E; Zrake, Jonathan; Yuan, Yajie; Blandford, Roger D

    2015-08-28

    In order to understand the conditions that lead to a highly magnetized, relativistic plasma becoming unstable, and in such cases how the plasma evolves, we study a prototypical class of magnetostatic equilibria in which the magnetic field satisfies ∇×B=αB, where α is spatially uniform, on a periodic domain. Using numerical solutions, we show that generic examples of such equilibria are unstable to ideal modes (including incompressible ones), which are marked by exponential growth in the linear phase. We characterize the unstable mode, showing how it can be understood in terms of merging magnetic and current structures, and explicitly demonstrate its instability using the energy principle. Following the nonlinear evolution of these solutions, we find that they rapidly develop regions with relativistic velocities and electric fields of comparable magnitude to the magnetic field, liberating magnetic energy on dynamical time scales and eventually settling into a configuration with the largest allowable wavelength. These properties make such solutions a promising setting for exploring the mechanisms behind extreme cosmic sources of gamma rays. PMID:26371660

  5. Spontaneous decay of periodic magnetostatic equilibria

    SciTech Connect

    East, William E.; Zrake, Jonathan; Yuan, Yajie; Blandford, Roger D.

    2015-08-28

    In order to understand the conditions which lead a highly magnetized, relativistic plasma to become unstable, and in such cases how the plasma evolves, we study a prototypical class of magnetostatic equilibria where the magnetic field satisfies ∇ x B = αB , where \\alpha is spatially uniform, on a periodic domain. Using numerical solutions we show that generic examples of such equilibria are unstable to ideal modes (including incompressible ones) which are marked by exponential growth in the linear phase. We characterize the unstable mode, showing how it can be understood in terms of merging magnetic and current structures, and explicitly demonstrate its instability using the energy principle. Following the nonlinear evolution of these solutions, we find that they rapidly develop regions with relativistic velocities and electric fields of comparable magnitude to the magnetic field, liberating magnetic energy on dynamical timescales and eventually settling into a configuration with the largest allowable wavelength. Furthermore, these properties make such solutions a promising setting for exploring the mechanisms behind extreme cosmic sources of gamma rays.

  6. Spontaneous Decay of Periodic Magnetostatic Equilibria.

    PubMed

    East, William E; Zrake, Jonathan; Yuan, Yajie; Blandford, Roger D

    2015-08-28

    In order to understand the conditions that lead to a highly magnetized, relativistic plasma becoming unstable, and in such cases how the plasma evolves, we study a prototypical class of magnetostatic equilibria in which the magnetic field satisfies ∇×B=αB, where α is spatially uniform, on a periodic domain. Using numerical solutions, we show that generic examples of such equilibria are unstable to ideal modes (including incompressible ones), which are marked by exponential growth in the linear phase. We characterize the unstable mode, showing how it can be understood in terms of merging magnetic and current structures, and explicitly demonstrate its instability using the energy principle. Following the nonlinear evolution of these solutions, we find that they rapidly develop regions with relativistic velocities and electric fields of comparable magnitude to the magnetic field, liberating magnetic energy on dynamical time scales and eventually settling into a configuration with the largest allowable wavelength. These properties make such solutions a promising setting for exploring the mechanisms behind extreme cosmic sources of gamma rays.

  7. Spontaneous decay of periodic magnetostatic equilibria

    DOE PAGES

    East, William E.; Zrake, Jonathan; Yuan, Yajie; Blandford, Roger D.

    2015-08-28

    In order to understand the conditions which lead a highly magnetized, relativistic plasma to become unstable, and in such cases how the plasma evolves, we study a prototypical class of magnetostatic equilibria where the magnetic field satisfies ∇ x B = αB , where \\alpha is spatially uniform, on a periodic domain. Using numerical solutions we show that generic examples of such equilibria are unstable to ideal modes (including incompressible ones) which are marked by exponential growth in the linear phase. We characterize the unstable mode, showing how it can be understood in terms of merging magnetic and current structures,more » and explicitly demonstrate its instability using the energy principle. Following the nonlinear evolution of these solutions, we find that they rapidly develop regions with relativistic velocities and electric fields of comparable magnitude to the magnetic field, liberating magnetic energy on dynamical timescales and eventually settling into a configuration with the largest allowable wavelength. Furthermore, these properties make such solutions a promising setting for exploring the mechanisms behind extreme cosmic sources of gamma rays.« less

  8. EQUILGAS: Program to estimate temperatures and in situ two-phase conditions in geothermal reservoirs using three combined FT-HSH gas equilibria models

    NASA Astrophysics Data System (ADS)

    Barragán, Rosa María; Núñez, José; Arellano, Víctor Manuel; Nieva, David

    2016-03-01

    Exploration and exploitation of geothermal resources require the estimation of important physical characteristics of reservoirs including temperatures, pressures and in situ two-phase conditions, in order to evaluate possible uses and/or investigate changes due to exploitation. As at relatively high temperatures (>150 °C) reservoir fluids usually attain chemical equilibrium in contact with hot rocks, different models based on the chemistry of fluids have been developed that allow deep conditions to be estimated. Currently either in water-dominated or steam-dominated reservoirs the chemistry of steam has been useful for working out reservoir conditions. In this context, three methods based on the Fischer-Tropsch (FT) and combined H2S-H2 (HSH) mineral-gas reactions have been developed for estimating temperatures and the quality of the in situ two-phase mixture prevailing in the reservoir. For these methods the mineral buffers considered to be controlling H2S-H2 composition of fluids are as follows. The pyrite-magnetite buffer (FT-HSH1); the pyrite-hematite buffer (FT-HSH2) and the pyrite-pyrrhotite buffer (FT-HSH3). Currently from such models the estimations of both, temperature and steam fraction in the two-phase fluid are obtained graphically by using a blank diagram with a background theoretical solution as reference. Thus large errors are involved since the isotherms are highly nonlinear functions while reservoir steam fractions are taken from a logarithmic scale. In order to facilitate the use of the three FT-HSH methods and minimize visual interpolation errors, the EQUILGAS program that numerically solves the equations of the FT-HSH methods was developed. In this work the FT-HSH methods and the EQUILGAS program are described. Illustrative examples for Mexican fields are also given in order to help the users in deciding which method could be more suitable for every specific data set.

  9. The clathrate Ba{sub 8}Cu{sub x}Ge{sub 46-x-y}square{sub y}: Phase equilibria and crystal structure

    SciTech Connect

    Melnychenko-Koblyuk, Nataliya; Grytsiv, Andriy; Rogl, Peter; Schmid, Harald; Giester, Gerald

    2009-07-15

    Phase relations at 700 deg. C, 800 deg. C and solidus temperatures have been derived for the clathrate system Ba{sub 8}Cu{sub x}Ge{sub 46-x-y}square{sub y} via X-ray single crystal and powder diffractometry combined with electron probe micro analysis and differential thermal analysis. The ternary clathrate phase derives from binary Ba{sub 8}Ge{sub 43}square{sub 3} and extends up to x=6. Structure investigations define cubic primitive symmetry with the space group type Pm3-barn consistent with a clathrate type I structure throughout the entire homogeneity region 0=5.5. - Graphical Abstract: Cages and atom thermal displacement parameters in clathrate Ba{sub 8}Cu{sub x}Ge{sub 46-x-y}square{sub y} for Ba{sub 8}Cu{sub 2}Ge{sub 42}square{sub 2} and Ba{sub 8}Cu{sub 6}Ge{sub 40}.

  10. Surface modification induced phase transformation and structure variation on the rapidly solidified recast layer of titanium

    SciTech Connect

    Tsai, Ming-Hung; Haung, Chiung-Fang; Shyu, Shih-Shiun; Chou, Yen-Ru; Lin, Ming-Hong; Peng, Pei-Wen; and others

    2015-08-15

    In this study, neodymium-doped yttrium orthovanadate (Nd:YVO{sub 4}) as a laser source with different scanning speeds was used on biomedical Ti surface. The microstructural and biological properties of laser-modified samples were investigated by means of optical microscope, electron microscope, X-ray diffraction, surface roughness instrument, contact angle and cell cytotoxicity assay. After laser modification, the rough volcano-like recast layer with micro-/nanoporous structure and wave-like recast layer with nanoporous structure were generated on the surfaces of laser-modified samples, respectively. It was also found out that, an α → (α + rutile-TiO{sub 2}) phase transition occurred on the recast layers of laser-modified samples. The Ti surface becomes hydrophilic at a high speed laser scanning. Moreover, the cell cytotoxicity assay demonstrated that laser-modified samples did not influence the cell adhesion and proliferation behaviors of osteoblast (MG-63) cell. The laser with 50 mm/s scanning speed induced formation of rough volcano-like recast layer accompanied with micro-/nanoporous structure, which can promote cell adhesion and proliferation of MG-63 cell on Ti surface. The results indicated that the laser treatment was a potential technology to enhance the biocompatibility for titanium. - Highlights: • Laser induced the formation of recast layer with micro-/nanoporous structure on Ti. • An α → (α + rutile-TiO{sub 2}) phase transition was observed within the recast layer. • The Ti surface becomes hydrophilic at a high speed laser scanning. • Laser-modified samples exhibit good biocompatibility to osteoblast (MG-63) cell.

  11. Crystal chemistry and phase equilibria of the CaO-½Eu2O3-CoOz system at 885 °C

    NASA Astrophysics Data System (ADS)

    Wong-Ng, W.; Laws, W.; Kaduk, J. A.

    2016-08-01

    The CaO-½Eu2O3-CoOz system prepared at 885 °C in air consists of two calcium cobaltate compounds, namely, the 2D thermoelectric oxide solid solution, (Ca3-xEux)Co4O9-z (0 ≤ x ≤ 0.5) which has a misfit layered structure, and the 1D Ca3Co2O6 compound which consists of chains of alternating CoO6 trigonal prisms and CoO6 octahedra. Ca3Co2O6 was found to be a point compound without the substitution of Eu on the Ca site when prepared at 885 °C. A solid solution region of distorted perovskite, (Eu1-xCax)CoO3-z (0 ≤ x ≤ 0.22, space group Pnma) was established. The (Eu0.91(1)Ca0.09(1))CoO3-z perovskite member has a distorted structure with tilt angles θ (17.37°), ϕ (8.20°), and ω (19.16°) which represent rotations of an octahedron about the pseudo-cubic perovskite [110]p, [001]p and [111]p axes. The reported Eu2CoO4 phase was not observed at 885 °C, but a ternary Ca-doped oxide, (Eu1+xCa1-x)CoO4-z (Bmab) where 0 ≤ x ≤ 0.10 was found to be stable at this temperature. In the peripheral binary systems, Eu was not present in the Ca site of CaO, while a small solid solution region was identified for (Eu1-xCax)O(3-z)/2 (0 ≤ x ≤ 0.05). Seven solid solution tie-line regions and six three-phase regions were determined in the CaO-½Eu2O3-CoOz system in air.

  12. Phase equilibria and crystal chemistry of the CaO-½Sm2O3-CoOz system at 885 °C in air

    NASA Astrophysics Data System (ADS)

    Wong-Ng, W.; Laws, W.; Lapidus, S. H.; Kaduk, J. A.

    2015-10-01

    The CaO-½Sm2O3-CoOz system prepared at 885 °C in air consists of two calcium cobaltate compounds, namely, the 2D thermoelectric oxide solid solution, (Ca3-xSmx)Co4O9-z (0 ≤ x ≤ 0.5) which has a misfit layered structure, and the 1D Ca3Co2O6 which consists of chains of alternating CoO6 trigonal prisms and CoO6 octahedra. Ca3Co2O6 was found to be a point compound without the substitution of Sm on the Ca site. A solid solution region of distorted perovskite, (Sm1-xCax)CoO3-z (0 ≤ x ≤ 0.22, space group Pnma) was established. The reported Sm2CoO4 phase was not observed at 885 °C, but a ternary Ca-doped oxide, (Sm1+xCa1-x)CoO4-z (Bmab) where 0 < x ≤ 0.15 was found to be stable at this temperature. In the peripheral binary systems, Sm was not present in the Ca site of CaO, while a small solid solution region was identified for (Sm1-xCax)O(3-z)/2 (0 ≤ x ≤ 0.075). Ten solid solution tie-line regions and six three-phase regions were determined in the CaO-½Sm2O3-CoOz system in air.

  13. Phase equilibria in the Tb-Mg-Co system at 500 °C, crystal structure and hydrogenation properties of selected compounds

    NASA Astrophysics Data System (ADS)

    Shtender, V. V.; Denys, R. V.; Zavaliy, I. Yu.; Zelinska, O. Ya.; Paul-Boncour, V.; Pavlyuk, V. V.

    2015-12-01

    The isothermal section of the Tb-Mg-Co phase diagram at 500 °C has been built on the basis of XRD analysis of forty samples prepared by powder metallurgy. The existence of two ternary compounds Tb4Mg3Co2 and Tb4MgCo was confirmed. The formation of two solid solutions, Tb1-xMgxCo3 (0≤x≤0.4) and Tb1--xMgxCo2 (0≤x≤0.6), was found for the first time. It is shown that Tb5Mg24 also dissolves a small amount of Co. Other binary compounds do not dissolve the third component. The Tb4MgCo and TbMgCo4 compounds form hydrides (12.7 and 5.3 at.H/f.u. capacity, respectively) that retain the original structure of metallic matrices. Upon thermal desorption the Tb4MgCoH12.7 hydride was stable up to 300 °C and disproportionated at higher temperature. Two other hydrides, Tb4Mg3Co2H∼4 and Tb2MgCo9H12, are unstable in air and decompose into the initial compounds.

  14. Scapolite phase equilibria and carbon isotope variations in high grade rocks: Tests of the CO sub 2 -flooding hypothesis of granulite gneiss

    SciTech Connect

    Moecher, D.P.

    1988-01-01

    Scapolite decarbonation reactions and carbon isotope analysis of CO{sub 2} extracted from scapolite are used to determine the presence, composition, and source of fluid components in high grade rocks. Scapolite-plagioclase-garnet-quartz assemblages, common to many lithologies in high grade terranes, monitors CO{sub 2} activity (aCO{sub 2}) by the reaction 2 Meionite + Quarts = 5 Anorthite + Grossular + 2 CO{sub 2}. The P-T-X location of this reaction was calculated using an internally consistent thermodynamic data set for meionite and phases in the CASCH system. Activity-composition relations for meionite in scapolite were calculated from the thermodynamic data set and compositional data on natural scapolite-plagioclase-calcite assemblages. Equilibration pressures of scapolite assemblages were calculated from clinopyroxene-garnet-plagioclass-quartz barometers calibrated for this study. The aCO{sub 2} was calculated for a variety of high grade gneisses from the southwestern Grenville Province and other terranes. Granulites typically yield low to moderate values of aCO{sub 2} (less than 0.5). Calc-silicates and meta-anorthosite yield moderate aCO{sub 2}. Deep crustal xenoliths yield a range of aCO{sub 2}.

  15. Two-population replicator dynamics and number of Nash equilibria in matrix games

    NASA Astrophysics Data System (ADS)

    Galla, T.

    2007-04-01

    We study the connection between the evolutionary replicator dynamics and the number of Nash equilibria in large random bi-matrix games. Using techniques of disordered systems theory we compute the statistical properties of both, the fixed points of the dynamics and the Nash equilibria. Except for the special case of zero-sum games, one finds a transition as a function of the so-called co-operation pressure between a phase in which there is a unique stable fixed point of the dynamics coinciding with a unique Nash equilibrium, and an unstable phase in which there are exponentially many Nash equilibria with statistical properties different from the stationary state of the replicator equations. Our analytical results are confirmed by numerical simulations of the replicator dynamics, and by explicit enumeration of Nash equilibria.

  16. Posttranslational modification of Birch and Ragweed allergen proteins by common gas phase pollutants, NO2 and O3

    NASA Astrophysics Data System (ADS)

    Mahmood, M. A.; Pope, F.; Bloss, W.

    2015-12-01

    The global incidence of hay fever has been rising for decades, however, the underlying reasons behind this rise remain unclear. It is hypothesized that exposure of pollen to common gas phase pollutants, such as nitrogen dioxide (NO2) and ozone (O3), increases the allergenicity of the pollen and thus increases hay fever incidence. Since atmospheric pollutants tend to have greater concentrations within urban areas (in particular NO2) the hypothesis suggests that greater allergenicity should occur in urban areas. Indeed, several studies do suggest higher hay fever incidence within urban areas compared to rural areas. Previous published work suggests a link between increased allergies with changes in the chemical composition of the pollen protein via posttranslational modification of the protein. This study investigates the posttranslational modification of two highly allergenic pollen species (Birch and Ragweed) that are common in Europe. Within the laboratory, we expose pollen grains to atmospherically relevant exposures of gas phase NO2, O3 and other common gas phase oxidants under a range of environmentally relevant conditions. The effects of the environmentally relevant exposures on the biochemistry of the pollen grains were probed using a proteomic approach (liquid chromatography coupled ultra-high resolution spectrometer). Our findings indicate the interaction between gas phase pollutants and pollen cause protein specific modifications; in particular, nitration occurs upon tyrosine residues and nitrosylation on cysteine residues. Possibly, these modifications may affect the immune response of the pollen protein, which may suggest a possible reason for increased allergies in reaction to such biologically altered protein. The laboratory-derived results will be supported with a time series analysis of asthma incidence rates for the London area, which take into account the pollen count, and pollutant concentrations. The implications of the results will be discussed

  17. Estimation of Fluid Properties and Phase Equilibria.

    ERIC Educational Resources Information Center

    Herskowitz, M.

    1985-01-01

    Describes a course (given to junior/senior students with strong background in thermodynamics and transport phenomena) that covers the theoretical and practical aspects of properties estimation. An outline for the course is included. (JN)

  18. Phase equilibria of chlorofluorocarbon alternative refrigerant mixtures

    SciTech Connect

    Lee, B.G.; Park, J.Y.; Lim, J.S.; Cho, S.Y.; Park, K.Y.

    1999-03-01

    Isothermal vapor-liquid equilibrium data were determined for binary systems of difluoromethane/1,1,1,2-tetrafluoroethane (HFC-32/HFC-134a), difluoromethane/pentafluoroethane (HFC-32/HFC-125), difluoromethane/1,1,1-trifluoroethane (HFC-32/HFC-143A), and difluoromethane/1,1-difluoroethane (HFC-32/HFC-152a). The vapor and liquid compositions and pressures were measured in a circulation-type apparatus at 303.15 K and 323.15 K. The experimental data were compared with literature results and correlated with the Canahan-Starling-De Santis equation of state within the uncertainty of {+-}1.0%.

  19. Steady State Tokamak Equilibria without Current Drive

    SciTech Connect

    Shaing, K.C.; Aydemir, A.Y.; Lin-Liu, Y.R.; Miller, R.L.

    1997-11-01

    Steady state tokamak equilibria without current drive are found. This is made possible by including the potato bootstrap current close to the magnetic axis. Tokamaks with this class of equilibria do not need seed current or current drive, and are intrinsically steady state. {copyright} {ital 1997} {ital The American Physical Society}

  20. Genetically engineered charge modifications to enhance protein separation in aqueous two-phase systems: Charge directed partitioning

    SciTech Connect

    Luther, J.R.; Glatz, C.E.

    1995-04-05

    This report continues the authors` examination of the effect of genetically engineered charge modifications on the partitioning behavior of proteins in aqueous two-phase extraction. The genetic modifications consisted of the fusion of charged peptide tails to {beta}-galactosidase and charge-change point mutations to T4 lysozyme. In this study, they examined charge directed partitioning behavior in PEG/dextran systems containing small amounts of the charged polymers diethylaminoethyl-dextran (DEAE-dextran) or dextran sulfate. The best results were obtained when attractive forces between the protein and polymer were present. Nearly 100% of the {beta}-galactosidase, which carries a net negative charge, partitioned to the DEAE-dextran-rich phase regardless of whether the phase was dextran or PEG. In these cases, cloudiness of the protein-rich phases suggest that strong charge interactions resulted in protein/polymer aggregation, which may have contribution to the extreme partitioning. Unlike the potential-driven partitioning reported previously, consistent partitioning trends were observed as a result of the fusion tails, with observed shifts in partition coefficient (K{sub p}) of up to 37-fold. However, these changes could not be solely attributed to charge-based interactions.

  1. MHD equilibria with diamagnetic effects

    NASA Astrophysics Data System (ADS)

    Tessarotto, M.; Zorat, R.; Johnson, J. L.; White, R. B.

    1997-11-01

    An outstanding issue in magnetic confinement is the establishment of MHD equilibria with enhanced flow shear profiles for which turbulence (and transport) may be locally effectively suppressed or at least substantially reduced with respect to standard weak turbulence models. Strong flows develop in the presence of equilibrium E× B-drifts produced by a strong radial electric field, as well as due to diamagnetic contributions produced by steep equilibrium radial profiles of number density, temperature and the flow velocity itself. In the framework of a kinetic description, this generally requires the construction of guiding-center variables correct to second order in the relevant expansion parameter. For this purpose, the Lagrangian approach developed recently by Tessarotto et al. [1] is adopted. In this paper the conditions of existence of such equilibria are analyzed and their basic physical properties are investigated in detail. 1 - M. Pozzo, M. Tessarotto and R. Zorat, in Theory of fusion Plasmas, E.Sindoni et al. eds. (Societá Italiana di Fisica, Editrice Compositori, Bologna, 1996), p.295.

  2. Signaling equilibria in sensorimotor interactions.

    PubMed

    Leibfried, Felix; Grau-Moya, Jordi; Braun, Daniel A

    2015-08-01

    Although complex forms of communication like human language are often assumed to have evolved out of more simple forms of sensorimotor signaling, less attention has been devoted to investigate the latter. Here, we study communicative sensorimotor behavior of humans in a two-person joint motor task where each player controls one dimension of a planar motion. We designed this joint task as a game where one player (the sender) possesses private information about a hidden target the other player (the receiver) wants to know about, and where the sender's actions are costly signals that influence the receiver's control strategy. We developed a game-theoretic model within the framework of signaling games to investigate whether subjects' behavior could be adequately described by the corresponding equilibrium solutions. The model predicts both separating and pooling equilibria, in which signaling does and does not occur respectively. We observed both kinds of equilibria in subjects and found that, in line with model predictions, the propensity of signaling decreased with increasing signaling costs and decreasing uncertainty on the part of the receiver. Our study demonstrates that signaling games, which have previously been applied to economic decision-making and animal communication, provide a framework for human signaling behavior arising during sensorimotor interactions in continuous and dynamic environments. PMID:25935748

  3. Experimental determination of phase equilibria of a basalt from Piton de la Fournaise (La Réunion island): 1 atm data and high pressure results in presence of volatiles.

    NASA Astrophysics Data System (ADS)

    Brugier, Yann-Aurélien; Pichavant, Michel; di Muro, Andréa

    2015-04-01

    To understand the petrogenetic relations between the 4 groups of lavas erupted at Piton de la Fournaise (PdF), constrain the structure of the feeding system and the magma storage conditions, experimental phase equilibria have been determined, both at 1 atm and high pressures (HP), on a lava representative of Steady State Basalts (SSB). The lava (SiO2=49.2 wt%, MgO=7.8 wt%, CaO/Al2O3= 0.81) was fused at 1400°C, 1 atm in air. The resulting glass was crushed and the powder directly used as starting material. The 1atm experiments were performed with the wire-loop method in a vertical CO-CO2 gas mixing furnace. To minimize Fe-loss from the charge, experiments were repeated under constant T-fO2 conditions to progressively saturate the suspension wire with Fe. Intermediate charges were dissolved in HF and the charge from the last cycle retained for detailed study. Analyses of experimental products are in progress. The HP experiments were carried out in an internally heated pressure vessel, at 50MPa and 400MPa, between 1100-1200°C and under fluid-present conditions. Glass (30-50 mg) plus 10% in mass of volatiles (H2O or H2O+CO2) were loaded in Au80Pd20 capsules. Distilled water and Ag2C2O4 (CO2 source) were weighted to give charges with xH2O initial (molar H2O / (H2O+CO2)) ranging from 1 to 0. Run durations lasted for 2-14h. Redox conditions were controlled by loading a given proportion of H2 gas in the vessel (3 bar H2 for 50MPa, 5 bar H2 for 400MPa). Experimental fH2 were determined by solid Pd-Co sensors, leading to fO2 conditions approaching NNO-1. All experiments were rapidly drop quenched and products analyzed by SEM, EMPA and µ-FTIR Spectroscopy. To overcome Fe-loss, both capsule Fe pre-saturation and charge Fe pre-enrichment were tested. The first method was shown to be time-consuming and fraught with difficulties while the second is still being developed. Consequently, the experimental data presented here were obtained with no attempt to circumvent Fe loss

  4. Reversible phase-structure modification of photostructurable glass ceramic by CO2 laser irradiation

    NASA Astrophysics Data System (ADS)

    Sergeev, Maksim M.; Veiko, Vadim P.; Savochkin, Denis A.; Zakoldaev, Roman A.

    2016-10-01

    Structural changes and phase transformations of the photostructurable glass (PhG) surfaces under the impact of 10.6-μm wavelength laser radiation are examined. The regimes initiating the formation and development of crystalline phase and its reversible (secondary) amorphization are determined. In addition, the kinetic of crystalline phase formation and its melting on the surface of PhG are investigated. The characteristics of multiple reversible phase-structure transformations in the temperature range of 470-800 °C are investigated.

  5. Vapor-Liquid Equilibria Using the Gibbs Energy and the Common Tangent Plane Criterion

    ERIC Educational Resources Information Center

    Olaya, Maria del Mar; Reyes-Labarta, Juan A.; Serrano, Maria Dolores; Marcilla, Antonio

    2010-01-01

    Phase thermodynamics is often perceived as a difficult subject with which many students never become fully comfortable. The Gibbsian geometrical framework can help students to gain a better understanding of phase equilibria. An exercise to interpret the vapor-liquid equilibrium of a binary azeotropic mixture, using the equilibrium condition based…

  6. Hydrogen exchange equilibria in thiols.

    PubMed

    Hofstetter, Dustin; Thalmann, Basil; Nauser, Thomas; Koppenol, Willem H

    2012-09-17

    Cysteine, cysteinyl-glycine, glutathione, phenylalanyl-cysteinyl-glycine, and histidyl-cysteinyl-glycine were dissolved in acidic and neutral D(2)O in the presence of the radical generator 2,2'-azobis(2-methylpropionamidine) dihydrochloride and radical mediator compounds (benzyl alcohol and 2-propanol). An exchange of H-atoms by D-atoms took place in these peptides due to intramolecular H-abstraction equilibria. NMR measurements allow one to follow the extent of H-D exchanges and to identify the sites where these exchanges take place. Significant exchanges occur in acidic media in GSH at positions Glu-β and Glu-γ, in Phe-Cys-Gly at positions Phe ortho, Phe-β, Cys-α, Cys-β, and Gly-α, and in His-Cys-Gly at positions His H1, His H2, His β, Cys β, and Gly α. In neutral media, exchanges occur in Cys-Gly at position Cys β and in GSH at position Cys α. Phe-Cys-Gly and His-Cys-Gly were not examined in neutral media. Sites participating in the radical exchange equilibria are highly dependent on structure and pH; the availability of electron density in the form of lone pairs appears to increase the extent of exchange. Interestingly, and unexpectedly, 2D NMR experiments show that GSH rearranges itself in acidic solution: the signals shift, but their patterns do not change. The formation of a thiolactone from Gly and Cys residues matches the changes observed.

  7. Investigation of the phase equilibria and phase transformations associated with the Bi{sub 2}Sr{sub 2}CaCu{sub 2}O{sub y} superconductor

    SciTech Connect

    Holesinger, T.

    1993-12-09

    The solid solution region and reaction kinetics of the Bi{sub 2}Sr{sub 2}CaCu{sub 2}O{sub y} (2212) superconductor were examined as a function of temperature and oxygen partial pressure. Crystallization studies from the glassy and molten states were undertaken to determine the phase transformation and kinetics associated with the formation of 2212 and other competing phases. Crystallization of nominal 2212 glasses was found to proceed in two steps with the formation of Bi{sub 2}Sr{sub 2{minus}x}Ca{sub x}CuO{sub y} (2201) and Cu{sub 2}O followed by Bi{sub 2}Sr{sub 3{minus}x}Ca{sub x}O{sub y}, CaO, and SrO. The 2212 phase converts from the 2201 phase with increasing temperatures. However, its formation below 800 C was kinetically limited. At 800 C and above, a nearly full conversion to the 2212 phase was achieved after only one minute although considerably longer anneal times were necessary for the system to reach equilibrium. In low oxygen partial pressures, the solidus is reduced to approximately 750 C. Solidification studies revealed an eutectic structure separating the incongruently melting 2212/2201 phases at high oxygen partial pressures from the congruently melting Bi{sub 2}Sr{sub 3{minus}x}Ca{sub x}O{sub y} (23x) and Bi{sub 2}Sr{sub 2{minus}x}Ca{sub x}O{sub y} (22x) phases present at low oxygen partial pressures. During solidification in various oxygen partial pressures, the separation of CaO in the melt and the initial crystallization of alkaline-earth cuprates leaves behind a Bi-rich liquid from which it is impossible to form single-phase 2212. Hence, significant amounts of 2201 were also present in these samples. These problems could be reduced by melt processing in inert atmospheres. Bulk 2212 material produced in this manner was found to possess high transition temperatures, high intergranular critical current densities below 20K, and modest critical current densities at 77K.

  8. Modification of the phase structure of black D6 branes in a canonical ensemble and its origin

    NASA Astrophysics Data System (ADS)

    Lu, J. X.; Ouyang, Jun; Roy, Shibaji

    2014-09-01

    It is well known that charged black Dp branes of type II string theory share a universal phase structure of van der Waals-Maxwell liquid-gas type except D5 and D6 branes. Interestingly, the phase structure of D5 and D6 branes can be changed to the universal form with the inclusion of particular delocalized charged lower-dimensional branes. For D5 branes, one needs to introduce delocalized D1 branes, and for D6 branes, one needs to introduce delocalized D0 branes to obtain the universal structure. In a previous paper [J. High Energy Phys. 04 (2013) 100], Lu with Wei study the phase structure of black D6 branes with the introduction of delocalized D0 branes in a special case when their charges are equal and the dilaton charge vanishes. In this paper, we look at the phase structure of the black D6/D0 system with the generic values of the parameters, which makes the analysis more involved but the structure more rich. We also provide reasons why the respective modifications of the phase structures to the universal form for the black D5 and D6 branes occur when specific delocalized lower-dimensional branes are introduced.

  9. Investigation into the effects of modification of the passive phase for improved manufacture of 1-3 connectivity piezocomposite transducers.

    PubMed

    O'Leary, R L; Hayward, G

    1999-01-01

    The 1-3 connectivity composite transducers comprise active piezoceramic pillars within a passive polymer matrix. The first stage in manufacturing the 1-3 material is to produce a bristle block (comprising a solid stock of active material with protruding pillars) by injection moulding or by dicing a piece of ceramic using precision sawing equipment. The bristle block is filled with a reactive polymer liquid that produces the passive polymer phase, and the filled block is machined to the desired dimensions. For optimum performance, the polymer phase should have complementary interaction with the ceramic phase as well as imparting dimensional stability. Epoxy-based polymers are the most usual passive materials because of their low viscosity in the uncured state and solvent resistance, coupled with their excellent adhesive, mechanical, and electrical properties. However, the curing of epoxy resins results in shrinkage of the polymer matrix and internal stress within the passive phase. This can lead to prestressing of the active ceramic material, distortion of pillars, reduction in the parallelism between the sides of pillars, acid, in certain circumstances, warpage of transducers. This is particularly evident when the solid stock in the bristle block is relatively thin. This paper reports the in situ modification of epoxy in the bristle block by UV-based low temperature polymerization of acrylate monomers within the epoxy matrix prior to polymerization of the epoxy resin. Internal stress measurements are presented to quantify the influence of this modification via a reduction of internal stress within the polymer matrix. Results from finite element analysis emphasise the conclusions of the experimental work, and examples of manufactured devices are presented. Composite transducer performance is assessed by laser measurement of surface displacement profiles, and a 50% improvement in surface displacement magnitude was observed for the modified devices. PMID:18238451

  10. Symmetry transforms for ideal magnetohydrodynamics equilibria.

    PubMed

    Bogoyavlenskij, Oleg I

    2002-11-01

    A method for constructing ideal magnetohydrodynamics (MHD) equilibria is introduced. The method consists of the application of symmetry transforms to any known MHD equilibrium [ O. I. Bogoyavlenskij, Phys. Rev. E. 62, 8616, (2000)]. The transforms break the geometrical symmetries of the field-aligned solutions and produce continuous families of the nonsymmetric MHD equilibria. The method of symmetry transforms also allows to obtain MHD equilibria with current sheets and exact solutions with noncollinear vector fields B and V. A model of the nonsymmetric astrophysical jets outside of their accretion disks is developed. The total magnetic and kinetic energy of the jet is finite in any layer c(1)equilibria that model ball lightning with dynamics of plasma inside the fireball.

  11. Braided magnetic fields: equilibria, relaxation and heating

    NASA Astrophysics Data System (ADS)

    Pontin, D. I.; Candelaresi, S.; Russell, A. J. B.; Hornig, G.

    2016-05-01

    We examine the dynamics of magnetic flux tubes containing non-trivial field line braiding (or linkage), using mathematical and computational modelling, in the context of testable predictions for the laboratory and their significance for solar coronal heating. We investigate the existence of braided force-free equilibria, and demonstrate that for a field anchored at perfectly-conducting plates, these equilibria exist and contain current sheets whose thickness scales inversely with the braid complexity—as measured for example by the topological entropy. By contrast, for a periodic domain braided exact equilibria typically do not exist, while approximate equilibria contain thin current sheets. In the presence of resistivity, reconnection is triggered at the current sheets and a turbulent relaxation ensues. We finish by discussing the properties of the turbulent relaxation and the existence of constraints that may mean that the final state is not the linear force-free field predicted by Taylor’s hypothesis.

  12. Symmetry transforms for ideal magnetohydrodynamics equilibria.

    PubMed

    Bogoyavlenskij, Oleg I

    2002-11-01

    A method for constructing ideal magnetohydrodynamics (MHD) equilibria is introduced. The method consists of the application of symmetry transforms to any known MHD equilibrium [ O. I. Bogoyavlenskij, Phys. Rev. E. 62, 8616, (2000)]. The transforms break the geometrical symmetries of the field-aligned solutions and produce continuous families of the nonsymmetric MHD equilibria. The method of symmetry transforms also allows to obtain MHD equilibria with current sheets and exact solutions with noncollinear vector fields B and V. A model of the nonsymmetric astrophysical jets outside of their accretion disks is developed. The total magnetic and kinetic energy of the jet is finite in any layer c(1)equilibria that model ball lightning with dynamics of plasma inside the fireball. PMID:12513610

  13. Stability analysis of cylindrical Vlasov equilibria

    SciTech Connect

    Short, R W

    1980-02-01

    A method is presented for the fully kinetic, nonlocal stability analysis of cylindrically symmetric equilibria. Applications to the lower hybrid drift instability and the modes associated with a finite-width relativistic E-layer are discussed.

  14. Equilibria of Constantin Popovici's Photogravitational Model Revisited

    NASA Astrophysics Data System (ADS)

    Mioc, Vasile

    The equilibria of the two-body problem associated to Constantin Popovici's photogravitational model are tackled again. We consider the motion in the infinity-blow-up coordinates provided by McGehee-type transformations. Then we study the vector field expressed in collision-regularizing Levi-Civita coordinates. This new framework provides the same location of the equilibria and the same information about their nature as the previous approaches.

  15. Equilibria of Seeliger's Problem. Analytic Approach

    NASA Astrophysics Data System (ADS)

    Popescu, E.; Pasca, D.; Mioc, V.; Popescu, N. A.

    2010-09-01

    We offer a deeper insight into the two-body problem associated to Seeliger's potential. We resort to McGehee-type transformations to write the motion equations and the integrals of energy and angular momentum. Then we search for equilibria, considering the whole interplay among the parameter A of the field, the constant K of the field, and the integration constants of energy h and angular momentum C. We find the number of equilibria for each such situation.

  16. Vapor-liquid equilibria of binary mixtures containing methane, ethane, and carbon dioxide from molecular simulation

    NASA Astrophysics Data System (ADS)

    Vrabec, J.; Fischer, J.

    1996-07-01

    The NpT + test particle method is used in order to predict vapor-liquid equilibria of the mixtures methane + ethane, methane + carbon dioxide, and carbon dioxide +ethane by molecular simulations. The pure-component molecular models were fitted to the experimental vapor pressures and saturated liquid densities in previous papers, which used the same simulation method for the determination of the phase equilibria. For each binary mixture the two unlike interaction parameters were determined from one experimental excess volume and one excess enthalpy. Based on these molecular models the vapor-liquid phase equilibria were calculated for each mixture at three temperatures. Comparison of the pressure-composition data with experimental results shows the high predictive power of this molecular based procedure. This statement is confirmed by additional comparisons of the pressure-composition diagrams and the pressure-density diagrams with results from equations of state.

  17. Simultaneous Phase Transfer and Surface Modification of TiO₂ Nanoparticles Using Alkylphosphonic Acids: Optimization and Structure of the Organosols.

    PubMed

    Schmitt Pauly, Céline; Genix, Anne-Caroline; Alauzun, Johan G; Guerrero, Gilles; Appavou, Marie-Sousai; Pérez, Javier; Oberdisse, Julian; Mutin, P Hubert

    2015-10-13

    An original protocol of simultaneous surface modification and transfer from aqueous to organic phases of anatase TiO2 nanoparticles (NPs) using alkylphosphonic acids (PAs) is studied. The influence of the solvent, the nature and concentration of the PA, and the size, concentration, and aggregation state of the TiO2 NPs was investigated. Complete transfer was observed for linear alkyl chains (5, 8, 12, and 18 C atoms), even at very high sol concentrations. After transfer, the grafted NPs were characterized by (31)P solid-state MAS NMR. The dispersion state of NPs before and after phase transfer was monitored by dynamic light scattering (DLS). Small-angle neutron scattering (SANS) was used to characterize the structure of PA-grafted NPs in the organic solvent. Using a quantitative core-shell model cross-checked under different contrast conditions, it is found that the primary particles making up the NPs are homogeneously grafted with a solvated PA-layer. The nanometric thickness of the latter is shown to increase with the length of the linear carbon chain of the PA, independent of the size of the primary TiO2 NP. Interestingly, a reversible temperature-dependent aggregation was evidenced visually for C18PA, and confirmed by DLS and SANS: heating the sample induces the breakup of aggregates, which reassemble upon cooling. Finally, in the case of NPs agglomerated by playing with the pH or the salt concentration of the sols, the phase transfer with PA is capable of redispersing the agglomerates. This new and highly versatile method of NP surface modification with PAs and simultaneous transfer is thus well suited for obtaining well-dispersed grafted NPs. PMID:26421961

  18. Histone modifications induced by MDV infection at early cytolytic and latency phases

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Background: Marek’s disease (MD) is a highly contagious, lymphomatous disease of chickens induced by a herpesvirus, Marek’s disease virus (MDV) that is the cause of major annual losses to the poultry industry. MD pathogenesis involves multiple stages including an early cytolytic phase and latency, a...

  19. Surface modification of polytetrafluoroethylene column for two-stationary phase separations by counter-current chromatography.

    PubMed

    Quan, Kai-jun; Huang, Xin-yi; Li, Xiao-ting; Wang, Gao-hong; Liu, Yan-juan; Duan, Wen-da; Di, Duo-long

    2015-11-27

    To improve the separation capability of CCC, a novel solid-liquid two-stationary phases CCC (ASP-CCC) column was prepared employing graphene oxide (GO) conjugated poly-dopamine (PD) coating (GO/PD) as auxiliary stationary phase (ASP). The results of Scanning electron microscopy (SEM), contact angle and X-ray photoelectron spectroscopy (XPS) indicated that nanostructured GO and PD were successfully grafted on the inner wall of the PTFE column. Three alkaloid compounds were selected as the target analytes to evaluate the performance of the novel column. Because of the intermolecular force (hydrogen bond, electrostatic interaction and π-π interaction) between the ASP and model compounds, three analytes were well separated with this novel ASP-CCC column. Additionally, the novel column exhibited higher stationary phase retention ratio, about 8%, than original column without changing the chromatographic condition. Furthermore, the eluotropic sequence of analytes on novel column was in accordance with that in the original column. This suggested that the novel column is a CCC column with auxiliary stationary phase (ASP) in its own right, and the present separation mode is the combination of partition chromatography and adsorption chromatography.

  20. Surface modification of polytetrafluoroethylene column for two-stationary phase separations by counter-current chromatography.

    PubMed

    Quan, Kai-jun; Huang, Xin-yi; Li, Xiao-ting; Wang, Gao-hong; Liu, Yan-juan; Duan, Wen-da; Di, Duo-long

    2015-11-27

    To improve the separation capability of CCC, a novel solid-liquid two-stationary phases CCC (ASP-CCC) column was prepared employing graphene oxide (GO) conjugated poly-dopamine (PD) coating (GO/PD) as auxiliary stationary phase (ASP). The results of Scanning electron microscopy (SEM), contact angle and X-ray photoelectron spectroscopy (XPS) indicated that nanostructured GO and PD were successfully grafted on the inner wall of the PTFE column. Three alkaloid compounds were selected as the target analytes to evaluate the performance of the novel column. Because of the intermolecular force (hydrogen bond, electrostatic interaction and π-π interaction) between the ASP and model compounds, three analytes were well separated with this novel ASP-CCC column. Additionally, the novel column exhibited higher stationary phase retention ratio, about 8%, than original column without changing the chromatographic condition. Furthermore, the eluotropic sequence of analytes on novel column was in accordance with that in the original column. This suggested that the novel column is a CCC column with auxiliary stationary phase (ASP) in its own right, and the present separation mode is the combination of partition chromatography and adsorption chromatography. PMID:26518492

  1. POTENTIAL USE AND MODIFICATION OF EXISTING MESOCOSMS FOR VAPOR PHASE PHOTOTOXICITY

    EPA Science Inventory

    With vapor phase plant toxicity testing becoming a requirement in Europe, there is a pressing need to develop and implement acceptable tests protocols. The quickest way to proceed is to examine and modify existing methodologies while determining if new technologies are needed. ...

  2. MODIFICATIONS TO WEEKEND RECOVERY SLEEP DELAY CIRCADIAN PHASE IN OLDER ADOLESCENTS

    PubMed Central

    Crowley, Stephanie J.; Carskadon, Mary A.

    2012-01-01

    Adolescents often report shorter time in bed and earlier wake-up times on school days compared to weekend days. Extending sleep on weekend nights may reflect a “recovery” process as youngsters try to compensate for an accumulated school-week sleep debt. The authors examined whether the circadian timing system of adolescents shifted after keeping a common late weekend “recovery” sleep schedule; it was hypothesized that a circadian phase delay shift would follow this later and longer weekend sleep. The second aim of this study was to test whether modifying sleep timing or light exposure on weekends while still providing recovery sleep can stabilize the circadian system. Two experiments addressed these aims. Experiment 1 was a 4-wk, within-subjects counterbalanced design comparing two weekend sleep schedule conditions, “TYPICAL” and “NAP.” Compared to weeknights, participants retired 1.5 h later and woke 3 h later on TYPICAL weekends but 1 h later on NAP weekends, which also included a 2-h afternoon nap. Experiment 2 was a 2-wk, between-subjects design with two groups (“TYPICAL” or “LIGHT”) that differed by weekend morning light exposure. TYPICAL and LIGHT groups followed the TYPICAL weekend schedule of Experiment 1, and the LIGHT group received 1 h of light (454–484 nm) upon weekend wake-up. Weekend time in bed was 1.5 h longer/night than week-nights in both experimental protocols. Participants slept at home during the study. Dim light melatonin onset (DLMO) phase was assessed in the laboratory before (Friday) and after (Sunday) each weekend. Participants were ages 15 to 17 yrs. Twelve participants (4 boys) were included in Experiment 1, and 33 (10 boys) were included in Experiment 2. DLMO phase delayed over TYPICAL weekends in Experiment 1 by (mean ± SD) 45 ± 31 min and Experiment 2 by 46 ± 34 min. DLMO phase also delayed over NAP weekends (41 ± 34 min) and did not differ from the TYPICAL condition of Experiment 1. DLMO phase delayed

  3. Dynamic phase transition in the prisoner's dilemma on a lattice with stochastic modifications

    NASA Astrophysics Data System (ADS)

    Saif, M. Ali; Gade, Prashant M.

    2010-03-01

    We present a detailed study of the prisoner's dilemma game with stochastic modifications on a two-dimensional lattice, in the presence of evolutionary dynamics. By very nature of the rules, the cooperators have incentives to cheat and fear being cheated. They may cheat even when this is not dictated by the evolutionary dynamics. We consider two variants here. In each case, the agents mimic the action (cooperation or defection) in the previous time step of the most successful agent in the neighborhood. But over and above this, the fraction p of cooperators spontaneously change their strategy to pure defector at every time step in the first variant. In the second variant, there are no pure cooperators. All cooperators keep defecting with probability p at every time step. In both cases, the system switches from a coexistence state to an all-defector state for higher values of p. We show that the transition between these states unambiguously belongs to the directed percolation universality class in 2 + 1 dimensions. We also study the local persistence. The persistence exponents obtained are higher than the ones obtained in previous studies, underlining their dependence on details of the dynamics.

  4. Modification of modulated plasma plumes for the quasi-phase-matching of high-order harmonics in different spectral ranges

    SciTech Connect

    Ganeev, R. A.; Boltaev, G. S.; Sobirov, B.; Reyimbaev, S.; Sherniyozov, H.; Usmanov, T.; Suzuki, M.; Yoneya, S.; Kuroda, H.

    2015-01-15

    We demonstrate the technique allowing the fine tuning of the distance between the laser-produced plasma plumes on the surfaces of different materials, as well as the variation of the sizes of these plumes. The modification of plasma formations is based on the tilting of the multi-slit mask placed between the heating laser beam and target surface, as well as the positioning of this mask in the telescope placed on the path of heating radiation. The modulated plasma plumes with the sizes of single plume ranging between 0.1 and 1 mm were produced on the manganese and silver targets. Modification of the geometrical parameters of plasma plumes proved to be useful for the fine tuning of the quasi-phase-matched high-order harmonics generated in such structures during propagation of the ultrashort laser pulses. We show the enhancement of some groups of harmonics along the plateau range and the tuning of maximally enhanced harmonic by variable modulation of the plasma.

  5. Gait modification strategies of trunk over left stance phase in patients with right anterior cruciate ligament deficiency

    PubMed Central

    Shi, Dongliang; Li, Nannan; Wang, Yubin; Jiang, Shuyun; Li, Jinglong; Zhu, Wenhui

    2015-01-01

    Purpose: To investigate the gait modification strategies of trunk over left stance phase in patients with right anterior cruciate ligament deficiency (ACL-D). Methods: Thirty-six patients with right ACL-D and thirty-six health subjects (control) were recruited to undergo a 3-dimensional (3D) gait analysis. Coordinate data from 26 reflective markers positioned on the body surface of participants were recorded with a 3D optical video motion capture system, as they walked on the ground, ascended and descended a custom-built staircase. Angle changes in the 3-planes under different walking conditions were analyzed. Results: There were statistically significant differences between the two groups in the trunk at the transverse plane angle in most measurements. With the walk pattern of stair descent, the trunk at all 3-plane angles, at the maximum value of the left knee sagittal/coronal/transverse plane moment, was significantly different between the two groups (P ≤ 0.03). Conclusions: Our findings suggested that special gait modification of trunk is apparent over stance of left (healthy) side in patients with right ACL-D. The results of this study may supply more insight with respect to improving the diagnosis and rehabilitation of ACL-D. This information may also be helpful for a better use of walk and stair tasks as part of a rehabilitation program and provide a safe guideline for the patients. PMID:26550279

  6. Regulation of Actin by Ion-Linked Equilibria

    PubMed Central

    Kang, Hyeran; Bradley, Michael J.; Elam, W. Austin; De La Cruz, Enrique M.

    2013-01-01

    Actin assembly, filament mechanical properties, and interactions with regulatory proteins depend on the types and concentrations of salts in solution. Salts modulate actin through both nonspecific electrostatic effects and specific binding to discrete sites. Multiple cation-binding site classes spanning a broad range of affinities (nanomolar to millimolar) have been identified on actin monomers and filaments. This review focuses on discrete, low-affinity cation-binding interactions that drive polymerization, regulate filament-bending mechanics, and modulate interactions with regulatory proteins. Cation binding may be perturbed by actin post-translational modifications and linked equilibria. Partial cation occupancy under physiological and commonly used in vitro solution conditions likely contribute to filament mechanical heterogeneity and structural polymorphism. Site-specific cation-binding residues are conserved in Arp2 and Arp3, and may play a role in Arp2/3 complex activation and actin-filament branching activity. Actin-salt interactions demonstrate the relevance of ion-linked equilibria in the operation and regulation of complex biological systems. PMID:24359734

  7. Gait modification strategies in trunk over right stance phase in patients with right anterior cruciate ligament deficiency.

    PubMed

    Shi, Dongliang; Li, Nannan; Wang, Yubin; Jiang, Shuyun; Lin, Jianping; Zhu, Wenhui

    2016-05-01

    This study aimed to investigate the gait modification strategies of trunk over right stance phase in patients with right anterior cruciate ligament deficiency (ACL-D). Thirty-six patients with right chronic ACL-D were recruited, as well as 36 controls. A 3D optical video motion capture system was used during gait and stair ambulation. Kinematic variables of the trunk and kinematic and kinetic variables of the knee were calculated. Patients with chronic right ACL-D exhibited many significant abnormalities compared with controls. Trunk rotation with right shoulder trailing over the right stance phase was lower in all five motion patterns (P<0.05). Compared with controls, trunk posterior lean was higher from descending stairs to walking when the knee sagittal plane moment ended (P<0.01). Trunk lateral flexion to the left was higher when ascending stairs at the start of right knee coronal plane moment (P=0.01), when descending stairs at the maximal knee coronal plane moment (P<0.01), and when descending stairs at the end of the knee coronal plane moment (P=0.03). Trunk rotation with right shoulder forward was higher at the minimal knee transverse plane moment (P<0.01) and when the knee transverse plane moment ended (P<0.01); during walking, trunk rotation with right shoulder trailing was lower at other knee moments during other walking patterns (all P<0.01). In conclusion, gait modification strategies of the trunk were apparent in patients with ACL-D. These results provide new insights about diagnosis and rehabilitation of chronic ACL-D (better use of walking and stair tasks as part of a rehabilitation program).

  8. Evaluation of surface, microstructure and phase modifications on various tungsten grades induced by pulsed plasma loading

    NASA Astrophysics Data System (ADS)

    Vilémová, M.; Pala, Z.; Jäger, A.; Matějíček, J.; Chernyshova, M.; Kowalska-Strzęciwilk, E.; Tonarová, D.; Gribkov, V. A.

    2016-03-01

    Progress in the field of nuclear fusion requires the development of a new generation of tungsten materials that are expected to meet specific property, lifetime and safety requirements. Pursuing this goal, the new materials must be properly tested in a wide range of conditions including cases where material is brought to the molten stage, such as with large fusion plasma instabilities. In this study, two prospective candidates from the family of dispersion strengthened (DS) tungsten materials, i.e., W-1%Y2O3 and W-2.5%TiC, were subjected to extreme heat loading exerted by the deuterium plasma generator PF6. The study focuses on the interaction of the tungsten matrix with the dispersed particles during material melting. The materials underwent significant changes in microstructure and phase content. Among the most serious was the loss of TiC particles and void formation in W-2.5%TiC and phase change of polymorphic Y2O3 particles in W-1% Y2O3.

  9. Effect of temperature on acid-base equilibria in separation techniques. A review.

    PubMed

    Gagliardi, Leonardo G; Tascon, Marcos; Castells, Cecilia B

    2015-08-19

    Studies on the theoretical principles of acid-base equilibria are reviewed and the influence of temperature on secondary chemical equilibria within the context of separation techniques, in water and also in aqueous-organic solvent mixtures, is discussed. In order to define the relationships between the retention in liquid chromatography or the migration velocity in capillary electrophoresis and temperature, the main properties of acid-base equilibria have to be taken into account for both, the analytes and the conjugate pairs chosen to control the solution pH. The focus of this review is based on liquid-liquid extraction (LLE), liquid chromatography (LC) and capillary electrophoresis (CE), with emphasis on the use of temperature as a useful variable to modify selectivity on a predictable basis. Simplified models were evaluated to achieve practical optimizations involving pH and temperature (in LLE and CE) as well as solvent composition in reversed-phase LC.

  10. Contributions of gas-phase plasma chemistry to surface modifications and gas-surface interactions: investigations of fluorocarbon rf plasmas

    NASA Astrophysics Data System (ADS)

    Cuddy, Michael F., II

    The fundamental aspects of inductively coupled fluorocarbon (FC) plasma chemistry were examined, with special emphasis on the contributions of gas-phase species to surface modifications. Characterization of the gas-phase constituents of single-source CF4-, C2F6-, C3F 8-, and C3F6-based plasmas was performed using spectroscopic and mass spectrometric techniques. The effects of varying plasma parameters, including applied rf power (P) and system pressure (p) were examined. Optical emission spectroscopy (OES) and laser-induced fluorescence (LIF) spectroscopy were employed to monitor the behavior of excited and ground CFx (x = 1,2) radicals, respectively. Mass spectrometric techniques, including ion energy analyses, elucidated behaviors of nascent ions in the FC plasmas. These gas-phase data were correlated with the net effect of substrate processing for Si and ZrO2 surfaces. Surface-specific analyses were performed for post-processed substrates via x-ray photoelectron spectroscopy (XPS) and contact angle goniometry. Generally, precursors with lower F/C ratios tended to deposit robust FC films of high surface energy. Precursors of higher F/C ratio, such as CF4, were associated with etching or removal of material from surfaces. Nonetheless, a net balance between deposition of FC moieties and etching of material exists for each plasma system. The imaging of radicals interacting with surfaces (IRIS) technique provided insight into the phenomena occurring at the interface of the plasma gas-phase and substrate of interest. IRIS results demonstrate that CFx radicals scatter copiously, with surface scatter coefficients, S, generally greater than unity under most experimental conditions. Such considerable S values imply surface-mediated production of the CFx radicals at FC-passivated sites. It is inferred that the primary route to surface production of CFx arises from energetic ion bombardment and ablation of surface FC films. Other factors which may influence the observed CFx

  11. On Nash equilibria in Eisert-Lewenstein-Wilkens game

    NASA Astrophysics Data System (ADS)

    Bolonek-Lasoń, Katarzyna; Kosiński, Piotr

    2015-12-01

    Landsburg method of classifying mixed Nash equilibria for maximally entangled Eisert-Lewenstein-Wilkens (ELW) game is analyzed with special emphasis on symmetries inherent to the problem. Nash equilibria for the original ELW game are determined.

  12. Phase equilibria and the thermodynamic properties of saturated solid solutions of BiTeI, Bi2TeI, and Bi4TeI1.25 compounds of the AgI-Bi-Bi2Te3-BiTeI system

    NASA Astrophysics Data System (ADS)

    Moroz, M. V.; Prokhorenko, M. V.

    2016-07-01

    The phase equilibria of the Ag-Bi-Te-I system in the part AgI-Bi-Bi2Te3-BiTeI is studied in the interval of 500-540 K by means of physicochemical analysis. Thermodynamic properties of phases are determined via EMF. Potential-forming processes occur in electrochemical cells (ECCs) of the C|Ag|glass Ag3GeS3I|D|C structure (where C denotes inert (graphite) electrodes; Ag, D denotes ECC electrodes; D denotes four-phase alloys of the AgI-Bi-Bi2Te3-BiTeI system; and Ag3GeS3I glass is the selective Ag+ conducting membrane). Linear dependences of the EMFs of cells E(T) in the interval of 505-535 K are used to calculate the values of the thermodynamic functions of BiTeI, Bi2TeI, and Bi4TeI1.25 phases saturated over silver.

  13. Influence of plasma treatment time on plasma induced vapor phase grafting modification of PBO fiber surface

    NASA Astrophysics Data System (ADS)

    Song, B.; Meng, L. H.; Huang, Y. D.

    2012-05-01

    The surface of poly-p-phenylene benzobisthiazole (PBO) fibers was treated through oxygen plasma induced vapor phase grafting (PIVPG) method under various oxygen plasma pre-treatment time conditions. The surface chemical composition, surface morphologies and surface free energy of pristine and treated PBO fibers were studied using X-ray photoelectron spectroscopy, atomic force microscopy, scanning electron microscopy, and Cahn DCAA system. The mechanics property of these fibers was evaluated by tensile strength and interfacial shear strength (IFSS). It was found that the surface characteristics of treated PBO fibers occurred significant change compare with the pristine PBO fibers. After treatment, the polar functional groups were introduced on the fiber surface. Carbon concentration decreased; oxygen concentration and elemental ratio of oxygen to carbon increased. Acrylic acid can react with the activated PBO fibers surface, which led to the fiber surface roughness increased. The surface free energy increased from 41.4 mN/m to 62.8 mN/m when PBO fibers were plasma pre-treated for 10 min, while the IFSS of PBO fibers with epoxy resin increased from 36.6 MPa to 55.8 MPa. Therefore, PIVPG can be used to enhance the interfacial bond between PBO fibers and epoxy resin.

  14. Finding Plasma Equilibria with Magnetic Islands

    NASA Astrophysics Data System (ADS)

    Miller, G.; Faber, V.; White, A. B., Jr.

    1988-12-01

    The traditional method of solving the helically symmetric plasma equilibrium equation, of the form L[ G] = F( G, r) where L is an elliptic linear operator, has been the simple iteration L[ Gn + 1 ]= F( Gn, r). A model of a Tokomak equilibrium is constructed and used to illustrate the divergence of the simple iteration for plasma equilibria with magnetic islands. Although the problem of equilibria with magnetic islands is two dimensional, for small islands the numerical stability of the simple iteration may be analyzed using a one-dimensional equation similar to the linearized equilibrium equation used to analyze physical (resistive) instability. This analysis is used to prove that any equilibria of the Tokamak type with small islands cannot be obtained by the simple iteration and to illustrate the superlinear convergence of Newton's method on these problems. The implementation of Newton's method is discussed and examples are given.

  15. Surface modification of superaustenitic and maraging stainless steels by low-temperature gas-phase carburization

    NASA Astrophysics Data System (ADS)

    Gentil, Johannes

    Low-temperature gas-phase carburization of 316L austenitic stainless steel was developed in recent years by the Swagelok company. This process generates great mechanical and electrochemical surface properties. Hardness, wear resistance, fatigue behavior, and corrosion resistance are dramatically improved, while the formation of carbides is effectively suppressed. This new technique is of technical, economical, but especially of scientific interest because the surface properties of common stainless steel can be enhanced to a level of more sophisticated and more expensive superalloys. The consequential continuation of previous research is the application of the carburization process to other steel grades. Differences in chemical composition, microstructure, and passivity between the various alloys may cause technical problems and it is expected that the initial process needs to be optimized for every specific material. This study presents results of low-temperature carburization of AL-6XN (superaustenitic stainless steel) and PH13-8Mo (precipitation-hardened martensitic stainless steel). Both alloys have been treated successfully in terms of creating a hardened surface by introducing high amounts of interstitially dissolved carbon. The surface hardness of AL-6XN was increased to 12GPa and is correlated with a colossal carbon supersaturation at the surface of up to 20 at.%. The hardened case develops a carburization time-dependent thickness between 10mum after one carburization cycle and up to 35mum after four treatments and remains highly ductile. Substantial broadening of X-ray diffraction peaks in low-temperature carburized superaustenitic stainless steels are attributed to the generation of very large compressive biaxial residual stresses. Those large stresses presumably cause relaxations of the surface, so-called undulations. Heavily expanded regions of carburized AL-6XN turn ferromagnetic. Non-carburized AL-6XN is known for its outstanding corrosion resistance

  16. Phase variation of a Type IIG restriction-modification enzyme alters site-specific methylation patterns and gene expression in Campylobacter jejuni strain NCTC11168

    PubMed Central

    Anjum, Awais; Brathwaite, Kelly J.; Aidley, Jack; Connerton, Phillippa L.; Cummings, Nicola J.; Parkhill, Julian; Connerton, Ian; Bayliss, Christopher D.

    2016-01-01

    Phase-variable restriction-modification systems are a feature of a diverse range of bacterial species. Stochastic, reversible switches in expression of the methyltransferase produces variation in methylation of specific sequences. Phase-variable methylation by both Type I and Type III methyltransferases is associated with altered gene expression and phenotypic variation. One phase-variable gene of Campylobacter jejuni encodes a homologue of an unusual Type IIG restriction-modification system in which the endonuclease and methyltransferase are encoded by a single gene. Using both inhibition of restriction and PacBio-derived methylome analyses of mutants and phase-variants, the cj0031c allele in C. jejuni strain NCTC11168 was demonstrated to specifically methylate adenine in 5′CCCGA and 5′CCTGA sequences. Alterations in the levels of specific transcripts were detected using RNA-Seq in phase-variants and mutants of cj0031c but these changes did not correlate with observed differences in phenotypic behaviour. Alterations in restriction of phage growth were also associated with phase variation (PV) of cj0031c and correlated with presence of sites in the genomes of these phages. We conclude that PV of a Type IIG restriction-modification system causes changes in site-specific methylation patterns and gene expression patterns that may indirectly change adaptive traits. PMID:26786317

  17. Phase variation of a Type IIG restriction-modification enzyme alters site-specific methylation patterns and gene expression in Campylobacter jejuni strain NCTC11168.

    PubMed

    Anjum, Awais; Brathwaite, Kelly J; Aidley, Jack; Connerton, Phillippa L; Cummings, Nicola J; Parkhill, Julian; Connerton, Ian; Bayliss, Christopher D

    2016-06-01

    Phase-variable restriction-modification systems are a feature of a diverse range of bacterial species. Stochastic, reversible switches in expression of the methyltransferase produces variation in methylation of specific sequences. Phase-variable methylation by both Type I and Type III methyltransferases is associated with altered gene expression and phenotypic variation. One phase-variable gene of Campylobacter jejuni encodes a homologue of an unusual Type IIG restriction-modification system in which the endonuclease and methyltransferase are encoded by a single gene. Using both inhibition of restriction and PacBio-derived methylome analyses of mutants and phase-variants, the cj0031c allele in C. jejuni strain NCTC11168 was demonstrated to specifically methylate adenine in 5'CCCGA and 5'CCTGA sequences. Alterations in the levels of specific transcripts were detected using RNA-Seq in phase-variants and mutants of cj0031c but these changes did not correlate with observed differences in phenotypic behaviour. Alterations in restriction of phage growth were also associated with phase variation (PV) of cj0031c and correlated with presence of sites in the genomes of these phages. We conclude that PV of a Type IIG restriction-modification system causes changes in site-specific methylation patterns and gene expression patterns that may indirectly change adaptive traits.

  18. Thermodynamic assessment of hydrothermal alkali feldspar-mica-aluminosilicate equilibria

    USGS Publications Warehouse

    Sverjensky, D.A.; Hemley, J.J.; d'Angelo, W. M.

    1991-01-01

    The thermodynamic properties of minerals retrieved from consideration of solid-solid and dehydration equilibria with calorimetric reference values, and those of aqueous species derived from studies of electrolytes, are not consistent with experimentally measured high-temperature solubilities in the systems K2O- and Na2O-Al2O3-SiO2-H2O-HCl (e.g., K-fs - Ms - Qtz - K+ - H+). This introduces major inaccuracies into the computation of ionic activity ratios and the acidities of diagenetic, metamorphic, and magmatic hydrothermal fluids buffered by alkali silicate-bearing assemblages. We report a thermodynamic analysis of revised solubility equilibria in these systems that integrates the thermodynamic properties of minerals obtained from phase equilibria studies (Berman, 1988) with the properties of aqueous species calculated from a calibrated equation of state (Shock and Helgeson, 1988). This was achieved in two separate steps. First, new values of the free energies and enthalpies of formation at 25??C and 1 bar for the alkali silicates muscovite and albite were retrieved from the experimental solubility equilibria at 300??C and Psat. Because the latter have stoichiometric reaction coefficients different from those for solid-solid and dehydration equilibria, our procedure preserves exactly the relative thermodynamic properties of the alkali-bearing silicates (Berman, 1988). Only simple arithmetic adjustments of -1,600 and -1,626 (??500) cal/mol to all the K- and Na-bearing silicates, respectively, in Berman (1988) are required. In all cases, the revised values are within ??0.2% of calorimetric values. Similar adjustments were derived for the properties of minerals from Helgeson et al. (1978). Second, new values of the dissociation constant of HCl were retrieved from the solubility equilibria at temperatures and pressures from 300-600??C and 0.5-2.0 kbars using a simple model for aqueous speciation. The results agree well with the conductance-derived dissociation

  19. Equilibrator: Modeling Chemical Equilibria with Excel

    ERIC Educational Resources Information Center

    Vander Griend, Douglas A.

    2011-01-01

    Equilibrator is a Microsoft Excel program for learning about chemical equilibria through modeling, similar in function to EQS4WIN, which is no longer supported and does not work well with newer Windows operating systems. Similar to EQS4WIN, Equilibrator allows the user to define a system with temperature, initial moles, and then either total…

  20. Equilibria with incompressible flows from symmetry analysis

    SciTech Connect

    Kuiroukidis, Ap E-mail: gthroum@cc.uoi.gr; Throumoulopoulos, G. N. E-mail: gthroum@cc.uoi.gr

    2015-08-15

    We identify and study new nonlinear axisymmetric equilibria with incompressible flow of arbitrary direction satisfying a generalized Grad Shafranov equation by extending the symmetry analysis presented by Cicogna and Pegoraro [Phys. Plasmas 22, 022520 (2015)]. In particular, we construct a typical tokamak D-shaped equilibrium with peaked toroidal current density, monotonically varying safety factor, and sheared electric field.

  1. Instability of magnetic equilibria in barotropic stars

    NASA Astrophysics Data System (ADS)

    Mitchell, J. P.; Braithwaite, J.; Reisenegger, A.; Spruit, H.; Valdivia, J. A.; Langer, N.

    2015-02-01

    In stably stratified stars, numerical magnetohydrodynamics simulations have shown that arbitrary initial magnetic fields evolve into stable equilibrium configurations, usually containing nearly axisymmetric, linked poloidal and toroidal fields that stabilize each other. In this work, we test the hypothesis that stable stratification is a requirement for the existence of such stable equilibria. For this purpose, we follow numerically the evolution of magnetic fields in barotropic (and thus neutrally stable) stars, starting from two different types of initial conditions, namely random disordered magnetic fields, as well as linked poloidal-toroidal configurations resembling the previously found equilibria. With many trials, we always find a decay of the magnetic field over a few Alfvén times, never a stable equilibrium. This strongly suggests that there are no stable equilibria in barotropic stars, thus clearly invalidating the assumption of barotropic equations of state often imposed on the search of magnetic equilibria. It also supports the hypothesis that, as dissipative processes erode the stable stratification, they might destabilize previously stable magnetic field configurations, leading to their decay.

  2. 5' modification of duplex DNA with a ruthenium electron donor-acceptor pair using solid-phase DNA synthesis

    NASA Technical Reports Server (NTRS)

    Frank, Natia L.; Meade, Thomas J.

    2003-01-01

    Incorporation of metalated nucleosides into DNA through covalent modification is crucial to measurement of thermal electron-transfer rates and the dependence of these rates with structure, distance, and position. Here, we report the first synthesis of an electron donor-acceptor pair of 5' metallonucleosides and their subsequent incorporation into oligonucleotides using solid-phase DNA synthesis techniques. Large-scale syntheses of metal-containing oligonucleotides are achieved using 5' modified phosporamidites containing [Ru(acac)(2)(IMPy)](2+) (acac is acetylacetonato; IMPy is 2'-iminomethylpyridyl-2'-deoxyuridine) (3) and [Ru(bpy)(2)(IMPy)](2+) (bpy is 2,2'-bipyridine; IMPy is 2'-iminomethylpyridyl-2'-deoxyuridine) (4). Duplexes formed with the metal-containing oligonucleotides exhibit thermal stability comparable to the corresponding unmetalated duplexes (T(m) of modified duplex = 49 degrees C vs T(m) of unmodified duplex = 47 degrees C). Electrochemical (3, E(1/2) = -0.04 V vs NHE; 4, E(1/2) = 1.12 V vs NHE), absorption (3, lambda(max) = 568, 369 nm; 4, lambda(max) = 480 nm), and emission (4, lambda(max) = 720 nm, tau = 55 ns, Phi = 1.2 x 10(-)(4)) data for the ruthenium-modified nucleosides and oligonucleotides indicate that incorporation into an oligonucleotide does not perturb the electronic properties of the ruthenium complex or the DNA significantly. In addition, the absence of any change in the emission properties upon metalated duplex formation suggests that the [Ru(bpy)(2)(IMPy)](2+)[Ru(acac)(2)(IMPy)](2+) pair will provide a valuable probe for DNA-mediated electron-transfer studies.

  3. Self-organized criticality and punctuated equilibria

    NASA Astrophysics Data System (ADS)

    Bak, Per; Boettcher, Stefan

    1997-02-01

    Many natural phenomena evolve intermittently, with periods of tranquillity interrupted by bursts of activity, rather than following a smooth gradual path. Examples include earthquakes, volcanic eruptions, solar flares, gamma-ray bursts, and biological evolution. Stephen Jay Gould and Niles Eldredge have coined the term “punctuated equilibria” for this behavior. We argue that punctuated equilibria reflects the tendency of dynamical systems to evolve towards a critical state, and review recent work on simple models. A good metaphoric picture is one where the systems are temporarily trapped in valleys of deformable, interacting landscapes. Similarities with spin glasses are pointed out. Punctuated equilibria are essential for the emergence of complex phenomena. The periods of stasis allow the system to remember its past history; yet the intermittent events permit further change.

  4. Symmetry breaking of quasihelical stellarator equilibria

    SciTech Connect

    Weening, R.H. )

    1993-04-01

    A mean-field Ohm's law is used to determine the effects of the bootstrap current on quasihelically symmetric stellarator equilibria. The Ohm's law leads to the conclusion that the effects of the bootstrap current break the quasihelical stellarator symmetry at second order in an inverse aspect ratio expansion of the magnetic field strength. The level of symmetry breaking suggests that good approximations to quasihelical stellarator fusion reactors may not be attainable.

  5. Magnetohydrodynamic equilibria with incompressible flows: Symmetry approach

    SciTech Connect

    Cicogna, G.; Pegoraro, F.

    2015-02-15

    We identify and discuss a family of azimuthally symmetric, incompressible, magnetohydrodynamic plasma equilibria with poloidal and toroidal flows in terms of solutions of the Generalized Grad Shafranov (GGS) equation. These solutions are derived by exploiting the incompressibility assumption, in order to rewrite the GGS equation in terms of a different dependent variable, and the continuous Lie symmetry properties of the resulting equation and, in particular, a special type of “weak” symmetries.

  6. ON MAGNETIC EQUILIBRIA IN BAROTROPIC STARS

    SciTech Connect

    Armaza, Cristóbal; Reisenegger, Andreas; Valdivia, Juan Alejandro

    2015-04-01

    Upper main-sequence stars, white dwarfs, and neutron stars are known to possess stable, large-scale magnetic fields. Numerical works have confirmed that stable magnetohydrodynamic equilibria can exist in non-barotropic, stably stratified stars. On the other hand, it is unclear whether stable equilibria are possible in barotropic stars, although the existing evidence suggests that they are all unstable. This work aims to construct barotropic equilibria in order to study their properties, as a first step to test their stability. We have assumed that the star is a perfectly conducting, axially symmetric fluid, allowing for both poloidal and toroidal components of the magnetic field. In addition, we made the astrophysically justified assumption that the magnetic force has a negligible influence on the fluid structure, in which case the equilibrium is governed by the Grad–Shafranov equation, involving two arbitrary functions of the poloidal flux. We built a numerical code to solve this equation, allowing for an arbitrary prescription for these functions. Taking particularly simple, but physically reasonable choices for these functions with a couple of adjustable parameters, all of the equilibria found present only a small (≲10%) fraction of the magnetic energy stored in the toroidal component, confirming previous results. We developed an analytical model in order to study in more detail the behavior of the magnetic energy over the full range of parameters. The model confirms that the toroidal fraction of the energy and the ratio of toroidal to poloidal flux are bounded from above for the whole range of parameters.

  7. Relative Equilibria in Continuous Stellar Dynamics

    NASA Astrophysics Data System (ADS)

    Campos, Juan; Del Pino, Manuel; Dolbeault, Jean

    2010-12-01

    We study a three dimensional continuous model of gravitating matter rotating at constant angular velocity. In the rotating reference frame, by a finite dimensional reduction, we prove the existence of non-radial stationary solutions whose supports are made of an arbitrarily large number of disjoint compact sets, in the low angular velocity and large scale limit. At first order, the solutions behave like point particles, thus making the link with the relative equilibria in N-body dynamics.

  8. Close relative equilibria of identical point vortices

    NASA Astrophysics Data System (ADS)

    Dirksen, Tobias; Aref, Hassan

    2011-11-01

    Via numerical solution of the classical problem of relative equilibria for identical point vortices on the unbounded plane we have found configurations that are very close to the analytically known, centered, symmetrically arranged, nested equilateral triangles. Numerical solutions of this kind were found for 3 n + 1 vortices, where n = 2 , 3 , ... , 30 . A sufficient, although apparently not necessary, condition for this phenomenon of close solutions is that the ``core'' of the configuration is marginally stable, as occurs for a central vortex surrounded by an equilateral triangle. The open, regular heptagon also has this property, and new relative equilibria close to the nested, symmetrically arranged, regular heptagons have been found. The centered regular nonagon is also marginally stable. Again, a new family of close relative equilibria has been found. The closest relative equilibrium pairs occur, however, for symmetrically nested equilateral triangles. The numerical evidence is surveyed and related recent work mentioned. A Letter in Physics of Fluids 23 (2011) 051706 is available. Supported in part by the Danish National Research Foundation through a Niels Bohr visiting professorship.

  9. Four motional invariants in axisymmetric tori equilibria

    SciTech Connect

    A ring gren, O.; Moiseenko, V.E.

    2006-05-15

    In addition to the standard set ({epsilon},{mu},p{sub {phi}}) of three invariants in axisymmetric tori, there exists a fourth independent radial drift invariant I{sub r}. For confined particles, the net radial drift has to be zero, whereby the drift orbit average I{sub r}= of the gyro center radial Clebsch coordinate is constant. To lowest order in the banana width, the radial invariant is the gyro center radial coordinate r{sub 0}(x,v), and to this order the gyro center moves on a magnetic flux surface. The gyro center orbit projected on the (r,z) plane determines the radial invariant and first order banana width corrections to I{sub r} are calculated. The radial drift invariant exists for trapped as well as passing particles. The new invariant is applied to construct Vlasov equilibria, where the magnetic field satisfies a generalized Grad-Shafranov equation with a poloidal plasma current and a bridge to ideal magnetohydrodynamic equilibria is found. For equilibria with sufficiently small banana widths and radial drift excursions, the approximation I{sub r}{approx_equal}r{sub 0}(x,v) can be used for the equilibrium state.

  10. Extended MHD Stabiliy Calculations of Spheromak Equilibria

    NASA Astrophysics Data System (ADS)

    Howell, E. C.; Sovinec, C. R.

    2013-10-01

    Linear extended MHD calculations of spheromak equilibria in a cylindrical flux conserver are performed using the NIMROD code (Sovinec et al., JCP 195, 2004). A series of Grad-Sharfranov equilibria are generated with β ranging from 0 . 4 % to 4 . 2 % , corresponding to peak electron temperatures ranging 50 to 300 eV. These equilibria use a λ profile representative of SSPX shot 14590, which measured a peak electron temperature of 325 eV (McLean et al., POP 13, 2006). Resistive MHD calculations find that the β = 0 . 4 % case is unstable to resonant resistive interchange modes with γτA <= 2 . 3 % . These modes transition to ideal interchange as the equilibrium pressure is increased. Growth rates as large as γτA = 20 % are calculated for the 4 . 2 % β case. Calculations including ion-gyroviscosity show a minimal reduction of growth rate. Effects from including the Hall and Electron pressure terms in Ohm's Law and the cross-field diamagnetic heat flux are investigated. Results of related nonlinear simulations are also presented. Work Supported by US DOE.

  11. Finding plasma equilibria with magnetic islands

    SciTech Connect

    Miller, G.; Faber, V.; White A.B. Jr.

    1988-12-01

    The traditional method of solving the helically symmetric plasma equilibrium equation, of the form L(G) = F(G, r) where L is an elliptic linear operator, has been the simple iteration L(G/sup n//sup +1/) = F(G/sup n/, r). A model of a Tokomak equilibrium is constructed and used to illustrate the divergence of the simple iteration for plasma equilibria with magnetic islands. Although the problem of equilibria with magnetic islands is two dimensional, for small islands the numerical stability of the simple iteration may be analyzed using a one-dimensional equation similar to the linearized equilibrium equation used to analyze physical (resistive) instability. This analysis is used to prove that any equilibria of the Tokamak type with small islands cannot be obtained by the simple iteration and to illustrate the superlinear convergence of Newton's method on these problems. The implementation of Newton's method is discussed and examples are given. copyright 1988 Academic Press, Inc.

  12. Fixed boundary toroidal plasma equilibria with toroidal flows

    NASA Astrophysics Data System (ADS)

    Hu, Yanqiang; Hu, Yemin; Xiang, Nong

    2016-04-01

    The fixed boundary toroidal plasma equilibria with toroidal flows are investigated by solving the modified Grad-Shafranov equation numerically in the cylindrical coordinate system. For normal equilibrium configurations with geometry and profiles similar to usual tokamaks with no flow, it is found that the effect of flow is to lead to an outward shift of the magnetic flux surfaces, together with the profiles of pressure, and mass and current densities. The shifts could become significant when the toroidal flow Mach number exceeds 0.5. For non-conventional current profiles, even for the usual tokamak geometry, novel current reversal equilibrium configurations may result, sometimes with changed topology in the poloidal flux function. This change in the topology of plasma equilibrium can be attributed to the large toroidal flow. The computed results may correspond to situations of intense tangential injection during the low toroidal current phase in expected experimental situations.

  13. A Magnetic Diagnostic Code for 3D Fusion Equilibria

    SciTech Connect

    Samuel A. Lazerson, S. Sakakibara and Y. Suzuki

    2013-03-12

    A synthetic magnetic diagnostics code for fusion equilibria is presented. This code calculates the response of various magnetic diagnostics to the equilibria produced by the VMEC and PIES codes. This allows for treatment of equilibria with both good nested flux surfaces and those with stochastic regions. DIAGNO v2.0 builds upon previous codes through the implementation of a virtual casing principle. The code is validated against a vacuum shot on the Large Helical Device (LHD) where the vertical field was ramped. As an exercise of the code, the diagnostic response for various equilibria are calculated on the LHD.

  14. A Magnetic Diagnostic Code for 3D Fusion Equilibria

    SciTech Connect

    Samuel Aaron Lazerson

    2012-07-27

    A synthetic magnetic diagnostics code for fusion equilibria is presented. This code calculates the response of various magnetic diagnostics to the equilibria produced by the VMEC and PIES codes. This allows for treatment of equilibria with both good nested flux surfaces and those with stochastic regions. DIAGNO v2.0 builds upon previous codes through the implementation of a virtual casing principle. The codes is validated against a vacuum shot on the Large Helical Device where the vertical field was ramped. As an exercise of the code, the diagnostic response for various equilibria are calculated on the Large Helical Device (LHD).

  15. The New Low Value for the Second Dissociation Constant for H2S: Its History, Its Best Value, and Its Impact on the Teaching of Sulfide Equilibria.

    ERIC Educational Resources Information Center

    Myers, Rollie J.

    1986-01-01

    Discusses the historical development of a new value of the second dissociation constant (K2) for hydrogen sulfide (H2S). Describes the differences between the traditional high values for K2. Suggests modification of teaching about sulfide equilibria in light of the new low value for K2. (TW)

  16. Computation of zero. beta. three-dimensional equilibria with magnetic islands

    SciTech Connect

    Reiman, A.H.; Greenside, H.S.

    1989-01-01

    A Picard iteration scheme has been implemented for the computation of toroidal, fully three-dimensional, zero ..beta.. equilibria with islands and stochastic regions. Representation of the variables in appropriate coordinate systems has been found to be a key to making the scheme work well. In particular, different coordinate systems are used for solving magnetic differential equations and Ampere's law. The current profile is adjusted when islands and stochastic regions appear. An underrelaxation of the current profile modifications is generally needed for stable iteration of the algorithm. Some examples of equilibrium calculations are presented. 16 refs., 6 figs., 1 tab.

  17. Discovering the Thermodynamics of Simultaneous Equilibria: An Entropy Analysis Activity Involving Consecutive Equilibria

    ERIC Educational Resources Information Center

    Bindel, Thomas H.

    2007-01-01

    An activity is presented in which the thermodynamics of simultaneous, consecutive equilibria are explored. The activity is appropriate for second-year high school or AP chemistry. Students discover that a reactant-favored (entropy-diminishing or endergonic) reaction can be caused to happen if it is coupled with a product-favored reaction of…

  18. Hydrolysis of iodine: equilibria at high temperatures

    SciTech Connect

    Palmer, D.A.; Ramette, R.W.; Mesmer, R.E.

    1984-01-01

    The hydrolysis (or disproportionation) of molecular iodine to form iodate and iodide ions has been studied by emf measurements over the temperature range, 3.8/sup 0/ to 209.0/sup 0/C. The interpretation of these results required a knowledge of the formation constant for triiodide ion and the acid dissociation constant of iodic acid, both of which were measured as a function of temperature. The resulting thermodynamic data have been incorporated into a general computer model describing the hydrolysis equilibria of iodine as a function of initial concentration, pH and temperature.

  19. Metal biosorption equilibria in a ternary system

    SciTech Connect

    Chong, K.H.; Volesky, B.

    1996-03-20

    Equilibrium metal uptake performance of a biosorbent prepared from Ascophyllum nodosum seaweed biomass was studied using aqueous solutions containing copper, cadmium, and zinc ions in binary and ternary mixtures. Triangular equilibrium diagrams can graphically represent all the ternary equilibrium sorption data. Application of the multicomponent Langmuir model to describe the three-metal system revealed its nonideal characteristics, whereby the value of apparent dissociation constants for the respective metals differed for each system. This restricted the prediction of the ternary equilibria from the binary systems. However, some predictions of the ternary system behavior from the model were consistent with experimental data and with conclusions postulated from the three possible binary subsystems.

  20. Inverse moments equilibria for helical anisotropic systems

    NASA Astrophysics Data System (ADS)

    Cooper, W. A.; Hirshman, S. P.; Depassier, M. C.

    1987-11-01

    An energy functional is devised for magnetic confinement schemes that have anisotropic plasma pressure. The minimization of this energy functional is demonstrated to reproduce components of the magnetohydrodynamic (MHD) force balance relation in systems with helical symmetry. An iterative steepest descent procedure is applied to the Fourier moments of the inverse magnetic flux coordinates to minimize the total energy and thus generate anisotropic pressure MHD equilibria. Applications to straight ELMO Snaky Torus (NTIS Document No. DE-84002406) configurations that have a magnetic well on the outermost flux surfaces have been obtained.

  1. Solid-liquid phase equilibria at 50 and 75°C in the NaCl + MgCl2 + H2O system and the pitzer model representations

    NASA Astrophysics Data System (ADS)

    Yang, Ji-min; Zhang, Rui-zhi; Liu, Hong; Ma, Si-hong

    2013-12-01

    The solubilities in the NaCl-MgCl2-H2O system were determined at 50 and 75°C and the phase diagrams were constructed on the base of experimental data. One invariant point, two univariant curves, and two crystallization zones, corresponding to sodium chloride and dihydrate (MgCl2 · 6H2O) showed up in the phase diagrams of the ternary system, The mixing parameters θNa,Mg and ΨNa,Mg, Cl and equilibrium constant K sp were evaluated in NaCl-MgCl2-H2O system by least-squares optimization procedure, in which the single-salt Pitzer parameters of NaCl and MgCl2β(0), β(1), and C φ were directly calculated from the literature. The results obtained were in good agreement with the experimental data.

  2. Erratum: "A new equation of state of a flexible-chain polyelectrolyte solution: Phase equilibria and osmotic pressure in the salt-free case" [J. Chem. Phys. 142, 174901 (2015)

    NASA Astrophysics Data System (ADS)

    Budkov, Yu. A.; Kolesnikov, A. L.; Georgi, N.; Nogovitsyn, E. A.; Kiselev, M. G.

    2015-11-01

    We develop a first-principle equation of state of salt-free polyelectrolyte solution in the limit of infinitely long flexible polymer chains in the framework of a field-theoretical formalism beyond the linear Debye-Hueckel theory and predict a liquid-liquid phase separation induced by a strong correlation attraction. As a reference system we choose a set of two subsystems - charged macromolecules immersed in a structureless oppositely charged background created by counterions (polymer one component plasma) and counterions immersed in oppositely charged background created by polymer chains (hard-core one component plasma). We calculate the excess free energy of polymer one component plasma in the framework of Modified Random Phase Approximation, whereas a contribution of charge densities fluctuations of neutralizing backgrounds we evaluate at the level of Gaussian approximation. We show that our theory is in a very good agreement with the results of Monte-Carlo and MD simulations for critical parameters of liquid-liquid phase separation and osmotic pressure in a wide range of monomer concentration above the critical point, respectively.

  3. Demonstrating the Possibility of Pareto Inferior Nash Equilibria.

    ERIC Educational Resources Information Center

    Vriend, Nicolaas J.

    2000-01-01

    Describes a classroom game that demonstrates to students that equilibria can occur naturally in order to encourage students to take unreasonable equilibria more seriously. Discusses the game, how to organize it in the classroom for a game theory course, and the results. (CMK)

  4. Phase equilibria and crystal chemistry of the CaO–1/2 Nd{sub 2}O{sub 3}–CoO{sub z} system at 885 °C in air

    SciTech Connect

    Wong-Ng, W.; Laws, W.; Talley, K.R.; Huang, Q.; Yan, Y.; Martin, J.; Kaduk, J.A.

    2014-07-01

    The phase diagram of the CaO–1/2 Nd{sub 2}O{sub 3}–CoO{sub z} system at 885 °C in air has been determined. The system consists of two calcium cobaltate compounds that have promising thermoelectric properties, namely, the 2D thermoelectric oxide solid solution, (Ca{sub 3−x}Nd{sub x})Co{sub 4}O{sub 9−z} (0≤x≤0.5), which has a misfit layered structure, and Ca{sub 3}Co{sub 2}O{sub 6} which consists of 1D chains of alternating CoO{sub 6} trigonal prisms and CoO{sub 6} octahedra. Ca{sub 3}Co{sub 2}O{sub 6} was found to be a point compound without the substitution of Nd on the Ca site. The reported Nd{sub 2}CoO{sub 4} phase was not observed at 885 °C. A ternary (Ca{sub 1−x}Nd{sub 1+x})CoO{sub 4−z} (x=0) phase, or (CaNdCo)O{sub 4−z}, was found to be stable at this temperature. A solid solution region of distorted perovskite (Nd{sub 1−x}Ca{sub x})CoO{sub 3−z} (0≤x≤0.25, space group Pnma) was established. In the peripheral binary systems, while a solid solution region was identified for (Nd{sub 1−x}Ca{sub x}){sub 2}O{sub 3−z} (0≤x≤0.2), Nd was not found to substitute in the Ca site of CaO. Six solid solution tie-line regions and six three-phase regions were determined in the CaO–Nd{sub 2}O{sub 3}–CoO{sub z} system in air. - Graphical abstract: Phase diagram of the 1/2 Nd{sub 2}O{sub 3}–CaO–CoO{sub x} system at 885 °C, showing the limits of various solid solutions, and the tie-line relationships of various phases. - Highlights: • Phase diagram of the CaO–1/2 Nd{sub 2}O{sub 3}–CoO{sub z} system constructed. • System consists of thermoelectric oxide (Ca{sub 3−x}Nd{sub x})Co{sub 4}O{sub 9−z} (0≤x≤0.5). • Structures of (Nd{sub 1−x}Ca{sub x})CoO{sub 3−z} and (CaNdCo)O{sub 4−z} determined.

  5. Phase and extraction equilibria in H2O-sulfonol-HCl (H2SO4) and H2O-sodium dodecyl sulfate-HCl (H2SO4) systems

    NASA Astrophysics Data System (ADS)

    Zabolotnykh, S. A.; Lesnov, A. E.; Denisova, S. A.

    2016-10-01

    Solubility isotherms of water-sulfonol-hydrochloric (or sulfuric) acid and water-sodium dodecyl sulfate-hydrochloric acid systems at 75°C and a water-sodium dodecyl sulfate-sulfuric acid system at 50°C are constructed. Regions of two-phase liquid equilibrium suitable for use in extraction are found. Concentration parameters for extraction are determined. The interfacial distribution of a series of metal ions with and without such additional complexing reagents as diantipyrylmethane and diantipyrylheptane is studied.

  6. High performance Aurivillius phase sodium-potassium bismuth titanate lead-free piezoelectric ceramics with lithium and cerium modification

    NASA Astrophysics Data System (ADS)

    Wang, Chun-Ming; Wang, Jin-Feng

    2006-11-01

    The piezoelectric properties of the lithium and cerium modified A-site vacancies sodium-potassium bismuth titanate (NKBT) lead-free piezoceramics are investigated. The piezoelectric activity of NKBT ceramics is significantly improved by the modification of lithium and cerium. The Curie temperature TC, piezoelectric coefficient d33, and mechanical quality factor Qm for the NKBT ceramics modified with 0.10mol% (LiCe) are found to be 660°C, 25pC/N, and 3135, respectively. The Curie temperature gradually decreases from 675to650°C with the increase of (LiCe) modification. The dielectric spectroscopy shows that all the samples possess stable piezoelectric properties, demonstrating that the (LiCe) modified NKBT-based ceramics are the promising candidates for high temperature applications.

  7. Nonambipolar Transport and Torque in Perturbed Equilibria

    NASA Astrophysics Data System (ADS)

    Logan, N. C.; Park, J.-K.; Wang, Z. R.; Berkery, J. W.; Kim, K.; Menard, J. E.

    2013-10-01

    A new Perturbed Equilibrium Nonambipolar Transport (PENT) code has been developed to calculate the neoclassical toroidal torque from radial current composed of both passing and trapped particles in perturbed equilibria. This presentation outlines the physics approach used in the development of the PENT code, with emphasis on the effects of retaining general aspect-ratio geometric effects. First, nonambipolar transport coefficients and corresponding neoclassical toroidal viscous (NTV) torque in perturbed equilibria are re-derived from the first order gyro-drift-kinetic equation in the ``combined-NTV'' PENT formalism. The equivalence of NTV torque and change in potential energy due to kinetic effects [J-K. Park, Phys. Plas., 2011] is then used to showcase computational challenges shared between PENT and stability codes MISK and MARS-K. Extensive comparisons to a reduced model, which makes numerous large aspect ratio approximations, are used throughout to emphasize geometry dependent physics such as pitch angle resonances. These applications make extensive use of the PENT code's native interfacing with the Ideal Perturbed Equilibrium Code (IPEC), and the combination of these codes is a key step towards an iterative solver for self-consistent perturbed equilibrium torque. Supported by US DOE contract #DE-AC02-09CH11466 and the DOE Office of Science Graduate Fellowship administered by the Oak Ridge Institute for Science & Education under contract #DE-AC05-06OR23100.

  8. On Learning Algorithms for Nash Equilibria

    NASA Astrophysics Data System (ADS)

    Daskalakis, Constantinos; Frongillo, Rafael; Papadimitriou, Christos H.; Pierrakos, George; Valiant, Gregory

    Can learning algorithms find a Nash equilibrium? This is a natural question for several reasons. Learning algorithms resemble the behavior of players in many naturally arising games, and thus results on the convergence or non-convergence properties of such dynamics may inform our understanding of the applicability of Nash equilibria as a plausible solution concept in some settings. A second reason for asking this question is in the hope of being able to prove an impossibility result, not dependent on complexity assumptions, for computing Nash equilibria via a restricted class of reasonable algorithms. In this work, we begin to answer this question by considering the dynamics of the standard multiplicative weights update learning algorithms (which are known to converge to a Nash equilibrium for zero-sum games). We revisit a 3×3 game defined by Shapley [10] in the 1950s in order to establish that fictitious play does not converge in general games. For this simple game, we show via a potential function argument that in a variety of settings the multiplicative updates algorithm impressively fails to find the unique Nash equilibrium, in that the cumulative distributions of players produced by learning dynamics actually drift away from the equilibrium.

  9. Fluorite solubility equilibria in selected geothermal waters

    USGS Publications Warehouse

    Nordstrom, D.K.; Jenne, E.A.

    1977-01-01

    Calculation of chemical equilibria in 351 hot springs and surface waters from selected geothermal areas in the western United States indicate that the solubility of the mineral fluorite, CaF2, provides an equilibrium control on dissolved fluoride activity. Waters that are undersaturated have undergone dilution by non-thermal waters as shown by decreased conductivity and temperature values, and only 2% of the samples are supersaturated by more than the expected error. Calculations also demonstrate that simultaneous chemical equilibria between the thermal waters and calcite as well as fluorite minerals exist under a variety of conditions. Testing for fluorite solubility required a critical review of the thermodynamic data for fluorite. By applying multiple regression of a mathematical model to selected published data we have obtained revised estimates of the pK (10,96), ??Gof (-280.08 kcal/mole), ??Hof (-292.59 kcal/mole), S?? (16.39 cal/deg/mole) and CoP (16.16 cal/deg/mole) for CaF2 at 25??C and 1 atm. Association constants and reaction enthalpies for fluoride complexes with boron, calcium and iron are included in this review. The excellent agreement between the computer-based activity products and the revised pK suggests that the chemistry of geothermal waters may also be a guide to evaluating mineral solubility data where major discrepancies are evident. ?? 1977.

  10. Practical modifications to the Time-to-Event Continual Reassessment Method for phase I cancer trials with fast patient accrual and late-onset toxicities

    PubMed Central

    Polley, Mei-Yin C.

    2014-01-01

    The goal of phase I cancer trials is to determine the highest dose of a treatment regimen with an acceptable toxicity rate. Traditional designs for phase I trials, such as the Continual Reassessment Method (CRM) and the 3+3 design, require each patient or a cohort of patients to be fully evaluated for the dose-limiting toxicity (DLT) before new patients can be enrolled. As such, the trial duration may be prohibitively long. The Time-to-Event Continual Reassessment Method (TITE-CRM, Cheung and Chappell, 2000) circumvents this limitation by allowing staggered patient accrual without the need for complete DLT follow-up of previously treated patients. However, in the setting of fast patient accrual and late-onset toxicities, the TITE-CRM results in overly aggressive dose escalation and exposes a considerable number of patients to toxic doses. We examine a modification to the TITE-CRM proposed by the original TITE-CRM creator and propose an alternative approach useful in this setting by incorporating an accrual suspension rule. A simulation study designed based on a neuro-oncology trial indicates that the modified methods provide a much improved degree of safety than the TITE-CRM while maintaining desirable design accuracy. The practical aspects of the proposed designs are discussed. The modifications presented are useful when planning phase I trials involving chemoradiation therapy. PMID:21590790

  11. Switching of localized surface plasmon resonance of gold nanoparticles on a GeSbTe film mediated by nanoscale phase change and modification of surface morphology

    SciTech Connect

    Hira, T.; Homma, T.; Uchiyama, T.; Kuwamura, K.; Saiki, T.

    2013-12-09

    As a platform for active nanophotonics, localized surface plasmon resonance (LSPR) switching via interaction with a chalcogenide phase change material (GeSbTe) was investigated. We performed single-particle spectroscopy of gold nanoparticles placed on a GeSbTe thin film. By irradiation with a femtosecond pulsed laser for amorphization and a continuous wave laser for crystallization, significant switching behavior of the LSPR band due to the interaction of GeSbTe was observed. The switching mechanism was explained in terms of both a change in the refractive index and a modification of surface morphology accompanying volume expansion and reduction of GeSbTe.

  12. Chemical equilibria of rare earth oxides in glow-discharge mass spectrometry

    SciTech Connect

    Mei, Y.

    1992-01-01

    This research centers around method development and fundamental exploration of the rare earth elements (REE) in glow discharge mass spectrometry (GDMS). The capability of GDMS to analyze directly solids materials eliminates the sample dissolution and preconcentration steps required by many other methods. The simplicity of sample preparation and instrumental operation makes GDMS a promising analytical technique for the field of earth science. Initial studies were dedicated to improving the detection sensitivity of GDMS in analyzing the REE. This was accomplished by eliminating water contamination, a factor that was found to prevent the conversion of the rare earth oxidized to their atomic form in the glow discharge plasma. Methods experimented for water elimination included the uses of both a cryogenic cooling device and getter reagents. When used to determine the REE concentrations in a standard rock sample, the chemical elimination approach yielded comparable results to that obtained by other analytical methods. Further studies focused on probing the chemical reactions involving the REE and other plasma constituents in the glow discharge. It is proposed that the availability of the atomic REE in the glow discharge is strongly influenced by the oxidant and reductant contents in the plasma. Species that contain oxygen tend to shift the redox equilibria of REE toward the formation of their oxides, whereas species that compete for oxygen help reduce the oxidant content in the plasma, and shift the REE redox equilibria toward the formation of the REE atoms. Factors that govern the reaction processes of the REE equilibria were investigated by means of plasma reagent introduction and time-resolved discharge operation. Results indicate that while redox equilibria between the elemental REE and their monoxides exist on the cathode surface and in the gas phase, interactions occurring in the gas phase are probably the main paths for this equilibration in the glow discharge.

  13. Phase Equilibria of the Sn-Ni-V System: The 980°C Isothermal Section and the Sn-Rich Corner at 600°C and 300°C

    NASA Astrophysics Data System (ADS)

    Wu, Changjun; Su, Xuping; Peng, Haoping; Liu, Ya; Tu, Hao; Wang, Jianhua

    2015-10-01

    Ternary Sn-Ni-V alloys were prepared and annealed at 980°C, 600°C, and 300°C for 15, 60 and 60 days, respectively. The annealed alloys were metallographically examined and the equilibrium phases formed were identified on the basis of determination of composition and x-ray diffraction analysis. The isothermal region of the ternary Sn-Ni-V system at 980°C was studied. Nine three-phase regions and more than 20 conjugate lines were detected at 980°C. The range of composition of VNi2Sn at 980°C spans 24.5-59.2 at.% V, 52.1-25.5 at.% Ni, and 15.3-23.4 at.% Sn. Its lattice constant increases with increasing V content. A sharp increase near 40.4 at.% V is indicative of a second-order transition. It is believed that atomic site occupation changed when the V content was >40.4 at.%. The maximum solubility of V in Ni3Sn2 can reach 23.3 at.%; that in Ni3Sn is below 0.6 at.%. Up to 3.4 at.% Ni dissolves in V3Sn. The Sn-rich corner of the Sn-Ni-V system at 600°C and 300°C was also investigated experimentally. The solubility of Ni in VSn2 and V in Ni3Sn4 at 600°C and 300°C are both less than 0.5 at.%.

  14. Effect of ZnO on phase emergence, microstructure and surface modifications of calcium phosphosilicate glass/glass-ceramics having iron oxide

    NASA Astrophysics Data System (ADS)

    Sharma, K.; Dixit, A.; Bhattacharya, S.; Jagannath; Deo, M. N.; Kothiyal, G. P.

    2010-03-01

    The effect of ZnO on phase emergence and microstructure properties of glass and glass-ceramics with composition 25SiO 2-50CaO-15P 2O 5-(10 - x)Fe 2O 3- xZnO (where x = 0, 2, 5, 7 mol%) has been studied. They have been characterized using X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and scanning electron microscopy (SEM). Surface modifications of these glass-ceramics in simulated body fluid have been studied using Fourier transform infrared reflection spectroscopy (FTIR), XPS and SEM. Results have shown a decrease in the fraction of non-bridging oxygen with increase in zinc oxide content. Emergence of crystalline phases in glass-ceramics at different heat treatment temperatures was studied using XRD. When glass is heat treated at 800 °C calcium phosphate, hematite and magnetite are developed as major phases in the glass-ceramics samples with ZnO up to 5 mol%. In addition to these, calcium silicate (Ca 3Si 2O 7) phase is also observed when glass is heat treated at 1000 °C. The microstructure of the glass-ceramics heat treated at 800 °C exhibits the formation of nano-size (40-50 nm) grains. On heat treatment at 1000 °C crystallites grow to above 50 nm size and more than one phase are observed in the microstructure. The formation of thin flake-like structure with coarse particles is observed at high zinc oxide concentration ( x = 7 mol%). In vitro studies have shown the surface modifications and formation of Ca-P-rich layer on the glass-ceramics when immersed in simulated body fluids (SBF) for different durations. The bioactive response was found to depend on ZnO content.

  15. The Growth and Characterization of Germanium-Carbon Alloy Thin Films and Solid Phase Equilibria for Metal-Silicon - Ternary Systems: Magnesium, Calcium, Strontium, Barium, Scandium, Yttrium, Lanthanum, Titanium, Zirconium and Hafnium

    NASA Astrophysics Data System (ADS)

    Yuan, Haojie

    1992-09-01

    Thin films of pure germanium-carbon alloys (Ge _{rm x}C _{rm 1-x} with 0 <=q x <=q 1) have been grown on Si and Al_2O_3 substrates by pulsed laser ablation in a high vacuum chamber. The films were analyzed by x-ray 0-20 diffraction (XRD), x-ray photoelectron spectroscopy (XPS), Auger electron spectroscopy (AES), conductivity measurements and optical absorption spectroscopy. The analyses of these new materials showed that films of all compositions were amorphous, free of contamination and uniform in composition. By changing the film composition, the optical band gap of these semiconducting films was varied from 0.00 eV to 0.85 eV for x = 0.0 to 1.0 respectively. According to the AES results, the carbon atoms in the Ge-C alloy thin film samples have a bonding structure that is a mixture of sp^2 and sp^3 hybridizations. The presence of the sp^2 C is apparently what causes the bandgap of amorphous Ge-C alloys to decrease with increasing carbon concentration. The solidus portion of the ternary phase diagrams of the type M-Si-O, where M = Mg, Ca, Sr, Ba, Sc, Y, La, Ti, Zr and Hf have been derived at 298K and 1 atm oxygen partial pressure by investigating the bulk reactions possible in these systems. These phase diagrams, which have been determined by experiments and by calculations using thermodynamic data available, can be used to predict the occurrence of the reaction products or the stability of the phases present at the interfaces between different solid materials. Hence, they provide guides in designing thin film structures and in selecting candidate materials to form chemically stable interfaces. A research effort has been made on the investigation of the growth of diamond thin films from a carbon containing solid-CI_4, using laser ablation technique. The film grown by laser ablation from CI _4 is mainly composed of carbon with very small amount of oxygen and iodine as indicated by x-ray photoelectron spectroscopy data. The Auger electron spectroscopy result shows

  16. Modification of linear prepolymers to tailor heterogeneous network formation through photo-initiated Polymerization-Induced Phase Separation

    PubMed Central

    Szczepanski, Caroline R.; Stansbury, Jeffrey W.

    2015-01-01

    Polymerization-induced phase separation (PIPS) was studied in ambient photopolymerizations of triethylene glycol dimethacrylate (TEGDMA) modified by poly(methyl methacrylate) (PMMA). The molecular weight of PMMA and the rate of network formation (through incident UV-irradiation) were varied to influence both the promotion of phase separation through increases in overall free energy, as well as the extent to which phase development occurs during polymerization through diffusion prior to network gelation. The overall free energy of the polymerizing system increases with PMMA molecular weight, such that PIPS is promoted thermodynamically at low loading levels (5 wt%) of a higher molecular weight PMMA (120 kDa), while a higher loading level (20 wt%) is needed to induce PIPS with lower PMMA molecular weight (11 kDa), and phase separation was not promoted at any loading level tested of the lowest molecular weight PMMA (1 kDa). Due to these differences in overall free energy, systems modified by PMMA (11 kDa) underwent phase separation via Nucleation and Growth, and systems modified by PMMA (120 kDa), followed the Spinodal Decomposition mechanism. Despite differences in phase structure, all materials form a continuous phase rich in TEGDMA homopolymer. At high irradiation intensity (Io=20mW/cm2), the rate of network formation prohibited significant phase separation, even when thermodynamically preferred. A staged curing approach, which utilizes low intensity irradiation (Io=300µW/cm2) for the first ~50% of reaction to allow phase separation via diffusion, followed by a high intensity flood-cure to achieve a high degree of conversion, was employed to form phase-separated networks with reduced polymerization stress yet equivalent final conversion and modulus. PMID:26190865

  17. On the existence of a high-temperature polymorph of Na2Ca6Si4O15—implications for the phase equilibria in the system Na2O-CaO-SiO2

    NASA Astrophysics Data System (ADS)

    Kahlenberg, Volker; Maier, Matthias

    2016-06-01

    Singe crystals of a new high-temperature polymorph of Na2Ca6Si4O15 have been obtained from solid state reactions performed at 1300 °C. The basic crystallographic data of this so-called β-phase at ambient conditions are as follows: space group P1c1, a = 9.0112(5) Å, b = 7.3171(5) Å, c = 10.9723(6) Å, β = 107.720(14)°, V = 689.14(7) Å3, Z = 2. The crystals showed twinning by reticular merohedry (mimicking an orthorhombic C-centred unit cell) which was accounted for during data processing and structure solution. Structure determination was accomplished by direct methods. Least-squares refinements resulted in a residual of R(|F|) = 0.043 for 5811 observed reflections with I > 2σ(I). From a structural point of view β-Na2Ca6Si4O15 can be attributed to the group of mixed-anion silicates containing [Si2O7]-dimers as well as isolated [SiO4]-tetrahedra in the ratio 1:2, i.e. more precisely the formula can be written as Na2Ca6[SiO4]2[Si2O7]. The tetrahedral groups are arranged in layers parallel to (100). Sodium and calcium cations are located between the silicate anions for charge compensation and are coordinated by six to eight nearest oxygen ligands. Alternatively, the structure can be described as a mixed tetrahedral-octahedral framework based on kröhnkite-type [Ca(SiO4)2O2]-chains in which the CaO6-octahedra are corner-linked to bridging SiO4-tetrahedra. The infinite chains are running parallel to [001] and are concentrated in layers parallel to (010). Adjacent layers are shifted relative to each other by an amount of +δ or -δ along a*. Consequently, a …ABABAB… stacking sequence is created. A detailed comparison with related structures such as α-Na2Ca6Si4O15 and other A2B6Si4O15 representatives including topological as well as group theoretical aspects is presented. There are strong indications that monoclinic Na2Ca3Si2O8 mentioned in earlier studies is actually misinterpreted β-Na2Ca6Si4O15. In addition to the detailed crystallographic analysis of the

  18. Ternary liquid-liquid equilibria measurement for epoxidized soybean oil + acetic acid + water.

    PubMed

    Cai, Shuang-Fei; Wang, Li-Sheng; Yan, Guo-Qing; Li, Yi; Feng, Yun-Xia; Linghu, Rong-Gang

    2012-01-01

    Liquid-liquid equilibria (LLE) data were measured for ternary system epoxidized soybean oil (ESO) + acetic acid + water at 313.15, 323.15 and 333.15 K, respectively. The consistency of the measured LLE data was tested, using Othmer-Tobias correlation and root-mean-square deviation (sigma) in mass fraction of water in the lower phase and average value of the absolute difference (AAD) between experimental mass fraction of epoxidized soybean oil in the upper phase and that calculated using Othmer-Tobias correlation.

  19. U-Pb zircon geochronology and phase equilibria modelling of a mafic eclogite from the Sumdo complex of south-east Tibet: Insights into prograde zircon growth and the assembly of the Tibetan plateau

    NASA Astrophysics Data System (ADS)

    Weller, O. M.; St-Onge, M. R.; Rayner, N.; Waters, D. J.; Searle, M. P.; Palin, R. M.

    2016-10-01

    The Sumdo complex is a Permian-Triassic eclogitic metamorphic belt in south-east Tibet, which marks the location of a suture zone that separates the northern and southern Lhasa terranes. An integrated geochronological and petrological study of a mafic eclogite from the complex has constrained its tectonometamorphic history and provides a case study of zircon growth in eclogite as a product of prograde dissolution-precipitation. In situ U-Pb geochronology indicates that the eclogite contains a single population of zircon with a crystallisation age of 273.6 ± 2.8 Ma. The morphology and chemistry of the zircon grains are consistent with growth by dissolution-precipitation of protolith magmatic zircon. The presence of zircon grains as inclusions in the cores of peak phases indicates that zircon dissolution-precipitation occurred during prograde metamorphism, and calculated pressure and temperature conditions over which mineral inclusions in zircon are stable suggest that the zircon most likely precipitated at ~15.5-16.5 kbar and 500-560 °C. Subsequent peak metamorphism is calculated to have reached pressure-temperature conditions of 27 ± 1 kbar and 670 ± 50 °C. Previous studies, which have documented a range of peak metamorphic conditions from high- to ultrahigh-pressure at c. 266-230 Ma, indicate that the Sumdo complex is a composite belt that experienced protracted eclogite exhumation. The results of this study are consistent with this interpretation, and extend the age range of high-pressure metamorphism in the complex to over 40 Myr. Analysis of published pressure-temperature-time data indicates two systematic behaviours within this spread. First, peak metamorphic temperatures declined over time. Second, eclogite exhumation occurred in two discrete intervals: soon after formation, and during the demise of the subduction zone. The latter behaviour serves as a reminder that eclogite exhumation is the exception rather than the rule.

  20. Vapor-liquid equilibria for the systems difluoromethane + hydrogen fluoride, dichlorodifluoromethane + hydrogen fluoride, and chlorine + hydrogen fluoride

    SciTech Connect

    Kang, Y.W.

    1998-01-01

    Isothermal vapor-liquid equilibria for difluoromethane + hydrogen fluoride, dichlorodifluoromethane + hydrogen fluoride, and chlorine + hydrogen fluoride have been measured. The experimental data for the binary systems are correlated with the NRTL equation with the vapor-phase association model for the mixtures containing hydrogen fluoride, and the relevant parameters are presented. The binary system difluoromethane + hydrogen fluoride forms a homogeneous liquid phase, and the others form minimum boiling heterogeneous azeotropes at the experimental conditions.

  1. Study on vapor-liquid equilibria and surface tensions for nonpolar fluids by renormalization group theory and density gradient theory.

    PubMed

    Fu, Dong

    2006-10-01

    An equation of state (EOS) applicable for both the uniform and nonuniform fluids is established by using the density-gradient theory (DGT). In the bulk phases, the EOS reduces to statistical associating fluid theory (SAFT). By combining the EOS with the renormalization group theory (RGT), the vapor-liquid-phase equilibria and surface tensions for 10 nonpolar chainlike fluids are investigated from low temperature up to the critical point. The obtained results agree well with the experimental data.

  2. Effects of the dynamic modification of stationary phases by sorbates in gas chromatography: The possibility of separating enantiomers in achiral systems

    NASA Astrophysics Data System (ADS)

    Zenkevich, I. G.; Pavlovskii, A. A.

    2016-10-01

    It is shown that the gas chromatographic separation of enantiomers on columns with achiral nonpolar stationary phases is principally possible as a result of the dynamic modification of stationary phases by sorbates under analysis. It is found that a number of key characteristic features is intrinsic to such separation: it can be only partial, it does not occur for all chromatographic columns, and it is observed only for some compounds and only within narrow ranges of quantities of sorbates that are close to the limits of mass overload of chromatographic systems. These characteristic features are illustrated by the examples of separating (1 R,5 R)-(+)- and (1 S,5 S)-(-)-α-pinenes on a WCOT column with an RTX-5 phase. The main characteristic feature of the separation of enantiomers as a result of the dynamic modification of stationary phases is the nonconformity of peaks in chromatograms with two individual enantiomers, compared to other ways and means for their separation; the first eluting peak belongs to the enantiomer that predominates in a mixture irrespective of its configuration, while the second peak corresponds to the racemic mixture of enantiomers; i.e., the ratio of peak areas in chromatograms does not correspond to the actual ratio of enantiomers in samples under analysis and is strongly distorted as a result of their incomplete separation. It is concluded that the separation of racemic mixtures in achiral systems is fundamentally impossible under any conditions, and this is one of the key criteria of the validity of the considered concept as a whole.

  3. High and low pressure phase equilibria of a mildly alkalic lava from the 1965 Surtsey eruption: Implications for the evolution of mildly alkalic and transitional basalts in the south-eastern propagating rift zone of Iceland.

    NASA Astrophysics Data System (ADS)

    Thy, P.

    1991-01-01

    The south-eastern propagating rift zone of Iceland shows a progression from tholeiitic, to transitional, and mildly alkalic basalts going toward the front of the propagator. A petrogenetic model has been formulated based on low and high pressure melting experiments. The evolution of the magmas behind the front of the propagating rift is dominated by near surface processes (e.g., Katla and Hekla volcanic systems). Compared with the one atmosphere liquid line of descent, the Vestmannaeyjar lavas, erupted at the front of the propagating rift, have systematically higher Al 2O 3 and Na 2O contents consistent with the experimentally determined effects of high pressure, Labradoritic plagioclase megacrysts, which occur in the early phase of the Surtsey eruption at the front of the propagator, are consistent with the predicted effect of high pressure on plagioclase composition. On the other hand, augites similar to those of the high pressure experiments are unknown among the phenocryst and xenolith assemblages of the Vestmannaeyjar lavas (and other Icelandic lavas). Petrographic evidence points toward a high water content in the evolved lavas of the Vestmannaeyjar. A relatively high water activity and high pressure in the magma chambers at the front of the propagator could have caused a significant suppression of the liquids temperature, in particular for plagioclase. Seismic and magnetotelluric evidence suggest that magma chambers behind the propagating front occur at the depth equivalent to 2-3 kbar of pressure. At the front, magma chambers have been located by geophysical evidence at significantly greater depths equivalent to 3-8 kbar. The lavas erupted at the front of the propagator are located to the alkalic side of the thermal divide and, therefore, can be expected to evolve toward nepheline saturation under slightly hydrous conditions. The most evolved of these lavas are of ferrobasaltic compositions and may be saturated with augite. The lavas erupted behind the

  4. Relative equilibria of vortices in two dimensions.

    PubMed

    Palmore, J I

    1982-01-01

    An old problem of the evolution of finitely many interacting point vortices in the plane is shown to be amenable to investigation by critical point theory in a way that is identical to the study of the planar n-body problem of celestial mechanics. For any choice of positive circulations of the vortices it is shown by critical point theory applied to Kirchhoff's function that there are many relative equilibria configurations. Each of these configurations gives rise to a stationary configuration of the vortices in a suitably chosen rotating coordinate system. A sharp lower bound on the number of stationary vortex configurations for the problem of point vortices interacting in the plane is given. The problem of point vortices in a circular disk is defined and it is shown that these estimates hold for stationary configurations of small size. PMID:16593155

  5. Relative equilibria of vortices in two dimensions.

    PubMed

    Palmore, J I

    1982-01-01

    An old problem of the evolution of finitely many interacting point vortices in the plane is shown to be amenable to investigation by critical point theory in a way that is identical to the study of the planar n-body problem of celestial mechanics. For any choice of positive circulations of the vortices it is shown by critical point theory applied to Kirchhoff's function that there are many relative equilibria configurations. Each of these configurations gives rise to a stationary configuration of the vortices in a suitably chosen rotating coordinate system. A sharp lower bound on the number of stationary vortex configurations for the problem of point vortices interacting in the plane is given. The problem of point vortices in a circular disk is defined and it is shown that these estimates hold for stationary configurations of small size.

  6. Simulating Dynamic Equilibria: A Class Experiment

    NASA Astrophysics Data System (ADS)

    Harrison, John A.; Buckley, Paul D.

    2000-08-01

    A first-order reversible reaction is simulated on an overhead projector using small coins or discs. A simulation is carried out in which initially there are 24 discs representing reactant A and none representing reactant B. At the end of each minute half of the reactant A discs get converted to reactant B, and one quarter of the reactant B discs get converted to reactant A discs. Equilibrium is established with 8 A discs and 16 B discs, and no further net change is observed as the simulation continues. Another simulation beginning with 48 A discs and 0 B discs leads at equilibrium to 16 A discs and 32 B discs. These results illustrate how dynamic equilibria are established and allow the introduction of the concept of an equilibrium constant. Le Châtelier's principle is illustrated by further simulations.

  7. Analysis of the statistical thermodynamic model for nonlinear binary protein adsorption equilibria.

    PubMed

    Zhou, Xiao-Peng; Su, Xue-Li; Sun, Yan

    2007-01-01

    The statistical thermodynamic (ST) model was used to study nonlinear binary protein adsorption equilibria on an anion exchanger. Single-component and binary protein adsorption isotherms of bovine hemoglobin (Hb) and bovine serum albumin (BSA) on DEAE Spherodex M were determined by batch adsorption experiments in 10 mM Tris-HCl buffer containing a specific NaCl concentration (0.05, 0.10, and 0.15 M) at pH 7.40. The ST model was found to depict the effect of ionic strength on the single-component equilibria well, with model parameters depending on ionic strength. Moreover, the ST model gave acceptable fitting to the binary adsorption data with the fitted single-component model parameters, leading to the estimation of the binary ST model parameter. The effects of ionic strength on the model parameters are reasonably interpreted by the electrostatic and thermodynamic theories. The effective charge of protein in adsorption phase can be separately calculated from the two categories of the model parameters, and the values obtained from the two methods are consistent. The results demonstrate the utility of the ST model for describing nonlinear binary protein adsorption equilibria.

  8. Vapor-Phase Deposition and Modification of Metal-Organic Frameworks: State-of-the-Art and Future Directions.

    PubMed

    Stassen, Ivo; De Vos, Dirk; Ameloot, Rob

    2016-10-01

    Materials processing, and thin-film deposition in particular, is decisive in the implementation of functional materials in industry and real-world applications. Vapor processing of materials plays a central role in manufacturing, especially in electronics. Metal-organic frameworks (MOFs) are a class of nanoporous crystalline materials on the brink of breakthrough in many application areas. Vapor deposition of MOF thin films will facilitate their implementation in micro- and nanofabrication research and industries. In addition, vapor-solid modification can be used for postsynthetic tailoring of MOF properties. In this context, we review the recent progress in vapor processing of MOFs, summarize the underpinning chemistry and principles, and highlight promising directions for future research.

  9. Vapor-Phase Deposition and Modification of Metal-Organic Frameworks: State-of-the-Art and Future Directions.

    PubMed

    Stassen, Ivo; De Vos, Dirk; Ameloot, Rob

    2016-10-01

    Materials processing, and thin-film deposition in particular, is decisive in the implementation of functional materials in industry and real-world applications. Vapor processing of materials plays a central role in manufacturing, especially in electronics. Metal-organic frameworks (MOFs) are a class of nanoporous crystalline materials on the brink of breakthrough in many application areas. Vapor deposition of MOF thin films will facilitate their implementation in micro- and nanofabrication research and industries. In addition, vapor-solid modification can be used for postsynthetic tailoring of MOF properties. In this context, we review the recent progress in vapor processing of MOFs, summarize the underpinning chemistry and principles, and highlight promising directions for future research. PMID:27483444

  10. Shock-wave-induced grain refinement and phase state modification in coarse-grained and nanocrystalline titanium

    NASA Astrophysics Data System (ADS)

    Kolobov, Yu. R.; Manokhin, S. S.; Kolobova, A. Yu.; Kudymova, Yu. E.; Betekhtin, V. I.; Golyshev, A. A.; Molodets, A. M.; Andrievskii, R. A.

    2016-09-01

    We have experimentally studied the structure and phase variations in polycrystalline titanium stimulated by stepwise shock compression at pressures up to 40 GPa with subsequent unloading. The experiments were performed on samples of commercial titanium (VT1-0 grade) in a broad range of initial grain sizes (0.2-50 μm). The phenomenon of grain refinement and phase composition variation in titanium under stepwise shock-wave action has been studied by transmission and scanning electron microscopy techniques. Specific features of these changes are discussed.

  11. Stable equilibria of elliptic roly-poly toys

    NASA Astrophysics Data System (ADS)

    Hong, Seok-In

    2016-11-01

    As an instructive (gravitational potential) energy approach, we show that the elliptic roly-poly has a richer and more useful profile (including the tilted configuration) of stable equilibria than conventional spherical or cylindrical roly-polys.

  12. Variational Principle and Stability of Nonmonotonic Vlasov-Poisson Equilibria

    NASA Astrophysics Data System (ADS)

    Morrison, P. J.

    1987-10-01

    The stability of nonmonotonic equilibria of the Vlasov-Poisson equation is assessed by using nonlinear constants of motion . The constants of motion make up the free energy of the system , which upon variation yields nonmonotonic equilibria. Such equilibria have not previously been obtainable from a variation principle, but here this is accomplished by the inclusion of a passively advected tracer field. Definiteness of the second variation of the free energy gives a sufficient condition for stability in agreement with Gardner's theorem [5], Previously, we have argued that indefiniteness implies either spectral in stability or negative energy modes, which are generically unstable when one adds dissipation or nonlinearity [6]. Such is the case for the nonmonotonic equilibria considered.

  13. The freedom to choose neutron star magnetic field equilibria

    NASA Astrophysics Data System (ADS)

    Glampedakis, Kostas; Lasky, Paul D.

    2016-08-01

    Our ability to interpret and glean useful information from the large body of observations of strongly magnetised neutron stars rests largely on our theoretical understanding of magnetic field equilibria. We answer the following question: is one free to arbitrarily prescribe magnetic equilibria such that fluid degrees of freedom can balance the equilibrium equations? We examine this question for various models for neutron star matter; from the simplest single-fluid barotrope to more realistic non-barotropic multifluid models with superfluid/superconducting components, muons and entropy. We do this for both axi- and non-axisymmetric equilibria, and in Newtonian gravity and general relativity. We show that, in axisymmetry, the most realistic model allows complete freedom in choosing a magnetic field equilibrium whereas non-axisymmetric equilibria are never completely arbitrary.

  14. Molecular equilibria and condensation sequences in carbon rich gases

    NASA Technical Reports Server (NTRS)

    Sharp, C. M.; Wasserburg, G. J.

    1993-01-01

    Chemical equilibria in stellar atmospheres have been investigated by many authors. Lattimer, Schramm, and Grossman presented calculations in both O rich and C rich environments and predicted possible presolar condensates. A recent paper by Cherchneff and Barker considered a C rich composition with PAH's included in the calculations. However, the condensation sequences of C bearing species have not been investigated in detail. In a carbon rich gas surrounding an AGB star, it is often assumed that graphite (or diamond) condenses out before TiC and SiC. However, Lattimer et al. found some conditions under which TiC condenses before graphite. We have performed molecular equilibrium calculations to establish the stability fields of C(s), TiC(s), and SiC(s) and other high temperature phases under conditions of different pressures and C/O. The preserved presolar interstellar dust grains so far discovered in meteorites are graphite, diamond, SiC, TiC, and possibly Al2O3.

  15. Additives and solvents-induced phase and morphology modification of NaYF4 for improving up-conversion emission

    NASA Astrophysics Data System (ADS)

    Zhuang, Jianle; Yang, Xianfeng; Wang, Jing; Lei, Bingfu; Liu, Yingliang; Wu, Mingmei

    2016-01-01

    Both cubic and hexagonal NaYF4 were synthesized in different reaction systems via hydro/solvo-thermal route. The effects of reaction temperature, solvents, and additives on the synthesis of NaYF4 have been studied in detail. It has been shown that phase transformation from cubic NaYF4 to hexagonal NaYF4 always occurred. The sequence of the ability for inducing the phase transformation was ethanol>H2O>acetic acid. It is found that ethanol can not only facilitate the formation of hexagonal NaYF4 but also control the growth of the crystal. This is quite unusual for the growth of H-NaYF4. The up-conversion emission properties of Yb/Er co-doped NaYF4 have also been investigated and the results demonstrated some general principles for improving up-conversion emission.

  16. Thermodynamic properties and phase equilibria for Pt-Rh alloys

    SciTech Connect

    Jacob, K.T.; Priya, S.; Waseda, Yoshio

    1998-06-01

    The activity of rhodium in solid Pt-Rh alloys is measured in the temperature range from 900 to 1,300 K using the solid-state cell Pt-Rh, Rh + Rh{sub 2}O{sub 3}/(Y{sub 2}O{sub 3})ZrO{sub 2}/Pt{sub 1{minus}x}Rh{sub x} + Rh{sub 2}O{sub 3}, Pt-Rh. The activity of platinum and the free energy, enthalpy, and entropy of mixing are derived. Activities exhibit moderate negative deviation from Raoult`s law. The mixing properties can be represented by a pseudosubregular solution model in which excess entropy has the same type of functional dependence on composition as the enthalpy of mixing, {Delta}H = X{sub Rh} (1 {minus} X{sub Rh})[{minus}10,970 + 45X{sub Rh}] J/mol, {Delta}S{sup E} = X{sub Rh} (1 {minus} X{sub Rh})[{minus}3.80 + 1.55 {times} 10{sup {minus}2} X{sub Rh}] J/mol{center_dot}K. The negative enthalpy of mixing obtained in this study is in qualitative agreement with predictions of semiempirical models of Miedema and co-workers and Colinet et al. The results of this study do not support the solid-state miscibility gap suggested in the literature, but are consistent with liquidus data within experimental uncertainty limits.

  17. Experimental Studies of Phase Equilibria of Meteorites and Planetary Bodies

    NASA Technical Reports Server (NTRS)

    Stolper, Edward M.

    2005-01-01

    The primary theme of this project was the application of experimental petrology and geochemistry to a variety of problems in meteoritics and planetary geology. The studies were designed to help develop constraints on the histories of primitive meteorites and their components, the environments in which they formed and evolved, and to understand quantitatively the processes involved in the evolution of igneous rocks on the earth and other planetary bodies. We undertook several projects relating to the origin of CAIs and chondrules. Systematics in the thermodynamic properties of CAI-like liquids were investigated and used to elucidate speciation of multi-valent cations and sulfide capacity of silicate melts and to constrain redox conditions and the vapor pressures of volatile species over molten chondrules. We experimentally determined vanadium speciation in meteoritic pyroxenes and in pyroxenes crystallized from CAI-like melts under very reducing conditions. We also found that bulk oxygen isotope compositions of chondrules in the moderately unequilibrated LL chondrites are related to the relative timing of plagioclase crystallization. We completed an experimental study on the vaporization of beta-SiC and SiO2 (glass or cristobalite) in reducing gases and established the conditions under which these presolar grains could have survived in the solar nebula. We expanded our technique for determining the thermodynamic properties of minerals and liquids to iron-bearing systems. We determined activity-composition relationships in Pt-Fe, Pt-Cr and Pt-Fe-Cr alloys. Results were used to determine the thermodynamic properties of chromite-picrochromite spinels including the free energy of formation of end-member FeCr2O4. We also established a new approach for evaluating Pt-Fe saturation experiments. We calculated the T-fO2 relationships in equilibrated ordinary chondrites and thereby constrained the conditions of metamorphism in their parent bodies.

  18. MOLECULAR SIMULATION OF PHASE EQUILIBRIA FOR COMPLEX FLUIDS

    SciTech Connect

    Athanassios Z. Panagiotopoulos

    2009-09-09

    The general area of this project was the development and application of novel molecular simulation methods for prediction of thermodynamic and structural properties of complex polymeric, surfactant and ionic fluids. Over this project period, we have made considerable progress in developing novel algorithms to meet the computational challenges presented by the strong or long-range interactions in these systems and have generated data for well-defined mod-els that can be used to test theories and compare to experimental data. Overall, 42 archival papers and many invited and contributed presentations and lectures have been based on work supported by this project. 6 PhD, 1 M.S. and 2 postdoctoral students have been associated with this work, as listed in the body of the report.

  19. Phase equilibria in systems of formates with isobutyl alcohol

    SciTech Connect

    Seselkin, I.V.; Garber, Y.N.; Mironenko, V.F.

    1985-09-01

    The borate method, based on esterification with boric acid, was proposed for isolation of isobutyl alchohol. The method inv olves formation and hydrolysis of alkyl borate esters; in particular, formation and hydrolysis of triisobutyl borate. Esterification of isobutyl alcohol with boric acid is a reversible equilibrium reaction, and therefore in order to obtain high yields the water formed in the reaction must be removed. The presence of other organic compounds, which do not react with boric acid, in the mixture does not affect esterification of the alcohol. The reaction proceeds at 95-100/sup 0/ under atmospheric pressure. It was found that up to 97% of the isobutyl alcohol combines with boric acid. The resultant triisobutyl borate is isolated by ordinary distillation and then hydrolyzed to form boric acid and isobutyl alcohol.

  20. Eutectic morphology evolution and Sr-modification in Al-Si based alloys studied by 3D phase-field simulation coupled to Calphad data

    NASA Astrophysics Data System (ADS)

    Eiken, J.; Apel, M.

    2015-06-01

    The mechanical properties of Al-Si cast alloys are mainly controlled by the morphology of the eutectic silicon. Phase-field simulations were carried out to study the evolution of the multidimensional branched eutectic structures in 3D. Coupling to a Calphad database provided thermodynamic data for the multicomponent multiphase Al-Si-Sr-P system. A major challenge was to model the effect of the trace element Sr. Minor amounts of Sr are known to modify the silicon morphology from coarse flakes to fine coral-like fibers. However, the underlying mechanisms are still not fully understood. Two different in literature most discussed mechanisms were modelled: a) an effect of Sr on the growth kinetics of eutectic silicon and b) the formation of Al2Si2Sr on AlP particles, which consumes most potent nucleation sites and forces eutectic silicon to form with lower frequency and higher undercooling. The phase-field simulations only revealed a successful modification of the eutectic morphology when both effects acted in combination. Only in this case a clear depression of the eutectic temperature was observed. The required phase formation sequence L → fcc-(Al) → AlP → Al2Si2Sr → (Si) determines critical values for the Sr and P content.

  1. On the use of the dual-process Langmuir model for correlating unary equilibria and predicting mixed-gas adsorption equilibria.

    PubMed

    Ritter, James A; Bhadra, Shubhra J; Ebner, Armin D

    2011-04-19

    A new model has been developed for predicting mixed-gas adsorption equilibria from multicomponent gas mixtures based on the dual-process Langmuir (DPL) formulation. It predicts ideal, nonideal, and azeotropic adsorbed solution behavior from a knowledge of only single-component adsorption isotherms and the assertion that each binary pair in the gas mixture correlates in either a perfect positive (PP) or perfect negative (PN) fashion on each of the two Langmuir sites. The strictly PP and strictly PN formulations thus provide a simple means for determining distinct and absolute bounds of the behavior of each binary pair, and the PP or PN behavior can be confirmed by comparing predictions to binary experimental adsorption equilibria or from intuitive knowledge of binary pairwise adsorbate-adsorbent interactions. The extension to ternary and higher-order systems is straightforward on the basis of the pairwise additivity of the binary adsorbent-adsorbate interactions and two rules that logically restrict the combinations of PP and PN behaviors between binary pairs in a multicomponent system. Many ideal and nonideal binary systems and two ternary systems were tested against the DPL model. Each binary adsorbate-adsorbent pair exhibited either PP or PN behavior but nothing in between. This binary information was used successfully to predict ternary adsorption equilibria based on binary pairwise additivity. Overall, predictions from the DPL model were comparable to or significantly better than those from other models in the literature, revealing that its correlative and predictive powers are universally applicable. Because it is loading-explicit, simple to use, and also accurate, the DPL model may be one of the best equilibrium models to use in gas-phase adsorption process simulation.

  2. Two-dimensional magnetohydrodynamic equilibria with flow and studies of equilibria fluctuations

    SciTech Connect

    Agim, Y.Z.

    1989-08-01

    A set of reduced ideal MHD equations is derived to investigate equilibria of plasmas with mass flow in general two-dimensional geometry. These equations provide a means of investigating the effects of flow on self-consistent equilibria in a number of new two-dimensional configurations such as helically symmetric configurations with helical axis, which are relevant to stellarators, as well as axisymmetric configurations. It is found that as in the axisymmetric case, general two-dimensional flow equilibria are governed by a second-order quasi-linear partial differential equation for a magnetic flux function, which is coupled to a Bernoulli-type equation for the density. The equation for the magnetic flux function becomes hyperbolic at certain critical flow speeds which follow from its characteristic equation. When the equation is hyperbolic, shock phenomena may exist. As a particular example, unidirectional flow along the lines of symmetry is considered. In this case, the equation mentioned above is always elliptic. An exact solution for the case of helically symmetric unidirectional flow is found and studied to determine flow effects on the magnetic topology. In second part of this thesis, magnetic fluctuations due to the thermally excited MHD waves are investigated using fluid and kinetic models to describe stable, uniform, compressible plasma in the range above the drift wave frequency and below the ion cyclotron frequency. It is shown that the fluid model with resistivity yields spectral densities which are roughly Lorentzian, exhibit equipartition with no apparent cutoff in wavenumber space and a Bohm-type diffusion coefficient. Under certain conditions, the ensuing transport may be comparable to classical values. For a phenomenological cutoff imposed on the spectrum, the typical fluctuating-to-equilibrium magnetic field ratio is found to be of the order of 10 {sup {minus}10}.

  3. A vapor phase hydrothermal modification method converting a honeycomb structured hybrid film into photoactive TiO2 film.

    PubMed

    Zhao, Huijun; Shen, Yanming; Zhang, Shanqing; Zhang, Haimin

    2009-09-15

    Transforming an organic/inorganic hybrid material into a pure inorganic material without losing its original structure is of interest for a range of applications. In this work, a simple and effective vapor phase hydrothermal method was developed to transform a 3D honeycomb structured PS/TTIP hybrid film into a photoactive TiO2 film without dismantling the originally templated 3D structure. The method utilizes the vapor phase hydrothermal process to create titania network/clusters with sufficient mechanical strength via the formation of Ti-oxo bridges. The organic components of the sample can be removed by means of pyrolysis while perfectly maintaining the original 3D honeycomb structure. The resultant film can be directly used for photocatalysis applications and could be further modified for other applications. In principle, this method can be used to preserve 3D structures of other organic/inorganic hybrid films during their conversion to pure inorganic films via a pyrolysis process, if mechanically strong networks can be formed as a result of hydrolysis reactions. The ability to preserve the preferred 3D structure during the subsequent conversion processes enables realization of the full benefit of unique architectures created by a templating method. PMID:19496571

  4. Tearing Mode Stability of Evolving Toroidal Equilibria

    NASA Astrophysics Data System (ADS)

    Pletzer, A.; McCune, D.; Manickam, J.; Jardin, S. C.

    2000-10-01

    There are a number of toroidal equilibrium (such as JSOLVER, ESC, EFIT, and VMEC) and transport codes (such as TRANSP, BALDUR, and TSC) in our community that utilize differing equilibrium representations. There are also many heating and current drive (LSC and TORRAY), and stability (PEST1-3, GATO, NOVA, MARS, DCON, M3D) codes that require this equilibrium information. In an effort to provide seamless compatibility between the codes that produce and need these equilibria, we have developed two Fortran 90 modules, MEQ and XPLASMA, that serve as common interfaces between these two classes of codes. XPLASMA provides a common equilibrium representation for the heating and current drive applications while MEQ provides common equilibrium and associated metric information needed by MHD stability codes. We illustrate the utility of this approach by presenting results of PEST-3 tearing stability calculations of an NSTX discharge performed on profiles provided by the TRANSP code. Using the MEQ module, the TRANSP equilibrium data are stored in a Fortran 90 derived type and passed to PEST3 as a subroutine argument. All calculations are performed on the fly, as the profiles evolve.

  5. Unifying dynamical and structural stability of equilibria

    NASA Astrophysics Data System (ADS)

    Arnoldi, Jean-François; Haegeman, Bart

    2016-09-01

    We exhibit a fundamental relationship between measures of dynamical and structural stability of linear dynamical systems-e.g. linearized models in the vicinity of equilibria. We show that dynamical stability, quantified via the response to external perturbations (i.e. perturbation of dynamical variables), coincides with the minimal internal perturbation (i.e. perturbations of interactions between variables) able to render the system unstable. First, by reformulating a result of control theory, we explain that harmonic external perturbations reflect the spectral sensitivity of the Jacobian matrix at the equilibrium, with respect to constant changes of its coefficients. However, for this equivalence to hold, imaginary changes of the Jacobian's coefficients have to be allowed. The connection with dynamical stability is thus lost for real dynamical systems. We show that this issue can be avoided, thus recovering the fundamental link between dynamical and structural stability, by considering stochastic noise as external and internal perturbations. More precisely, we demonstrate that a linear system's response to white-noise perturbations directly reflects the intensity of internal white-noise disturbance that it can accommodate before becoming stochastically unstable.

  6. Phase relations in the system NaCl-KCl-H2O: IV. Differential thermal analysis of the sylvite liquidus in the KCl-H2O binary, the liquidus in the NaCl-KCl-H2O ternary, and the solidus in the NaCl-KCl binary to 2 kb pressure, and a summary of experimental data for thermodynamic-PTX analysis of solid-liquid equilibria at elevated P-T conditions

    USGS Publications Warehouse

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

    1992-01-01

    The sylvite liquidus in the binary system KCl-H2O and the liquidus in the ternary system NaCl-KCl-H2O were determined by using isobaric differential thermal analysis (DTA) cooling scans at pressures up to 2 kbars. Sylvite solubilities along the three-phase curve in the binary system KCl-H2O were obtained by the intersection of sylvite-liquidus isopleths with the three-phase curve in a P-T plot. These solubility data can be represented by the equation Wt.% KCl (??0.2) = 12.19 + 0.1557T - 5.4071 ?? 10-5 T2, where 400 ??? T ??? 770??C. These data are consistent with previous experimental observations. The solidus in the binary system NaCl-KCl was determined by using isobaric DTA heating scans at pressures up to 2 kbars. Using these liquidus and solidus data and other published information, a thermodynamic-PTX analysis of solid-liquid equilibria at high pressures and temperatures for the ternary system has been performed and is presented in an accompanying paper (Part V of this series). However, all experimental liquidus, solidus, and solvus data used in this analysis are summarized in this report (Part IV) and they are compared with the calculated values based on the analysis. ?? 1992.

  7. Some Phase Equilibrium Systematics of Martian Volatiles

    NASA Astrophysics Data System (ADS)

    Longhi, J.

    2010-03-01

    Binary pressure (P) - temperature (T) phase diagrams were constructed for the N2-, CH4-, and SO2-H2O systems making use of published triple points, critical points, and limited experimental determination of univariant equilibria.

  8. Modification of Solid Phase Red Cell Adherence Assay for the Detection of Platelet Antibodies in Patients With Thrombocytopenia

    PubMed Central

    Vongchan, Preeyanat; Nawarawong, Weerasak; Linhardt, Robert J.

    2009-01-01

    Platelet refractoriness is caused by HLA antibodies and platelet-specific antibodies. Current methods used to detect antiplatelet antibodies have limitations. Solid phase red cell adherence (SPRCA) lacks sensitivity and requires a second assay using chloroquine-treated intact platelets to specify the response due to anti-HLA. We modified SPRCA by using 2 types of antihuman platelet antibodies with different specificities toward platelet lysate and tested samples from 361 patients (69 with unexplained thrombocytopenia and 292 with poor response to platelet transfusions not explicable by alloimmunization or the clinical situation) and 50 from healthy volunteers. Our method compared favorably with platelet suspension direct immunofluorescence. All samples from healthy volunteers were negative; of the samples from the patient population, 240 were positive (147 samples had only antiplatelet and 3 samples had only anti-HLA antibodies). This modified technique had a sensitivity of 98% and a specificity of 91%. PMID:18701420

  9. Modification of solid phase red cell adherence assay for the detection of platelet antibodies in patients with thrombocytopenia.

    PubMed

    Vongchan, Preeyanat; Nawarawong, Weerasak; Linhardt, Robert J

    2008-09-01

    Platelet refractoriness is caused by HLA antibodies and platelet-specific antibodies. Current methods used to detect antiplatelet antibodies have limitations. Solid phase red cell adherence (SPRCA) lacks sensitivity and requires a second assay using chloroquine-treated intact platelets to specify the response due to anti-HLA. We modified SPRCA by using 2 types of antihuman platelet antibodies with different specificities toward platelet lysate and tested samples from 361 patients (69 with unexplained thrombocytopenia and 292 with poor response to platelet transfusions not explicable by alloimmunization or the clinical situation) and 50 from healthy volunteers. Our method compared favorably with platelet suspension direct immunofluorescence. All samples from healthy volunteers were negative; of the samples from the patient population, 240 were positive (147 samples had only antiplatelet and 3 samples had only anti-HLA antibodies). This modified technique had a sensitivity of 98% and a specificity of 91%.

  10. Eutectic equilibria in the quaternary system Fe-Cr-Mn-C

    NASA Technical Reports Server (NTRS)

    Nowotny, H.; Wayne, S.; Schuster, J. C.

    1982-01-01

    The constitution of the quaternary system, Fe-Cr-Mn-C and to a lesser extent of the quinary system, Fe-Cr-Mn-Al-C were examined for in situ composite alloy candidates. Multivariant eutectic compositions were determined from phase equilibria studies wherein M7C3 carbides (approximately 30% by volume) formed from the melt within gamma iron. An extended field of the hexagonal carbide, (Cr, Fe, Mn)7 C3, was found without undergoing transformation to the orthorhombic structure. Increasing stability for this carbide was found for higher ratios of Cr/Fe(+) Cr + Mn. Aluminum additions promoted a ferritic matrix while manganese favored the desired gamma austenitic matrix. In coexistence with the matrix phase, chromium enters preferentially the carbide phase while manganese distributes equally between the gamma matrix and the M7C3 carbide. The composition and lattice parameters of the carbide and matrix phases were determined to establish their respective stabilities.

  11. Chemical equilibria model analysis of Hope Creek eastern oil shale lysimeter leachate data

    SciTech Connect

    Essington, M.E.

    1989-09-01

    Leachates from field lysimeters containing an eastern oil shale, a retorted eastern oil shale, and an oil shale fines/retorted oil shale mixture were subjected to chemical equilibria analysis by the GEOCHEM model. Results of the chemical equilibria model analysis provided a more detailed characterization of the chemistry of oil shale materials. The aqueous chemistry of the lysimeter leachates is dominated by free ionic metal species and metal sulfate ion pairs. Activity diagrams shows that free metal ion activities (with the exception of Ca{sup 2+}) are directly related to SO{sub 4}{sup 2{minus}} activities. This suggests that the aqueous activities of the metals examined are not supported by metal sulfate solid phases. However, an examination of metal sulfate ion activity products (IAPs) as a function of time shows that the IAPs approach constant values after approximately 800 days of the field study. For the great majority of the metals examined, the IAP values suggest leachate undersaturation with respect to even the most stable metal sulfate phases. Leachates from all three materials are predicted by GEOCHEM to approach equilibrium with respect to gypsum and goethite. In addition, leachates from the oil shale lysimeter are predicted by GEOCHEM to approach equilibrium with respect to melanterite, Fe-jurbanite, franklinite, molybdite, and molybdic acid. Aluminum activities in all three lysimeter leachates fall within the stability region of several basic aluminum sulfates. However, Al{sup 3+} activities in the lysimeter leachates are not supported by sulfate phases. 34 refs., 15 figs., 2 tabs.

  12. Facile modification of multi-walled carbon nanotubes-polymeric ionic liquids-coated solid-phase microextraction fibers by on-fiber anion exchange.

    PubMed

    Feng, Juanjuan; Sun, Min; Bu, Yanan; Luo, Chuannan

    2015-05-01

    In situ anion exchange has been proved to be an efficient method for facile modification of polymeric ionic liquids (PILs)-based stationary phases. In this work, an on-fiber anion exchange process was utilized to tune the extraction performance of a multi-walled carbon nanotubes (MWCNTs)-poly(1-vinyl-3-octylimidazolium bromide) (poly(VOIm(+)Br(-)))-coated solid-phase microextraction (SPME) fiber. MWCNTs were first coated onto the stainless steel wire through a layer-by-layer fabrication method and then the PILs were coated onto the MWCNTs physically. Anion of the MWCNTs-poly(VOIm(+)Br(-)) fiber was changed into bis(triflroromethanesulfonyl)imide (NTf2(-)) and 2-naphthalene-sulfonate (NapSO3(-)) by on-fiber anion exchange. Coupled to gas chromatography, the MWCNTs-poly(VOIm(+)Br(-)) fiber showed acceptable extraction efficiency for hydrophilic and hydrogen-bonding-donating alcohols, with limits of detection (LODs) in the range of 0.005-0.05μgmL(-1); after the anion exchange with NTf2(-), the obtained MWCNTs-poly(VOIm(+)NTf2(-)) fiber brought wide linear ranges for hydrophobic n-alkanes with correlation coefficient (R) ranging from 0.994 to 0.997; aromatic property of the fiber was enhanced by aromatic NapSO3(-) anions to get sufficient extraction capacity for phthalate esters and halogenated aromatic hydrocarbons. The MWCNTs-poly(VOIm(+)NapSO3(-)) fiber was finally applied to determine several halogenated aromatic hydrocarbons in groundwater of industrial park.

  13. Morphology and phase modifications of MoO{sub 3} obtained by metallo-organic decomposition processes

    SciTech Connect

    Barros Santos, Elias de; Martins de Souza e Silva, Juliana; Odone Mazali, Italo

    2010-11-15

    Molybdenum oxide samples were prepared using different temperatures and atmospheric conditions by metallo-organic decomposition processes and were characterized by XRD, SEM and DRS UV/Vis and Raman spectroscopies. Variation in the synthesis conditions resulted in solids with different morphologies and oxygen vacancy concentrations. Intense characteristic Raman bands of crystalline orthorhombic {alpha}-MoO{sub 3}, occurring at 992 cm{sup -1} and 820 cm{sup -1}, are observed and their shifts can be related to the differences in the structure of the solids obtained. The sample obtained under nitrogen flow at 1073 K is a phase mixture of orthorhombic {alpha}-MoO{sub 3} and monoclinic {beta}-MoO{sub 3}. The characterization results suggest that the molybdenum oxide samples are non-stoichiometric and are described as MoO{sub x} with x < 2.94. Variations in the reaction conditions make it possible to tune the number of oxygen defects and the band gap of the final material.

  14. Bilinear relative equilibria of identical point vortices

    NASA Astrophysics Data System (ADS)

    Aref, Hassan; Beelen, Peter; Brøns, Morten

    2011-11-01

    A new class of bilinear relative equilibria of identical point vortices in which the vortices are constrained to be on two perpendicular lines, taken to be the x- and y-axes of a cartesian coordinate system, is introduced and studied. In general we have m vortices on the y-axis and n on the x- axis. We define generating polynomials q (z) and p (z) , respectively, for each set of vortices. A second order, linear ODE for p (z) given q (z) is derived. Several results relating the general solution of the ODE to relative equilibrium configurations are established. Our strongest result, obtained using Sturm's comparison theorem, is that if p (z) satisfies the ODE for a given q (z) with its imaginary zeros symmetric relative to the x-axis, then it must have at least n - m + 2 simple, real zeros. For m = 2 this provides a complete characterization of all zeros, and we study this case in some detail. In particular, we show that given q (z) =z2 +η2 , where η is real, there is a unique p (z) of degree n, and a unique value of η2 =An , such that the zeros of q (z) and p (z) form a relative equilibrium of n + 2 point vortices. We show that An ~2/3 n +1/2 , as n --> ∞ , where the coefficient of n is determined analytically, the next order term numerically. Supported in part by the Danish National Research Foundation through a Niels Bohr visiting professorship.

  15. Comparison of the mantle modification of the mantle column between two phases of kimberlite intrusion in Dalnyaya pipe, Yakutia

    NASA Astrophysics Data System (ADS)

    Ashchepkov, Igor; Spetsius, Zdislav; Salikhov, Ravil; Khmelnikova, Olga

    2013-04-01

    Dalnaya pipe is one of the largest in Daldyn field, Yakutia is composed of autolite breccia (AKB) and porphyric kimberlite (PK). Minerals from concentrates of both phases were compared and with the peridotite xenoliths minerals. Cpx from Dalnyaya are showing common tendencies Fe--Ti rise and Cr, Al, Na decrease. Garnets belong to lherzolite field with more deviation to harzbuirgitic one for (PK) . The chromites show two subtrends for Cr Fe, Ni vs TiO2. In general the variations of the AKB minerals and dispersion are higher but amount of depleted varieties is higher in PK. We used >50 xenoliths and ~1200 concentrate minerals for PT reconstructions. Combine PTX diagram show deep SCLM root beneath Dalnyaya with the main heating ~7 GPa. The HT 45mwm-2 branch is traced by some xenoliths from base to 2GPa. Essential inflection and heating detected by PT for OPx ~3GPa referring to Ca- enriched pyroxenitic garnets . Small Fe enrichment for Cpx and Gar found near 6 GPa referring to heated porhyroclastic varieties. Continuous and irregular growth of Fe# for Gar and low Fe Cpx Fe# 6 to 12# suggest that primary mantle layering beneath this pipe was smoothed by the high scale interaction with melts. The refertilization trend with Fe#9-15% rising upward in two branches refer to the Ilm and Cpx parental melt evolutions produced the intergrowth sometimes with garnets. In the PFO2 diagrams garnets and Cpx show continuous reduction to the lithosphere base to 4QMF higher for Cpx. Ilm - garnet trend is rising upward between -2 -0 QMF. The PT diagram for the AKB minerals from Dalnyaya pipe is nearly the same with the high dispersion to Fe rich varieties and smaller amount o f Mg rich minerals. Since the diamond grade is often determined by the amount of depleted varieties it is higher for the PK. Trace elements determined for Gar and Cpx from 13 xenoliths from the middle part of mantle section reveal very similar patterns in general. Supported by RBRF grant 11-05-00060.

  16. Ballooning mode second stability region for sequences of tokamak equilibria

    SciTech Connect

    Sugiyama, L.; Mark, J. W-K.

    1980-01-01

    A numerical study of several sequences of tokamak equilibria derived from two flux conserving sequences confirms the tendency of high n ideal MHD ballooning modes to stabilize for values of the plasma beta greater than a second critical beta, for sufficiently favorable equilibria. The major stabilizing effect of increasing the inverse rotational transform profile q(Psi) for equilibria with the same flux surface geometry is shown. The unstable region shifts toward larger shear d ln q/d ln ..gamma.. and the width of the region measured in terms of the poloidal beta or a pressure gradient parameter, for fixed shear, decreases. The smaller aspect ratio sequences are more sensitive to changes in q and have less stringent limits on the attainable value of the plasma beta in the high beta stable region. Finally, the disconnected mode approximation is shown to provide a reasonable description of the second high beta stability boundary.

  17. Extended fluid models: Pressure tensor effects and equilibria

    SciTech Connect

    Cerri, S. S.; Henri, P.; Califano, F.; Pegoraro, F.; Del Sarto, D.; Faganello, M.

    2013-11-15

    We consider the use of “extended fluid models” as a viable alternative to computationally demanding kinetic simulations in order to manage the global large scale evolution of a collisionless plasma while accounting for the main effects that come into play when spatial micro-scales of the order of the ion inertial scale d{sub i} and of the thermal ion Larmor radius ρ{sub i} are formed. We present an extended two-fluid model that retains finite Larmor radius (FLR) corrections to the ion pressure tensor while electron inertia terms and heat fluxes are neglected. Within this model we calculate analytic FLR plasma equilibria in the presence of a shear flow and elucidate the role of the magnetic field asymmetry. Using a Hybrid Vlasov code, we show that these analytic equilibria offer a significant improvement with respect to conventional magnetohydrodynamic shear-flow equilibria when initializing kinetic simulations.

  18. Predictions of adsorption equilibria of nonpolar hydrocarbons onto activated carbon

    SciTech Connect

    Do, D.D.; Wang, K.

    1998-12-08

    This paper presents a new approach to analyze the adsorption equilibria of nonpolar hydrocarbons onto activated carbon. The kinetic theory of gases and the 10-4-3 potential energy were employed to describe the adsorption process inside micropores. On the basis of this theory, a general isotherm model was proposed which possesses the potential capability of predicting the adsorption equilibria of an adsorbent by using the knowledge of its microporous structure and molecular properties of adsorbates. Experimental data of gases and vapors on Ajax activated carbon were employed to examine the model. Adsorption equilibria of binary mixtures were also investigated with the model, and it is shown that the model is capable of simulating the nonideal, or azeotropic, adsorption behaviors resulting from the structural heterogeneity of the adsorbent.

  19. Three-dimensional force-free looplike magnetohydrodynamic equilibria

    NASA Technical Reports Server (NTRS)

    Finn, John M.; Guzdar, Parvez N.; Usikov, Daniel

    1994-01-01

    Computations of three-dimensional force-free magnetohydrodynamic (MHD) equilibria, del x B = lambdaB with lambda = lambda(sub 0), a constant are presented. These equilibria are determined by boundary conditions on a surface corresponding to the solar photosphere. The specific boundary conditions used correspond to looplike magnetic fields in the corona. It is found that as lambda(sub 0) is increased, the loops of flux become kinked, and for sufficiently large lambda(sub 0), develop knots. The relationship between the kinking and knotting properties of these equilibria and the presence of a kink instability and related loss of equilibrium is explored. Clearly, magnetic reconnection must be involved for an unknotted loop equilibrium to become knotted, and speculations are made about the creation of a closed hyperbolic field line (X-line) about which this reconnection creating knotted field lines is centered.

  20. Water-Nafion equilibria. absence of Schroeder's paradox.

    PubMed

    Onishi, Lisa M; Prausnitz, John M; Newman, John

    2007-08-30

    Water-Nafion phase equilibria and proton conductivities were measured in two ways. First, Nafion was in contact with saturated water vapor. Second, Nafion was in contact with liquid water at the same temperature. At 29 degrees C, for preboiled, vapor-equilibrated Nafion exposed to water with an activity = 1 and air pressures ranging from 0 to 0.96 bar, the water content was lambda = 23 +/- 1 mol H(2)O/mol SO3-. For the preboiled, liquid-equilibrated membrane, lambda = 24 +/- 2. At 100% relative humidity (RH), the water content of preboiled Nafion decreased as the temperature rose from 30 to 80 degrees C but did not recover its initial water content when the temperature returned to 30 degrees C. The water content of predried Nafion at 1 atm and 30 degrees C was lambda = 13.7 +/- 0.2 when vapor-equilibrated and lambda = 13.1 +/- 0.5 when liquid-equilibrated. A Nafion membrane originally boiled in water had much higher liquid- and 100% RH vapor-equilibrated proton conductivities than the same membrane originally dried at 110 degrees C with a RH less than 2%. The liquid-equilibrated and 100% RH vapor-equilibrated membrane conductivities were the same when the membrane had the same thermal history. The conductivity data was fit to a model, and the water content was determined at different temperatures. The predried membrane water content increased with temperature, and the preboiled membrane's water content changed slightly with temperature. Both water sorption and proton-conductivity data do not exhibit Schroeder's paradox. These studies and previous results suggest that Schroeder's paradox is resolved when attention is given to the thermal history of the absorbing polymer.

  1. Higher-order equilibria of temporal soliton molecules in dispersion-managed fibers

    NASA Astrophysics Data System (ADS)

    Hause, A.; Mitschke, F.

    2013-12-01

    Bound states of two or three solitons in dispersion-managed fibers (soliton molecules) were experimentally demonstrated recently. We investigate with a modified perturbation analysis whether the binding mechanism creates a unique stable equilibrium of the relative positions of the solitons in the molecule. Indeed, we find a multitude of equilibrium states, alternatingly stable and unstable. This holds for either case: nearest neighbor solitons having the same or the opposite phase. The number of equilibria are limited by the level of the radiation background. The state with the smallest separation and the highest binding energy ("ground state") always occurs for opposite-phase pulses; the lowest-order state for in-phase pulses is always unstable. Stable long-chain molecules can be built with a mixture of different nearest-neighbor equilibrium separations. Our results agree with our numerical simulations and experimental results, and connect well with certain results in the literature.

  2. Solid–liquid equilibria of binary mixtures of fluorinated ionic liquids†

    PubMed Central

    Teles, Ana Rita R.; Correia, Helga; Maximo, Guilherme J.; Rebelo, Luís P. N.; Freire, Mara G.; Pereiro, Ana B.; Coutinho, João A. P.

    2016-01-01

    Within ionic liquids, fluorinated ionic liquids (FILs) present unique physico-chemical properties and potential applications in several fields. However, the melting point of these neoteric compounds is usually higher due to the presence of fluorine atoms. This drawback may be resolved by, for instance, mixing different FILs to create eutectic mixtures. In this work, binary mixtures of fluoro-containing and fluorinated ionic liquids were considered with the aim of decreasing their melting temperatures as well as understanding and characterizing these mixtures and their phase transitions. Five FILs were selected, allowing the investigation of four binary mixtures, each of them with a common ion. Their solid–liquid and solid–solid equilibria were studied by differential scanning calorimetry and the non-ideality of the mixtures was investigated. Overall, a variety of solid–liquid equilibria with systems exhibiting eutectic behavior, polymorphs with solid–solid phase transitions, and the formation of intermediate compounds and solid solutions were surprisingly found. In addition to these intriguing behaviours, novel FILs with lower melting temperatures were obtained by the formation of binary systems, thus enlarging the application range of FILs at lower temperatures. PMID:27603428

  3. Solid-liquid equilibria of binary mixtures of fluorinated ionic liquids.

    PubMed

    Teles, Ana Rita R; Correia, Helga; Maximo, Guilherme J; Rebelo, Luís P N; Freire, Mara G; Pereiro, Ana B; Coutinho, João A P

    2016-09-28

    Within ionic liquids, fluorinated ionic liquids (FILs) present unique physico-chemical properties and potential applications in several fields. However, the melting point of these neoteric compounds is usually higher due to the presence of fluorine atoms. This drawback may be resolved by, for instance, mixing different FILs to create eutectic mixtures. In this work, binary mixtures of fluoro-containing and fluorinated ionic liquids were considered with the aim of decreasing their melting temperatures as well as understanding and characterizing these mixtures and their phase transitions. Five FILs were selected, allowing the investigation of four binary mixtures, each of them with a common ion. Their solid-liquid and solid-solid equilibria were studied by differential scanning calorimetry and the non-ideality of the mixtures was investigated. Overall, a variety of solid-liquid equilibria with systems exhibiting eutectic behavior, polymorphs with solid-solid phase transitions, and the formation of intermediate compounds and solid solutions were surprisingly found. In addition to these intriguing behaviours, novel FILs with lower melting temperatures were obtained by the formation of binary systems, thus enlarging the application range of FILs at lower temperatures. PMID:27603428

  4. Solid-liquid equilibria of binary mixtures of fluorinated ionic liquids.

    PubMed

    Teles, Ana Rita R; Correia, Helga; Maximo, Guilherme J; Rebelo, Luís P N; Freire, Mara G; Pereiro, Ana B; Coutinho, João A P

    2016-09-28

    Within ionic liquids, fluorinated ionic liquids (FILs) present unique physico-chemical properties and potential applications in several fields. However, the melting point of these neoteric compounds is usually higher due to the presence of fluorine atoms. This drawback may be resolved by, for instance, mixing different FILs to create eutectic mixtures. In this work, binary mixtures of fluoro-containing and fluorinated ionic liquids were considered with the aim of decreasing their melting temperatures as well as understanding and characterizing these mixtures and their phase transitions. Five FILs were selected, allowing the investigation of four binary mixtures, each of them with a common ion. Their solid-liquid and solid-solid equilibria were studied by differential scanning calorimetry and the non-ideality of the mixtures was investigated. Overall, a variety of solid-liquid equilibria with systems exhibiting eutectic behavior, polymorphs with solid-solid phase transitions, and the formation of intermediate compounds and solid solutions were surprisingly found. In addition to these intriguing behaviours, novel FILs with lower melting temperatures were obtained by the formation of binary systems, thus enlarging the application range of FILs at lower temperatures.

  5. Force-free Jacobian equilibria for Vlasov-Maxwell plasmas

    SciTech Connect

    Abraham-Shrauner, B.

    2013-10-15

    New analytic force-free Vlasov-Maxwell equilibria for thin current sheets are presented. The magnetic flux densities are expressed in terms of Jacobian elliptic functions of one Cartesian spatial coordinate. The magnetic flux densities reduce to previously reported hyperbolic functions in one limit and sinusoidal functions in another limit of the modulus k. A much wider class of nonlinear force-free Vlasov-Maxwell equilibria open expanded possibilities for modeling of solar system, astrophysical and laboratory plasmas. Modified Maxwellian distribution functions are determined explicitly in terms of Jacobian elliptic functions. Conditions for double peaked distribution functions that could be unstable are developed.

  6. Long-range correlations and coherent structures in magnetohydrodynamic equilibria.

    PubMed

    Weichman, Peter B

    2012-12-01

    The equilibrium theory of the 2D magnetohydrodynamic equations is derived, accounting for the full infinite hierarchies of conserved integrals. An exact description in terms of two coupled elastic membranes emerges, producing long-ranged correlations between the magnetic and velocity fields. This is quite different from the results of previous variational treatments, which relied on a local product ansatz for the thermodynamic Gibbs distribution. The equilibria display the same type of coherent structures, such as compact eddies and zonal jets, previously found in pure fluid equilibria. Possible consequences of this for recent simulations of the solar tachocline are discussed.

  7. A method of computational magnetohydrodynamics defining stable Scyllac equilibria

    PubMed Central

    Betancourt, Octavio; Garabedian, Paul

    1977-01-01

    A computer code has been developed for the numerical calculation of sharp boundary equilibria of a toroidal plasma with diffuse pressure profile. This generalizes earlier work that was done separately on the sharp boundary and diffuse models, and it allows for large amplitude distortions of the plasma in three-dimensional space. By running the code, equilibria that are stable to the so-called m = 1, k = 0 mode have been found for Scyllac, which is a high beta toroidal confinement device of very large aspect ratio. PMID:16592383

  8. Ideal MHD beta-limits of poloidally asymmetric equilibria

    SciTech Connect

    Todd, A.M.M.; Miller, A.E.; Grimm, R.C.; Okabayashi, M.; Dalhed, H.E. Jr.

    1981-05-01

    The ideal MHD stability of poloidally asymmetric equilibria, which are typical of a tokamak reactor design with a single-null poloidal divertor is examined. As with symmetric equilibria, stability to non-axisymmetric modes improves with increasing triangularity and ellipticity, and with lower edge safety factor. Pressure profiles optimized with respect to ballooning stability are obtained for an asymmetric shape, resulting in ..beta../sub critical/ approx. = 5.7%. The corresponding value for an equivalent symmetric shape is ..beta../sub critical/ approx. = 6.5%.

  9. Metastable Equilibria Among Aqueous Organic Compounds

    NASA Astrophysics Data System (ADS)

    Shock, E.; Shipp, J.; Yang, Z.; Gould, I. R.

    2011-12-01

    compounds chosen for study include structural features that provide mechanistic insight into the reactions. By including cyclic and aromatic compounds, these results expand the diversity of organic compounds that react reversibly in geochemical processes. It follows that metastable equilibria among organic compounds may be inescapable during hydrothermal alteration and petroleum generation.

  10. Surface modification of La(0.8)Sr(0.2)CrO(3-δ)-YSZ dual-phase membranes for syngas production.

    PubMed

    Yu, Anthony S; Oh, Tae-Sik; Zhu, Ran; Gallegos, Alexa; Gorte, Raymond J; Vohs, John M

    2015-01-01

    Oxygen permeation fluxes were studied in Mixed Ionic and Electronic Conducting (MIEC) membranes based on composites of 40 vol% La(0.8)Sr(0.2)CrO3 (LSCr) and 60 vol% yttria-stabilized zirconia (YSZ), using ambient air and flowing CO to establish a P(O2) gradient. The ambipolar conductivity of the dense LSCr-YSZ composite was determined for membranes with dense layers that were 115 μm and 650 μm thick. Other parts of the investigation focused on how modifications to the surface on the CO side affected the fluxes. Using a porous LSCr-YSZ composite on the surface as the base case, oxygen fluxes were shown to increase dramatically upon addition of 5 wt% CeO2 as a catalyst and an additional increase was observed with 1 wt% Pt. Changes in the structure of the porous composite LSCr-YSZ surface to improve connectivity of the YSZ phase also led to large increases in the oxygen fluxes.

  11. A Simple Chaotic Flow with a Plane of Equilibria

    NASA Astrophysics Data System (ADS)

    Jafari, Sajad; Sprott, J. C.; Molaie, Malihe

    2016-06-01

    Using a systematic computer search, a simple four-dimensional chaotic flow was found that has the unusual feature of having a plane of equilibria. Such a system belongs to a newly introduced category of chaotic systems with hidden attractors that are important and potentially problematic in engineering applications.

  12. Substituent Effects on Keto-Enol Equilibria Using NMR Spectroscopy

    ERIC Educational Resources Information Center

    Manbeck, Kimberly A.; Boaz, Nicholas C.; Bair, Nathaniel C.; Sanders, Allix M. S.; Marsh, Anderson L.

    2011-01-01

    In this extension to a classic physical chemistry experiment, students record the proton nuclear magnetic resonance spectra of the [beta]-diketones 2,4-pentanedione, 3-methyl-2,4-pentanedione, and 3-chloro-2,4-pentanedione to investigate the effect of substituents on keto-enol tautomerization equilibria. From the integrated intensities of keto and…

  13. Acid-Base and Precipitation Equilibria in Wine

    ERIC Educational Resources Information Center

    Palma, Miguel; Barroso, Carmelo G.

    2004-01-01

    Experiments are performed to establish the changes of pH during the precipitation of potassium hydrogen tartrate, with its unfavorable impact on the stability of wine. Students, thus, obtain a clearer understanding of the interplay between a variety of chemical equilibria within a single medium.

  14. Chaotic magnetic fields in Vlasov-Maxwell equilibria

    SciTech Connect

    Ghosh, Abhijit; Janaki, M. S.; Dasgupta, Brahmananda; Bandyopadhyay, Alak

    2014-03-15

    Stationary solutions of Vlasov-Maxwell equations are obtained by exploiting the invariants of single particle motion leading to linear or nonlinear functional relations between current and vector potential. For a specific combination of invariants, it is shown that Vlasov-Maxwell equilibria have an associated Hamiltonian that exhibits chaos.

  15. Graphic Representation of Carbon Dioxide Equilibria in Biological Systems.

    ERIC Educational Resources Information Center

    Kindig, Neal B.; Filley, Giles F.

    1983-01-01

    The log C-pH diagram is a useful means of displaying quantitatively the many variables (including temperature) that determine acid-base equilibria in biological systems. Presents the diagram as extended to open/closed biological systems and derives a new water-ion balance method for determining equilibrium pH. (JN)

  16. Synthesis, phase composition modification, and optical properties of Ce{sup 3+}/Tb{sup 3+} activated KGdF{sub 4} and GdF{sub 3} submicrocrystals

    SciTech Connect

    Cao Chunyan; Yang, Hyun Kyoung; Moon, Byung Kee; Choi, Byung Chun; Jeong, Jung Hyun; Kim, Kwang Ho

    2012-03-15

    Ce{sup 3+}/Tb{sup 3+} co-doped series of samples have been synthesized based on a citric acid assisted hydrothermal method. By controlling the hydrothermal treating time, the samples evolve from the Ce{sup 3+}/Tb{sup 3+} co-doped cubic phase KGdF{sub 4} with spherical morphology into the Ce{sup 3+}/Tb{sup 3+} co-doped orthorhombic phase GdF{sub 3} with rhombic shape finally. The X-ray diffraction data illustrate the phase composition modification process of the samples. The field emission scanning electron microscopy and the transmission electron microscopy images suggest the transformation in the morphology of final products. The spectra of the energy-dispersive spectroscopy reveal the constituents of the samples. And the selected area electronic diffraction patterns prove the crystalline phases of the samples. Based on previous studies and the experimental data, one possible phase composition modification process has been summarized. The photoluminescence excitation and emission spectra and the luminescent dynamic decay curves demonstrate the variations in optical properties of the Ce{sup 3+}/Tb{sup 3+} co-doped final products. - Graphical abstract: Schematic illustration for the phase composition modification from the Ce{sup 3+}/Tb{sup 3+} doped KGdF{sub 4} to the Ce{sup 3+}/Tb{sup 3+}doped GdF{sub 3} with multiform morphologies and different sizes. (C presents cubic phase, H presents hexagonal phase, and O presents orthorhombic phase.) Highlights: Black-Right-Pointing-Pointer The samples were synthesized by a hydrothermal method. Black-Right-Pointing-Pointer The samples evolved from the cubic phase KGdF{sub 4} into the orthorhombic phase GdF{sub 3}. Black-Right-Pointing-Pointer The morphology evolved from the spherical shape into the rhombic shape finally. Black-Right-Pointing-Pointer A possible phase composition modification process was summarized. Black-Right-Pointing-Pointer The optical properties of final products were compared and studied.

  17. Home Modification

    MedlinePlus

    ... it is important to consider certain safety modifications. Adaptations such as those in the following list can ... The importance of a Consumer Perspective in Home Adaptation of Alzheimer’s Households” (Chapter 6 pp 91-112) ...

  18. Physical and reactive extraction equilibria of penicillin G in a hydrogen-bond acceptor solvent system.

    PubMed

    Lee, Sang Cheol

    2006-01-01

    Physical and reactive extraction equilibria of penicillin G were investigated experimentally and theoretically in the existence of n-butyl acetate as a hydrogen-bond acceptor solvent. Physical extraction equilibrium experiments were carried out varying the pH of aqueous phase and overall penicillin concentration. We compared the experimental data with the calculated results from four physical extraction equilibrium models suggested here and obtained the most reasonable model. Also, penicillin G was reactively extracted using Amberlite LA-2 in n-butyl acetate. The experimental variables were pH of the aqueous phase, overall amine concentration, and overall penicillin concentration. A combined equilibrium model including our physical extraction equilibrium expression and the reactive extraction equilibrium expression suggested by Reschke and Schügerl was used so as to analyze the current reactive extraction equilibrium system. The calculated results from the reactive extraction equilibrium model were in good agreement with the experimental data.

  19. On Nash-Equilibria of Approximation-Stable Games

    NASA Astrophysics Data System (ADS)

    Awasthi, Pranjal; Balcan, Maria-Florina; Blum, Avrim; Sheffet, Or; Vempala, Santosh

    One reason for wanting to compute an (approximate) Nash equilibrium of a game is to predict how players will play. However, if the game has multiple equilibria that are far apart, or ɛ-equilibria that are far in variation distance from the true Nash equilibrium strategies, then this prediction may not be possible even in principle. Motivated by this consideration, in this paper we define the notion of games that are approximation stable, meaning that all ɛ-approximate equilibria are contained inside a small ball of radius Δ around a true equilibrium, and investigate a number of their properties. Many natural small games such as matching pennies and rock-paper-scissors are indeed approximation stable. We show furthermore there exist 2-player n-by-n approximation-stable games in which the Nash equilibrium and all approximate equilibria have support Ω(log n). On the other hand, we show all (ɛ,Δ) approximation-stable games must have an ɛ-equilibrium of support O(Δ^{2-o(1)}/ɛ2{log n}), yielding an immediate n^{O(Δ^{2-o(1)}/ɛ^2log n)}-time algorithm, improving over the bound of [11] for games satisfying this condition. We in addition give a polynomial-time algorithm for the case that Δ and ɛ are sufficiently close together. We also consider an inverse property, namely that all non-approximate equilibria are far from some true equilibrium, and give an efficient algorithm for games satisfying that condition.

  20. Ubiquitin modifications

    PubMed Central

    Swatek, Kirby N; Komander, David

    2016-01-01

    Protein ubiquitination is a dynamic multifaceted post-translational modification involved in nearly all aspects of eukaryotic biology. Once attached to a substrate, the 76-amino acid protein ubiquitin is subjected to further modifications, creating a multitude of distinct signals with distinct cellular outcomes, referred to as the 'ubiquitin code'. Ubiquitin can be ubiquitinated on seven lysine (Lys) residues or on the N-terminus, leading to polyubiquitin chains that can encompass complex topologies. Alternatively or in addition, ubiquitin Lys residues can be modified by ubiquitin-like molecules (such as SUMO or NEDD8). Finally, ubiquitin can also be acetylated on Lys, or phosphorylated on Ser, Thr or Tyr residues, and each modification has the potential to dramatically alter the signaling outcome. While the number of distinctly modified ubiquitin species in cells is mind-boggling, much progress has been made to characterize the roles of distinct ubiquitin modifications, and many enzymes and receptors have been identified that create, recognize or remove these ubiquitin modifications. We here provide an overview of the various ubiquitin modifications present in cells, and highlight recent progress on ubiquitin chain biology. We then discuss the recent findings in the field of ubiquitin acetylation and phosphorylation, with a focus on Ser65-phosphorylation and its role in mitophagy and Parkin activation. PMID:27012465

  1. Comprehensive profiling of ribonucleosides modification by affinity zirconium oxide-silica composite monolithic column online solid-phase microextraction - Mass spectrometry analysis.

    PubMed

    Jiang, Han-Peng; Chu, Jie-Mei; Lan, Meng-Dan; Liu, Ping; Yang, Na; Zheng, Fang; Yuan, Bi-Feng; Feng, Yu-Qi

    2016-09-01

    More than 140 modified ribonucleosides have been identified in RNA. Determination of endogenous modified ribonucleosides in biological fluids may serve as non-invasive disease diagnostic strategy. However, detection of the modified ribonucleosides in biological fluids is challenging, especially for the low abundant modified ribonucleosides due to the serious matrix interferences of biological fluids. Here, we developed a facile preparation strategy and successfully synthesized zirconium oxide-silica (ZrO2/SiO2) composite capillary monolithic column that exhibited excellent performance for the selective enrichment of cis-diol-containing compounds. Compared with the boronate-based affinity monolith, the ZrO2/SiO2 monolith showed ∼2 orders of magnitude higher extraction capacity and can be used under physiological pH (pH 6.5-7.5). Using the prepared ZrO2/SiO2 composite monolith as the trapping column and reversed-phase C18 column as the analytical column, we further established an online solid-phase microextraction (SPME) in combination with liquid chromatography-mass spectrometry (online SPME-LC-MS/MS) analysis for the comprehensive profiling of ribonucleosides modification in human urine. Our results showed that 68 cis-diol-containing ribosylated compounds were identified in human urine, which is, to the best of our knowledge, the highest numbers of cis-diol-containing compounds were determined in a single analysis. It is worth noting that four modified ribonucleosides were discovered in the human urine for the first time. In addition, the quantification results from the pooled urine samples showed that compared to healthy controls, the contents of sixteen ribose conjugates in the urine of gastric cancer, eleven in esophagus cancer and seven in lymphoma increased more than two folds. Among these ribose conjugates, four ribose conjugates increased more than two folds in both gastric cancer and esophagus cancer; three ribose conjugates increased more than two

  2. Comprehensive profiling of ribonucleosides modification by affinity zirconium oxide-silica composite monolithic column online solid-phase microextraction - Mass spectrometry analysis.

    PubMed

    Jiang, Han-Peng; Chu, Jie-Mei; Lan, Meng-Dan; Liu, Ping; Yang, Na; Zheng, Fang; Yuan, Bi-Feng; Feng, Yu-Qi

    2016-09-01

    More than 140 modified ribonucleosides have been identified in RNA. Determination of endogenous modified ribonucleosides in biological fluids may serve as non-invasive disease diagnostic strategy. However, detection of the modified ribonucleosides in biological fluids is challenging, especially for the low abundant modified ribonucleosides due to the serious matrix interferences of biological fluids. Here, we developed a facile preparation strategy and successfully synthesized zirconium oxide-silica (ZrO2/SiO2) composite capillary monolithic column that exhibited excellent performance for the selective enrichment of cis-diol-containing compounds. Compared with the boronate-based affinity monolith, the ZrO2/SiO2 monolith showed ∼2 orders of magnitude higher extraction capacity and can be used under physiological pH (pH 6.5-7.5). Using the prepared ZrO2/SiO2 composite monolith as the trapping column and reversed-phase C18 column as the analytical column, we further established an online solid-phase microextraction (SPME) in combination with liquid chromatography-mass spectrometry (online SPME-LC-MS/MS) analysis for the comprehensive profiling of ribonucleosides modification in human urine. Our results showed that 68 cis-diol-containing ribosylated compounds were identified in human urine, which is, to the best of our knowledge, the highest numbers of cis-diol-containing compounds were determined in a single analysis. It is worth noting that four modified ribonucleosides were discovered in the human urine for the first time. In addition, the quantification results from the pooled urine samples showed that compared to healthy controls, the contents of sixteen ribose conjugates in the urine of gastric cancer, eleven in esophagus cancer and seven in lymphoma increased more than two folds. Among these ribose conjugates, four ribose conjugates increased more than two folds in both gastric cancer and esophagus cancer; three ribose conjugates increased more than two

  3. Generalized magnetotail equilibria: Effects of the dipole field, thin current sheets, and magnetic flux accumulation

    NASA Astrophysics Data System (ADS)

    Sitnov, M. I.; Merkin, V. G.

    2016-08-01

    Generalizations of the class of quasi-1-D solutions of the 2-D Grad-Shafranov equation, first considered by Schindler in 1972, are investigated. It is shown that the effect of the dipole field, treated as a perturbation, can be included into the original 1972 class solution by modification of the boundary conditions. Some of the solutions imply the formation of singularly thin current sheets. Equilibrium solutions for such sheets resolving their singular current structure on the scales comparable to the thermal ion gyroradius can be obtained assuming anisotropic and nongyrotropic plasma distributions. It is shown that one class of such equilibria with the dipole-like boundary perturbation describes bifurcation of the near-Earth current sheet. Another class of weakly anisotropic equilibria with thin current sheets embedded into a thicker plasma sheet helps explain the formation of thin current sheets in a relatively distant tail, where such sheets can provide ion Landau dissipation for spontaneous magnetic reconnection. The free energy for spontaneous reconnection can be provided due to accumulation of the magnetic flux at the tailward end of the closed field line region. The corresponding hump in the normal magnetic field profile Bz(x,z = 0) creates a nonzero gradient along the tail. The resulting gradient of the equatorial magnetic field pressure is shown to be balanced by the pressure gradient and the magnetic tension force due to the higher-order correction of the latter in the asymptotic expansion of the tail equilibrium in the ratio of the characteristic tail current sheet variations across and along the tail.

  4. [Lifestyle modifications].

    PubMed

    Kawano, Yuhei

    2015-11-01

    Lifestyle modifications are important in the prevention and treatment of hypertension. The Japanese Society of Hypertension Guidelines for the Management of Hypertension (JSH2014) recommend salt reduction (< 6 g/day), increased intake of vegetables/fruit and fish (fish oil), reduced intake of cholesterol and saturated fatty acids, weight loss (body mass index < 25kg/m2), exercise (≥ 30 min/day), reduction of alcohol intake (≤ 20-30 mL/day in men, ≤ 10-20 mL/day in women as ethanol), and quitting smoking. These lifestyle modifications are capable of reducing blood pressure and ameliorating other cardiovascular risk factors. However, the reduction in blood pressure is mild to moderate and the adherence to lifestyle modifications has been still suboptimal. PMID:26619658

  5. Effect of substituents and structural modification on conformational equilibrium in bis-quinolizidine system

    NASA Astrophysics Data System (ADS)

    Wysocka, Waleria; Brukwicki, Tadeusz; Włodarczak, Jacek

    2012-06-01

    On the basis of literature interpretation of 13C NMR and 1H NMR spectra of bis-quinolizidine alkaloids, the values of free enthalpy ΔG of conformational equilibria of those compounds were calculated. The results were analysed together with the X-ray and DFT data to discuss the effects of different substituents attached to the sparteine system in various positions as well as the effects of structural modifications on conformational equilibria. The measure of the effect was expressed by ΔΔG value, defined as the difference in ΔG of the compound under consideration and its parent compound without a given substituent.

  6. Vlasov tokamak equilibria with shearad toroidal flow and anisotropic pressure

    NASA Astrophysics Data System (ADS)

    Throumoulopoulos, George; Kuiroukidis, Apostolos; Tasso, Henri

    2015-11-01

    By choosing appropriate deformed Maxwellian ion and electron distribution functions depending on the two particle constants of motion, i.e. the energy and toroidal angular momentum, we reduce the Vlasov axisymmetric equilibrium problem for quasineutral plasmas to a transcendental Grad-Shafranov-like equation. This equation is then solved numerically under the Dirichlet boundary condition for an analytically prescribed boundary possessing a lower X-point to construct tokamak equilibria with toroidal sheared ion flow and anisotropic pressure. Depending on the deformation of the distribution functions these steady states can have toroidal current densities either peaked on the magnetic axis or hollow. These two kinds of equilibria may be regarded as a bifurcation in connection with symmetry properties of the distribution functions on the magnetic axis. This work has received funding from (a) the National Programme for the Controlled Thermonuclear Fusion, Hellenic Republic, (b) Euratom research and training programme 2014-2018 under grant agreement No 633053.

  7. Topology of tokamak plasma equilibria with toroidal current reversal

    SciTech Connect

    Rodrigues, Paulo; Bizarro, Joao P. S.

    2012-01-15

    Some general principles about scalar functions with critical points are used to rigorously ascertain that magnetic equilibria with both toroidal current reversal and nested magnetic surfaces are atypical solutions and highly unstable to arbitrary perturbations of boundary conditions and other parameters. The cause for such is shown to lie in the condition of nested magnetic surfaces and not in the possibility of current reversal and consequent vanishing of the poloidal field inside the plasma. Rather than supporting the claim that instability against experimentally driven perturbations forbids configurations with toroidal current reversal, it is argued that these can be attained if an axisymmetric island system is allowed for in order to break the condition of nested magnetic surfaces. A number of results previously reported in the literature are discussed and reinterpreted under the proposed framework, providing some physical insight on the nature of equilibria with toroidal current reversal.

  8. Sloshing-ion equilibria in the TARA endplugs

    SciTech Connect

    Hokin, S.; Kesner, J.

    1983-11-01

    We have employed a modified version of the LLNL Bounce-average Fokker-Planck code to model neutral beam-produced sloshing-ion equilibria in the TARA endplugs. The questions we have addressed concern the effect of deuterium beam operation as opposed to hydrogen operation, and the advantage of using full-energy beams rather than the usual three-component beams. We find that, for the expected base case TARA operating parameters, a 40% savings in required beam power is attained by using deuterium beams rather than hydrogen beams, and that the use of full-energy beams results in an additional 26% power savings for these parameters. For higher plasma temperatures the use of full-energy beams becomes significantly advantagous. We have also investigated the equilibria of two possible alternate mirror configurations for the TARA endplugs, believed to be more stable to trapped particle modes, and report those results here.

  9. Finding Bounded Rational Equilibria. Part 1; Iterative Focusing

    NASA Technical Reports Server (NTRS)

    Wolpert, David H.

    2004-01-01

    A long-running difficulty with conventional game theory has been how to modify it to accommodate the bounded rationality characterizing all real-world players. A recurring issue in statistical physics is how best to approximate joint probability distributions with decoupled (and therefore far more tractable) distributions. It has recently been shown that the same information theoretic mathematical structure, known as Probability Collectives (PC) underlies both issues. This relationship between statistical physics and game theory allows techniques and insights from the one field to be applied to the other. In particular, PC provides a formal model-independent definition of the degree of rationality of a player and of bounded rationality equilibria. This pair of papers extends previous work on PC by introducing new computational approaches to effectively find bounded rationality equilibria of common-interest (team) games.

  10. Braided coronal loops: equilibria, heating, and observational signatures

    NASA Astrophysics Data System (ADS)

    Pontin, David Iain; Hornig, Gunnar; Candelaresi, Simon

    2016-05-01

    We examine the dynamics of coronal loops containing non-trivial magnetic field line braiding. We discuss the existence of braided force-free equilibria, and demonstrate that these equilibria must contain current layers whose thickness becomes increasingly small for increasing field complexity. In practical terms, the implication is that if one considers a line-tied coronal loop that is driven by photospheric motions, then the eventual onset of reconnection and energy release is inevitable. Once the initial reconnection event is triggered a turbulent relaxation ensues. We discuss the relation with Parker’s braiding mechanism for coronal heating, and go on to describe the expected observational signatures of energy release in such a braided coronal loop.

  11. Vlasov tokamak equilibria with sheared toroidal flow and anisotropic pressure

    SciTech Connect

    Kuiroukidis, Ap; Throumoulopoulos, G. N.; Tasso, H.

    2015-08-15

    By choosing appropriate deformed Maxwellian ion and electron distribution functions depending on the two particle constants of motion, i.e., the energy and toroidal angular momentum, we reduce the Vlasov axisymmetric equilibrium problem for quasineutral plasmas to a transcendental Grad-Shafranov-like equation. This equation is then solved numerically under the Dirichlet boundary condition for an analytically prescribed boundary possessing a lower X-point to construct tokamak equilibria with toroidal sheared ion flow and anisotropic pressure. Depending on the deformation of the distribution functions, these steady states can have toroidal current densities either peaked on the magnetic axis or hollow. These two kinds of equilibria may be regarded as a bifurcation in connection with symmetry properties of the distribution functions on the magnetic axis.

  12. Generalized statistical model for multicomponent adsorption equilibria on zeolites

    SciTech Connect

    Rota, R.; Gamba, G.; Paludetto, R.; Carra, S.; Morbidelli, M. )

    1988-05-01

    The statistical thermodynamic approach to multicomponent adsorption equilibria on zeolites has been extended to nonideal systems, through the correction of cross coefficients characterizing the interaction between unlike molecules. Estimation of the model parameters requires experimental binary equilibrium data. Comparisons with the classical model based on adsorbed solution theory are reported for three nonideal ternary systems. The two approaches provide comparable results in the simulation of binary and ternary adsorption equilibrium data at constant temperature and pressure.

  13. Beltrami–Bernoulli equilibria in plasmas with degenerate electrons

    SciTech Connect

    Berezhiani, V. I.; Shatashvili, N. L.; Mahajan, S. M.

    2015-02-15

    A new class of Double Beltrami–Bernoulli equilibria, sustained by electron degeneracy pressure, is investigated. It is shown that due to electron degeneracy, a nontrivial Beltrami–Bernoulli equilibrium state is possible even for a zero temperature plasma. These states are, conceptually, studied to show the existence of new energy transformation pathways converting, for instance, the degeneracy energy into fluid kinetic energy. Such states may be of relevance to compact astrophysical objects like white dwarfs, neutron stars, etc.

  14. Vapor-liquid and vapor-liquid-liquid equilibria of carbon dioxide/n-perfluoroalkane/n-alkane ternary mixtures.

    PubMed

    Colina, Coray M; Gubbins, Keith E

    2005-02-24

    Perfluoroalkanes have numerous applications (e.g., in the medical field and the chemical industry), and their high affinity for carbon dioxide makes them attractive as surfactants and cosolvents. Although research in this area has grown in the past few years, very little phase-equilibrium data is available in the open literature for these systems. In this work, we present, for the first time, predictions of vapor-liquid and vapor-liquid-liquid equilibria of binary and ternary systems of carbon dioxide/n-perfluoroalkane/n-alkane. Our results are based on the SAFT-VR EOS (statistical associating fluid theory of variable range, equation of state), and we study the influence of temperature, pressure, composition, and chain length on the phase diagram. The predicted phase diagrams are based on temperature-independent binary interaction parameters, and no ternary parameters are introduced. Comparisons to the available experimental and molecular simulation data show that the predicted diagrams should provide a good representation of the phase equilibria.

  15. Solution influence on biomolecular equilibria - Nucleic acid base associations

    NASA Technical Reports Server (NTRS)

    Pohorille, A.; Pratt, L. R.; Burt, S. K.; Macelroy, R. D.

    1984-01-01

    Various attempts to construct an understanding of the influence of solution environment on biomolecular equilibria at the molecular level using computer simulation are discussed. First, the application of the formal statistical thermodynamic program for investigating biomolecular equilibria in solution is presented, addressing modeling and conceptual simplications such as perturbative methods, long-range interaction approximations, surface thermodynamics, and hydration shell. Then, Monte Carlo calculations on the associations of nucleic acid bases in both polar and nonpolar solvents such as water and carbon tetrachloride are carried out. The solvent contribution to the enthalpy of base association is positive (destabilizing) in both polar and nonpolar solvents while negative enthalpies for stacked complexes are obtained only when the solute-solute in vacuo energy is added to the total energy. The release upon association of solvent molecules from the first hydration layer around a solute to the bulk is accompanied by an increase in solute-solvent energy and decrease in solvent-solvent energy. The techniques presented are expectd to displace less molecular and more heuristic modeling of biomolecular equilibria in solution.

  16. Nash Equilibria in Multi-Agent Motor Interactions

    PubMed Central

    Braun, Daniel A.; Ortega, Pedro A.; Wolpert, Daniel M.

    2009-01-01

    Social interactions in classic cognitive games like the ultimatum game or the prisoner's dilemma typically lead to Nash equilibria when multiple competitive decision makers with perfect knowledge select optimal strategies. However, in evolutionary game theory it has been shown that Nash equilibria can also arise as attractors in dynamical systems that can describe, for example, the population dynamics of microorganisms. Similar to such evolutionary dynamics, we find that Nash equilibria arise naturally in motor interactions in which players vie for control and try to minimize effort. When confronted with sensorimotor interaction tasks that correspond to the classical prisoner's dilemma and the rope-pulling game, two-player motor interactions led predominantly to Nash solutions. In contrast, when a single player took both roles, playing the sensorimotor game bimanually, cooperative solutions were found. Our methodology opens up a new avenue for the study of human motor interactions within a game theoretic framework, suggesting that the coupling of motor systems can lead to game theoretic solutions. PMID:19680426

  17. Direct calculation of solid-liquid equilibria from density-of-states Monte Carlo simulations.

    PubMed

    Mastny, Ethan A; de Pablo, Juan J

    2005-03-22

    A density-of-states Monte Carlo method is proposed for simulations of solid-liquid phase equilibria. A modified Wang-Landau density-of-states sampling approach is used to perform a random walk in regions of potential energy and volume relevant to solid-liquid equilibrium. The method provides a direct estimate of the relative density of states [Omega(U,V)] and thus the relative free energy within these regions, which is subsequently used to determine portions of the melting curve over wide ranges of pressure and temperature. The validity and usefulness of the method are demonstrated by performing crystallization simulations for the Lennard-Jones fluid and for NaCl.

  18. Relative Equilibria in the Spherical, Finite Density Three-Body Problem

    NASA Astrophysics Data System (ADS)

    Scheeres, D. J.

    2016-05-01

    The relative equilibria for the spherical, finite density three-body problem are identified. Specifically, there are 28 distinct relative equilibria in this problem which include the classical five relative equilibria for the point-mass three-body problem. None of the identified relative equilibria exist or are stable over all values of angular momentum. The stability and bifurcation pathways of these relative equilibria are mapped out as the angular momentum of the system is increased. This is done under the assumption that they have equal and constant densities and that the entire system rotates about its maximum moment of inertia. The transition to finite density greatly increases the number of relative equilibria in the three-body problem and ensures that minimum energy configurations exist for all values of angular momentum.

  19. Relative Equilibria in the Spherical, Finite Density Three-Body Problem

    NASA Astrophysics Data System (ADS)

    Scheeres, D. J.

    2016-10-01

    The relative equilibria for the spherical, finite density three-body problem are identified. Specifically, there are 28 distinct relative equilibria in this problem which include the classical five relative equilibria for the point-mass three-body problem. None of the identified relative equilibria exist or are stable over all values of angular momentum. The stability and bifurcation pathways of these relative equilibria are mapped out as the angular momentum of the system is increased. This is done under the assumption that they have equal and constant densities and that the entire system rotates about its maximum moment of inertia. The transition to finite density greatly increases the number of relative equilibria in the three-body problem and ensures that minimum energy configurations exist for all values of angular momentum.

  20. Isothermal vapor-liquid equilibria for the systems 1-chloro-1,1-difluoroethane + hydrogen fluoride, 1,1-dichloro-1-fluoroethane + hydrogen fluoride, and chlorodifluoromethane + hydrogen fluoride

    SciTech Connect

    Kang, Y.W.; Lee, Y.Y.

    1997-03-01

    Isothermal vapor-liquid equilibria for the three binary systems (1-chloro-1,1-difluoroethane + hydrogen fluoride, 1,1-dichloro-1-fluoroethane + hydrogen fluoride, and chlorodifluoromethane + hydrogen fluoride) have been measured. The experimental data for the binary systems are correlated with the NRTL equation with the vapor-phase association model for the mixtures containing hydrogen fluoride, and the relevant parameters are presented. All of the systems form minimum boiling heterogeneous azeotropes.

  1. Isobaric vapor-liquid equilibria of octane + 1-butanol, + 2-butanol, and + 2-methyl-2-propanol at 101.3 kPa

    SciTech Connect

    Hiaki, T.; Taniguchi, A.; Tsuji, T.; Hongo, M.; Kojima, K.

    1996-09-01

    Isobaric vapor-liquid equilibria were measured for three binary systems of 1-butanol + octane, 2-butanol + octane, and 2-methyl-2-propanol + octane at 101.3 kPa. The measurements were made in an equilibrium still with circulation of both the vapor and liquid phases. Both 1-butanol + octane and 2-butanol + octane form a minimum boiling azeotrope. 2-Methyl-2-propanol + octane is a nonazeotrope. The activity coefficients of three binary systems were best correlated with the Wilson equation.

  2. Impact of the In-medium Nucleon-nucleon Cross Section Modification on Early-reaction-phase Dynamics Below 100 A MeV

    SciTech Connect

    Basrak, Z.; Zoric, M.; Eudes, P.; Sebille, F.

    2009-08-26

    With a semi-classical transport model studied is the impact of the in-medium NN cross section modifications on the early energy transformation, dynamical emission and quasiprojectile properties of the Ar+Ni and Ni+Ni reactions at 52, 74 and 95(90) A MeV.

  3. Investigating the Role of the Stringent Response in Lipid Modifications during the Stationary Phase in E. coli by Direct Analysis with Time-of-Flight-Secondary Ion Mass Spectrometry.

    PubMed

    Wehrli, Patrick M; Angerer, Tina B; Farewell, Anne; Fletcher, John S; Gottfries, Johan

    2016-09-01

    Escherichia coli is able to rapidly adjust the biophysical properties of its membrane phospholipids to adapt to environmental challenges including starvation stress. These membrane lipid modifications were investigated in glucose starved E. coli cultures and compared to a ΔrelAΔspoT (ppGpp(0)) mutant strain of E. coli, deficient in the stringent response, by means of time-of-flight-secondary ion mass spectrometry (TOF-SIMS). Recent advances in TOF-SIMS, through the implementation of gas cluster ion beams (GCIBs), now permit the analysis of higher mass species from native, underivatized, biological specimen, i.e., intact bacterial cells. Cultures in stationary phase were found to exhibit a radically different lipid composition as compared to cultures in the exponential growth phase. Wild-type E. coli reacted upon carbon starvation by lipid modifications including elongation, cyclopropanation, and increased cardiolipin formation. Observations are consistent with variants of cardiolipins (CL), phosphatidylglycerols (PG), phosphatidylethanolamines (PE), phosphatidic acids (PA), and fatty acids. Notably, despite having a proteomic profile and a gene expression profile somewhat similar to the wild-type during growth, the ppGpp(0) mutant E. coli strain was found to exhibit modified phospholipids corresponding to unsaturated analogues of those found in the wild-type. We concluded that the ppGpp(0) mutant reacts upon starvation stress by elongation and desaturation of fatty acyl chains, implying that only the last step of the lipid modification, the cyclopropanation, is under stringent control. These observations suggest alternative stress response mechanisms and illustrate the role of the RelA and SpoT enzymes in the biosynthetic pathway underlying these lipid modifications.

  4. Computation of Multi-region Relaxed Magnetohydrodynamic Equilibria

    SciTech Connect

    Hudson, S. R.; Dewar, R. L.; Dennis, G.; Hole, M. J.; McGann, M.; von Nessi, G.; Lazerson, S.

    2013-03-29

    We describe the construction of stepped-pressure equilibria as extrema of a multi-region, relaxed magnetohydrodynamic (MHD) energy functional that combines elements of ideal MHD and Taylor relaxation, and which we call MRXMHD. The model is compatible with Hamiltonian chaos theory and allows the three-dimensional MHD equilibrium problem to be formulated in a well-posed manner suitable for computation. The energy-functional is discretized using a mixed finite-element, Fourier representation for the magnetic vector potential and the equilibrium geometry; and numerical solutions are constructed using the stepped-pressure equilibrium code, SPEC. Convergence studies with respect to radial and Fourier resolution are presented.

  5. Boson stars: Gravitational equilibria of self-interacting scalar fields

    SciTech Connect

    Colpi, M.; Shapiro, S.L.; Wasserman, I.

    1986-11-17

    Spherically symmetric gravitational equilibria of self-interacting scalar fields phi with interaction potential V(phi) = (1/4)lambdachemically bondphichemically bond/sup 4/ are determined. Surprisingly, the resulting configurations may differ markedly from the noninteracting case even when lambda<<1. Contrary to generally accepted astrophysical folklore, it is found that the maximum masses of such boson stars may be comparable to the Chandrasekhar mass for fermions of mass m/sub fermion/--lambda/sup -1/4/m/sub boson/. .AE

  6. Nitroxides as redox probes of melanins: dark-induced and photoinduced changes in redox equilibria

    SciTech Connect

    Sarna, T.; Korytowski, W.; Sealy, R.C.

    1985-05-15

    The interaction of nitroxide free radicals and their reduced products (hydroxylamines) with synthetic and natural melanins has been studied. Electron spin resonance spectroscopy was used to measure changes in radical concentration in the dark and during irradiation with visible or uv light. Some reduction of nitroxide occurs in the dark, and is reversible: the nitroxide can be completely regenerated by the one-electron oxidant ferricyanide. The kinetics of the process depend strongly on radical charge and pH. For positively charged nitroxides the rate is much faster than for either neutral or anionic radicals. At pH 10 the rate is about 20 times faster than at pH 5. Oxidation of hydroxylamine also can occur so that a redox equilibrium is established. The equilibrium constant has been estimated for the reaction between a nitroxide and melanin from autoxidation of 3,4-dihydroxyphenylalanine. Results are also dependent upon the type of melanin used and chemical modification (oxidation or reduction) of the melanin. Redox equilibria are altered during irradiation with either visible or uv light. Rapid oxidation of hydroxylamine to nitroxide is apparent, together with a slower reduction of nitroxide. Action spectra for these processes are related to those for melanin radical production and oxygen consumption in nitroxide-free melanin systems. Reduction of nitroxide is inhibited by oxygen, suggesting a competition between nitroxide and oxygen for photoinduced reducing equivalents.

  7. A thermodynamic solution model for calcium carbonate: Towards an understanding of multi-equilibria precipitation pathways.

    PubMed

    Donnet, Marcel; Bowen, Paul; Lemaître, Jacques

    2009-12-15

    Thermodynamic solubility calculations are normally only related to thermodynamic equilibria in solution. In this paper, we extend the use of such solubility calculations to help elucidate possible precipitation reaction pathways during the entire reaction. We also estimate the interfacial energy of particles using only solubility data by a modification of Mersmann's approach. We have carried this out by considering precipitation reactions as a succession of small quasi-equilibrium states. Thus possible equilibrium precipitation pathways can be evaluated by calculating the evolution of surface charge, particle size and/or interfacial energy during the ongoing reaction. The approach includes the use of the Kelvin's law to express the influence of particle size on the solubility constant of precipitates, the use of Nernst's law to calculate surface potentials from solubility calculations and relate this to experimentally measured zeta potentials. Calcium carbonate precipitation and zeta potential measurements of well characterised high purity calcite have been used as a model system to validate the calculated values. The clarification of the change in zeta potential on titration illustrates the power of this approach as a tool for reaction pathway prediction and hence knowledge based tailoring of precipitation reactions.

  8. Protonation Equilibria of Biologically Active Ligands in Mixed Aqueous Organic Solvents

    PubMed Central

    El-Sherif, Ahmed A.; Shoukry, Mohamed M.; Abd Elkarim, Abeer T.; Barakat, Mohammad H.

    2014-01-01

    The review is mainly concerned with the protonation equilibria of biologically active ligands like amino acids, peptides, DNA constituents, and amino acid esters in nonaqueous media. Equilibrium concentrations of proton-ligand formation as a function of pH were investigated. Also, thermodynamics associated with protonation equilibria were also discussed. PMID:25197267

  9. Total System Performance Assessment-License Application Design Selection (LADS) Phase 1 Analysis of Surface Modification Consisting of Addition of Alluvium (Feature 23a)

    SciTech Connect

    N. Erb

    1999-06-11

    The objective of this report is to document the analysis that was conducted to evaluate the effect of a potential change to the TSPA-VA base case design that could improve long-term repository performance. The design feature evaluated in this report is a modification of the topographic surface of Yucca Mountain. The modification consists of covering the land surface immediately above the repository foot-print with a thick layer of unconsolidated material utilizing rip-rap and plants to mitigate erosion. This surface modification is designated as Feature 23a or simply abbreviated as F23a. The fundamental aim of F23a is to reduce the net infiltration into the unsaturated zone by enhancing the potential for evapotranspiratiration at the surface; such a change would, in turn, reduce the seepage flux and the rate of radionuclide releases from the repository. Field and modeling studies of water movement in the unsaturated zone have indicated that shallow infiltration at the surface is almost negligible in locations where the bedrock is covered by a sufficiently thick soil layer. In addition to providing storage for meteoric water, a thick soil layer would slow the downward movement of soil moisture to such an extent that evaporation and transpiration could easily transfer most of the soil-water back to the atmosphere. Generic requirements for the effectiveness of this design feature are two-fold. First, the soil layer above the repository foot-print must be thick enough to provide sufficient storage of meteoric water (from episodic precipitation events) and accommodate plant roots. Second, the added soil layer must be engineered so as to mitigate thinning by erosional processes and have sufficient thickness to accommodate the roots of common desert plants. Under these two conditions, it is reasonable to expect that modification would be effective for a significant time period and the net infiltration and deep percolation flux would be reduced by orders of magnitude lower

  10. Modification of the Electro-optical Properties of the B1 Liquid Crystal Phase using a Rod-like Liquid Crystal Dopant

    SciTech Connect

    J Kirchhoff; L Hirst

    2011-12-31

    It has recently been observed that on application of an alternating electric field, the B1 liquid-crystalline phase may be induced to form a switchable phase. This induced phase has been shown to have an almost thresholdless dielectric response. In this paper we examine this E-field-induced transition as a function of temperature both with and without a ferroelectric liquid-crystal dopant. Although the aim of this experiment was to enhance and stabilize the field-induced phase on addition of dopant, we find that the opposite is the case. The ferroelectric dopant actually increases the threshold E-fields required for transformation to the switching phase and at just 5 wt?% dopant a smectic-A phase is formed. Addition of the dopant also acts against the low-field switching and significantly speeds relaxation back to the B1 phase on field removal. In addition we find that the field-induced phase experiences a slower crystallization. We use polarized optical microscopy, differential scanning calorimetry, and x-ray scattering experiments to characterize the physical properties of the mixtures.

  11. Calculation for liquid-liquid equilibria of quaternary alkane-ethyl acetate-methanol-water systems used in counter-current chromatography.

    PubMed

    Chen, Jian; Zhao, Mengqiang; Yu, Yanmei; Li, Zongcheng

    2007-06-01

    The calculation of liquid-liquid equilibrium compositions of solvent systems is very important for the work on counter-current chromatography (CCC), especially the phase composition and volume ratio obtained from liquid-liquid equilibrium calculation. In this work, liquid-liquid equilibria of quaternary Arizona solvent systems, alkane-ethyl acetate-methanol-water, and related ternary systems are correlated and predicted using the non-random two-liquid model (NRTL). Hexane, heptane and isooctane are the used alkanes. The parameters in the model are regressed only with the special systems considered. Detailed comparison with experimental data shows that liquid-liquid equilibria of these systems can be predicted with greatly improved accuracy as compared to the group contribution method (UNIFAC).

  12. Axisymmetric equilibria with pressure anisotropy and plasma flow

    NASA Astrophysics Data System (ADS)

    Throumoulopoulos, George; Evangelias, Achilleas

    2015-11-01

    A generalised Grad-Shafranov equation that governs the equilibrium of an axisymmetric toroidal plasma with anisotropic pressure and incompressible flow of arbitrary direction is derived. This equation includes six free surface functions and recovers known Grad-Shafranov-like equations in the literature as well as the usual static, isotropic one. The form of the generalised equation indicates that pressure anisotropy and flow act additively on equilibrium. In addition, two sets of analytical solutions, an extended Solovev one with a free boundary and an extended Hernegger-Maschke one for a plasma surrounded by a fixed boundary possessing an X-point, are constructed, particularly in relevance to the ITER and NSTX tokamaks. Furthermore, the impacts both of pressure anisotropy and plasma flow on these equilibria are examined. It turns out that depending on the maximum value and the shape of an anisotropy function, the anisotropy can act either paramagnetically or diamagnetically. Also, in most of the cases considered both the anisotropy and the flow have stronger effects on NSTX equilibria than on ITER ones. This work has been carried out within the framework of the EUROfusion Consortium and has received funding from (a) the National Programme for the Controlled Thermonuclear Fusion, Hellenic Republic, (b) Euratom research and training programme 2014-2018.

  13. Tokamak equilibria with toroidal current reversal: properties and computational issues

    SciTech Connect

    Rodrigues, Paulo; Bizarro, Joao P. S.

    2006-11-30

    Several properties of axisymmetric plasma equilibria with toroidal-current reversal (TCR) are discussed using some unifying concepts from catastrophe theory. Namely, those of structural stability of functions near critical points, singularity unfolding by small perturbations, and model parameter-space division by bifurcation sets are found to be of particular usefulness. Magnetic configurations displaying, simultaneously, TCR and nested flux surfaces are thence shown to be necessarily degenerate and structurally unstable, meaning that they are easily transformed into non-nested ones by small perturbations in the model parameter set. This should lead to a new paradigm when discussing TCR equilibria, as most of present knowledge relies mainly on the properties of nested solutions, which is expected to favor the study of the broader class of non-nested configurations that recently attracted a considerable discussion in the fusion community. In addition, it is also shown how TCR imposes some constraints on plasma profiles, and how these may be dealt with computationally while keeping the ability to manipulate the shape of the inner island system.

  14. Equilibria near asteroids for solar sails with reflection control devices

    NASA Astrophysics Data System (ADS)

    Gong, Shengping; Li, Junfeng

    2015-02-01

    Solar sails are well-suited for long-term, multiple-asteroid missions. The dynamics of solar sails near an asteroid have not yet been studied in detail. In this paper, out-of-plane artificial equilibria in a Sun-asteroid rotating frame and hovering points in a body-fixed rotating frame are studied (using a solar sail equipped with reflection control devices). First, the dynamics and the stability of out-of-plane artificial equilibria are studied as an elliptical restricted three body problem. Next, the body-fixed hovering problem is discussed as a two-body problem. Hovering flight is only possible for certain values of the latitude of the asteroid's orbit. In addition, the feasible range of latitudes is determined for each landmark on the asteroid's surface. The influence of the sail lightness number on the feasible range is also illustrated. Several special families of hovering points are discussed. These points include points above the equator and poles and points with an altitude equal to the radius of the synchronous orbit. In both of these types of problems, the solar sail (equipped with reflection control devices) can equilibrate over a large range of locations.

  15. An Energy Principle for Ideal MHD Equilibria with Flows

    SciTech Connect

    Yao Zhou and Hong Qin

    2013-03-11

    In the standard ideal MHD energy principle for equilibria with no flows, the stability criterion, which is the defi niteness of the perturbed potential energy, is usually constructed from the linearized equation of motion. Equivalently while more straightforwardly, it can also be obtained from the second variation of the Hamiltonian calculated with proper constraints. For equilibria with flows, a stability criterion was proposed from the linearized equation of motion, but not explained as an energy principle1. In this paper, the second variation of the Hamiltonian is found to provide a stability criterion equivalent to, while more straightforward than, what was constructed from the linearized equation of motion. To calculate the variations of the Hamiltonian, a complete set of constraints on the dynamics of the perturbations is derived from the Euler-Poincare structure of the ideal MHD. In addition, a previous calculation of the second variation of the Hamiltonian was claimed to give a different stability criterion2, and in this paper we argue such a claim is incorrect.

  16. Expansions of non-symmetric toroidal magnetohydrodynamic equilibria

    NASA Astrophysics Data System (ADS)

    Weitzner, Harold

    2016-06-01

    Expansions of non-symmetric toroidal ideal magnetohydrodynamic equilibria with nested flux surfaces are carried out for two cases. The first expansion is in a topological torus in three dimensions, in which physical quantities are periodic of period 2 π in y and z. Data is given on the flux surface x = 0. Despite the possibility of magnetic resonances the power series expansion can be carried to all orders in a parameter which measures the flux between x = 0 and the surface in question. Resonances are resolved by appropriate addition resonant fields, as by Weitzner, [Phys. Plasmas 21, 022515 (2014)]. The second expansion is about a circular magnetic axis in a true torus. It is also assumed that the cross section of a flux surface at constant toroidal angle is approximately circular. The expansion is in an analogous flux coordinate, and despite potential resonance singularities, may be carried to all orders. Non-analytic behavior occurs near the magnetic axis. Physical quantities have a finite number of derivatives there. The results, even though no convergence proofs are given, support the possibility of smooth, well-behaved non-symmetric toroidal equilibria.

  17. Equilibria occurring between beryllium (II) and salicylate ions.

    PubMed

    Furia, Emilia; Porto, Raffaella

    2003-12-01

    The complexation equilibria between Be2+ and the hydrogen salicylate (HL-) ions have been studied, at 25 degrees C, by potentiometric measurements with a glass electrode in 3 M NaClO4. The concentrations of metal (CM) and ligand (CL) were varied between 10(-3) and 0.03 M and 2 x 10(-3) and 0.03 M, respectively, while 1 < or = CL/CM < or = 3. The hydrogen ion concentration ranged from 10(-3) to 10(-5.3) M when basic salts start to precipitate. The equilibria can be written in the general form as: pBe2+ + rHL- <==> Be(p)H(-q) (HL)r(2p-r-q) + qH+, log beta(pqr). The experimental data have been explained with the formation of BeHL+ (log beta101 = 1.46 +/- 0.05), BeL (log beta111 = -0.897 +/- 0.018), BeL2(2-) (log beta122 = -3.746 +/- 0.021), Be2(OH)L2- (log beta232 = -5.23 +/- 0.09), Be3(OH)3L3(3-) (log beta363 = -14.39 +/- 0.12). The uncertainties represent 3sigma. The predominant complex in the whole concentration range studied is the uncharged mononuclear species BeL.

  18. Stability of Hall equilibria in neutron star crusts

    SciTech Connect

    Marchant, Pablo; Reisenegger, Andreas; Valdivia, Juan Alejandro; Hoyos, Jaime H.

    2014-12-01

    In the solid crusts of neutron stars, the advection of the magnetic field by the current-carrying electrons, an effect known as Hall drift, should play a very important role as the ions remain essentially fixed (as long as the solid does not break). Although Hall drift preserves the magnetic field energy, it has been argued that it may drive a turbulent cascade to scales at which ohmic dissipation becomes effective, allowing a much faster decay in objects with very strong fields. On the other hand, it has been found that there are 'Hall equilibria', i.e., field configurations that are unaffected by Hall drift. Here we address the crucial question of the stability of these equilibria through axially symmetric (two-dimensional (2D)) numerical simulations of Hall drift and ohmic diffusion, with the simplifying assumption of uniform electron density and conductivity. We demonstrate the 2D stability of a purely poloidal equilibrium, for which ohmic dissipation makes the field evolve toward an attractor state through adjacent stable configurations, around which damped oscillations occur. For this field, the decay scales with the ohmic timescale. We also study the case of an unstable equilibrium consisting of both poloidal and toroidal field components that are confined within the crust. This field evolves into a stable configuration, which undergoes damped oscillations superimposed on a slow evolution toward an attractor, just as the purely poloidal one.

  19. Social Interactions under Incomplete Information: Games, Equilibria, and Expectations

    NASA Astrophysics Data System (ADS)

    Yang, Chao

    My dissertation research investigates interactions of agents' behaviors through social networks when some information is not shared publicly, focusing on solutions to a series of challenging problems in empirical research, including heterogeneous expectations and multiple equilibria. The first chapter, "Social Interactions under Incomplete Information with Heterogeneous Expectations", extends the current literature in social interactions by devising econometric models and estimation tools with private information in not only the idiosyncratic shocks but also some exogenous covariates. For example, when analyzing peer effects in class performances, it was previously assumed that all control variables, including individual IQ and SAT scores, are known to the whole class, which is unrealistic. This chapter allows such exogenous variables to be private information and models agents' behaviors as outcomes of a Bayesian Nash Equilibrium in an incomplete information game. The distribution of equilibrium outcomes can be described by the equilibrium conditional expectations, which is unique when the parameters are within a reasonable range according to the contraction mapping theorem in function spaces. The equilibrium conditional expectations are heterogeneous in both exogenous characteristics and the private information, which makes estimation in this model more demanding than in previous ones. This problem is solved in a computationally efficient way by combining the quadrature method and the nested fixed point maximum likelihood estimation. In Monte Carlo experiments, if some exogenous characteristics are private information and the model is estimated under the mis-specified hypothesis that they are known to the public, estimates will be biased. Applying this model to municipal public spending in North Carolina, significant negative correlations between contiguous municipalities are found, showing free-riding effects. The Second chapter "A Tobit Model with Social

  20. Double universality of a quantum phase transition in spinor condensates: modification of the Kibble-Żurek mechanism by a conservation law.

    PubMed

    Świsłocki, Tomasz; Witkowska, Emilia; Dziarmaga, Jacek; Matuszewski, Michał

    2013-01-25

    We consider a phase transition from an antiferromagnetic to a phase separated ground state in a spin-1 Bose-Einstein condensate of ultracold atoms. We demonstrate the occurrence of two scaling laws, for the number of spin domain seeds just after the phase transition, and for the number of spin domains in the final, stable configuration. Only the first scaling can be explained by the standard Kibble-Żurek mechanism. We explain the occurrence of two scaling laws by a model including postselection of spin domains due to the conservation of condensate magnetization.

  1. Effects of crystallization temperature of poly(vinylidene fluoride) on crystal modification and phase transition of poly(butylene adipate) in their blends: a novel approach for polymorphic control.

    PubMed

    Yang, Jinjun; Pan, Pengju; Hua, Lei; Feng, Xin; Yue, Junjie; Ge, Yanhui; Inoue, Yoshio

    2012-02-01

    Effects of the isothermal crystallization temperatures of poly(vinylidene fluoride), T(IC,PVDF), on polymorphic crystalline structure, phase transition, fractional crystallization, and enzymatic degradation of poly(butylene adipate) (PBA) in crystalline/crystalline blends have been investigated. The crystal modifications of PBA can be regulated by T(IC,PVDF). Lower T(IC,PVDF) (e.g., 80 °C) facilitates the formation of PBA α crystals in both the isothermal and nonisothermal melt crystallizations and also favors the β-to-α phase transition of PBA upon annealing at elevated temperatures. This might be attributable to the decreased equilibrium melting temperature of PBA when T(IC,PVDF) is decreased. Higher T(IC,PVDF) is favorable for the fractional crystallization of PBA, which tends to segregate in the interlamellar regions of the PVDF matrix under these conditions. PBA shows faster enzymatic degradation in the blends with a lower T(IC,PVDF) than those with a higher T(IC,PVDF), attributable to the preferential formation of α crystals at a lower T(IC,PVDF). This study provides a new method to control the crystal modification and physical properties of polymorphic polymers in their blend systems.

  2. Thermodynamic analysis of reaction equilibria in ionic and molecular liquid systems by high-temperature Raman spectroscopy.

    PubMed

    Kalampounias, Angelos G; Boghosian, Soghomon

    2009-09-01

    A formalism for correlating relative Raman band intensities with the stoichiometric coefficients, the equilibrium constant, and the thermodynamics of reaction equilibria in solution is derived. The proposed method is used for studying: (1) the thermal dissociation of molten KHSO(4) in the temperature range 240-450 degrees C; (2) the dinuclear complex formation in molten TaCl(5)-AlCl(3) mixtures at temperatures between 125 and 235 degrees C. The experimental and calculational procedures for exploiting the temperature-dependent Raman band intensities in the molten phase as well as (if applicable) in the vapors thereof are described and used for determining the enthalpy of the equilibria: (1) 2HSO(4)(-)(l) <--> S(2)O(7)(2-)(l) + H(2)O(g), DeltaH(0)=64.9 +/- 2.9 kJ mol(-1); and (2) 1/2Ta(2)Cl(10)(l) + 1/2Al(2)Cl(6)(l) <--> TaAlCl(8)(l), DeltaH(0)=-12.1 +/- 1.5 kJ mol(-1).

  3. Testing EQ3/6 and GEMBOCHS using fluid-mineral equilibria in the wairakei geothermal system

    SciTech Connect

    Bruton, C.J.

    1995-08-28

    The ability of the EQ3 and EQ6 geochemical modeling codes and the GEMBOCHS thermodynamic data bases to simulate geochemical changes in the post-emplacement environment at the potential Yucca Mountain, Nevada repository is being tested using observed mineral-fluid relations in the Taupo Volcanic Zone of New Zealand. In this report, comparisons between observed equilibria and simulations of field relations in the Wairakei geothermal system are used to test the codes and data bases in high temperature systems. Analysis of trends in water and gas chemistries and well discharge characteristics with time were used to identify a set of representative water and gas analyses from zones producing at about 250{degrees}C. The most common vein minerals at this temperature are: wairakite, adularia, epidote, quartz, albite, chlorite, calcite, prehnite, and pyrite. Calculations were carried out using version 7.2a R134 of EQ3 and version 7.2a R130 of EQ6 and the SUPCRT and COM subsets of the R24 version of GEMBOCHS. Thermodynamic data bases using different data for Al aqueous species were sued to identify the data set which produced the best matches between observed and calculated equilibria. The simulations described in this paper suggest that EQ6 can be used to identify facies of minerals that will be stable in various environments, but can not be used to predict the exact phase assemblage that is in equilibrium with a given water.

  4. Bootstrap currents in radio-frequency-driven tokamak equilibria

    SciTech Connect

    Hsiao, Ming-Yuan; Ehst, D.A.; Evans, K. Jr.

    1988-05-01

    Interest in the bootstrap current arising from neoclassical transport in tokamaks has increased recently in view of certain experimental observations. In this study, the bootstrap current is calculated for a number of rf current-driven tokamaks. Two-dimensional, self-consistent, steady-state tokamak MHD equilibria are obtained by including both the transport-driven bootstrap current and the externally driven rf current. The self-consistency is acomplished by iterating between two-dimensional MHD equilibrium calculations and the current calculations (including bootstrap and rf ray-tracing). Calculations for other reactor parameters of interest are also carried out. It is found that for reactor-grade plasmas, the bootstrap current contribution to the toroidal current is, in general, important. An approxiamte scaling law for GAMMA, based on parametric survey performed, is also obtained. 16 refs., 8 figs., 1 tab.

  5. Navigable networks as Nash equilibria of navigation games

    NASA Astrophysics Data System (ADS)

    Gulyás, András; Bíró, József J.; Kőrösi, Attila; Rétvári, Gábor; Krioukov, Dmitri

    2015-07-01

    Common sense suggests that networks are not random mazes of purposeless connections, but that these connections are organized so that networks can perform their functions well. One function common to many networks is targeted transport or navigation. Here, using game theory, we show that minimalistic networks designed to maximize the navigation efficiency at minimal cost share basic structural properties with real networks. These idealistic networks are Nash equilibria of a network construction game whose purpose is to find an optimal trade-off between the network cost and navigability. We show that these skeletons are present in the Internet, metabolic, English word, US airport, Hungarian road networks, and in a structural network of the human brain. The knowledge of these skeletons allows one to identify the minimal number of edges, by altering which one can efficiently improve or paralyse navigation in the network.

  6. Swelling equilibria for temperature-sensitive ampholytic hydrogels

    SciTech Connect

    Baker, J.P.; Stephens, D.R.; Blanch, H.W.; Prausnitz, J.M.

    1992-09-01

    Temperature-sensitive N-isopropylacrylamide (NIPA)-based ampho-lytic hydrogels were synthesized by copolymerizing NIPA with the cationic monomer methacrylamidopropyl trimethylammonium chloride (MAPTAC) and the anionic monomer sodium styrene sulfonate (SSS). The total nominal charge density of the hydrogels was held constant at 8 mol % (dry basis), while the molar ratio of anionic to cationic moieties within the hydrogels was varied. Swelling equilibria were measured in water at 6C, and in aqueous sodium chloride solutions ranging in concentration from 10{sup {minus}5}to 5 M and temperature ranging from 6 to 56C. Consistent with expectations, the swelling behavior of the hydrogels was found to be controlled by temperature at low salt concentrations; as the sodium chloride concentration increased, temperature control of hydrogel swelling decreased. Slight antipolyelectrolyte behavior was observed for the hydrogel prepared with equal molar amounts of MAPTAC and SSS.

  7. Efficiently Finding Trends in Macroscopic MHD Stability Using Perturbed Equilibria

    NASA Astrophysics Data System (ADS)

    Comer, K. J.; Callen, J. D.; Hegna, C. C.; Turnbull, A. D.; Cowley, S. C.

    2001-10-01

    The effects of equilibrium shaping and profiles on long wavelength ideal MHD instabilities in toroidal plasmas are traditionally studied using numerical parameter scans. Previously, we introduced a new perturbative technique to explore these dependencies: assuming small equilibrium variations, new stability properties are found using a perturbation of the energy principle rather than with a traditional stability code. With this approach, stability dependencies can be efficiently examined without numerically generating complete MHD stability results for every set of parameters (which can be time-intensive for accurate representations of several configurations). Here, we briefly expand on previous successful perturbed stability analyses for screw pinch equilibria by discussing cases where the approach fails. Next, we extend the approach to toroidal geometry using the GATO and TOQ codes, and present cases that both validate the approach and suggest caution in its application.

  8. Resonances and oscillatory behavior near multi-species plasma equilibria

    SciTech Connect

    Núñez, Manuel

    2014-03-15

    We consider dynamic multi-species plasma equilibria whose variables depend on a single spatial coordinate and linear perturbations of these. The linearized system may be reduced to a second-order one satisfied by the respective fluid streamfunctions. For the two-species case, the electron mass is a parameter small enough for a WKB asymptotic analysis to be justified. It turns out that the points where either the ion or electron equilibrium velocity equals the ratio between the temporal and transversal frequencies of the perturbation are turning or singular points of the system, connecting exponentially increasing or decreasing solutions to oscillatory ones. The crucial role of singular points in the balance between the different contributions to the electron kinetic energy is explored.

  9. Navigable networks as Nash equilibria of navigation games.

    PubMed

    Gulyás, András; Bíró, József J; Kőrösi, Attila; Rétvári, Gábor; Krioukov, Dmitri

    2015-07-03

    Common sense suggests that networks are not random mazes of purposeless connections, but that these connections are organized so that networks can perform their functions well. One function common to many networks is targeted transport or navigation. Here, using game theory, we show that minimalistic networks designed to maximize the navigation efficiency at minimal cost share basic structural properties with real networks. These idealistic networks are Nash equilibria of a network construction game whose purpose is to find an optimal trade-off between the network cost and navigability. We show that these skeletons are present in the Internet, metabolic, English word, US airport, Hungarian road networks, and in a structural network of the human brain. The knowledge of these skeletons allows one to identify the minimal number of edges, by altering which one can efficiently improve or paralyse navigation in the network.

  10. Boric acid equilibria in near-critical and supercritical water

    SciTech Connect

    Wofford, W.T.; Gloyna, E.F.; Johnston, K.P.

    1998-05-01

    Greater knowledge of acid-base equilibria is crucial to understanding the chemistry of hydrothermal processes including oxidation of organics, corrosion, catalysis, hydrolysis reactions, crystal growth and formation, precipitation of metal complexes and steam power cycles. The pH values of aqueous solutions of boric acid and KOH were measured with the optical indicator 2-naphthol at temperatures from 300 to 380 C. The equilibrium constant K{sub b}{sup {minus}1} for the reaction B(OH){sub 3} + OH{sup {minus}} = B(OH){sub 4}{sup {minus}} was determined from the pH measurements and correlated with a modified Born model. The titration curve for the addition of HCl to sodium borate exhibits strong acid-strong base behavior even at 350 C and 24.1 MPa. At these conditions, aqueous solutions of sodium borate buffer the pH at 9.6 {+-} 0.25.

  11. Three-dimensional equilibria in axially symmetric tokamaks

    PubMed Central

    Garabedian, Paul R.

    2006-01-01

    The NSTAB and TRAN computer codes have been developed to study equilibrium, stability, and transport in fusion plasmas with three-dimensional (3D) geometry. The numerical method that is applied calculates islands in tokamaks like the Doublet III-D at General Atomic and the International Thermonuclear Experimental Reactor. When bifurcated 3D solutions are used in Monte Carlo computations of the energy confinement time, a realistic simulation of transport is obtained. The significance of finding many 3D magnetohydrodynamic equilibria in axially symmetric tokamaks needs attention because their cumulative effect may contribute to the prompt loss of α particles or to crashes and disruptions that are observed. The 3D theory predicts good performance for stellarators. PMID:17159158

  12. A generalized procedure for the prediction of multicomponent adsorption equilibria

    SciTech Connect

    Ladshaw, Austin; Yiacoumi, Sotira; Tsouris, Costas

    2015-01-01

    Prediction of multicomponent adsorption equilibria has been investigated for several decades. While there are theories available to predict the adsorption behavior of ideal mixtures, there are few purely predictive theories to account for nonidealities in real systems. Most models available for dealing with nonidealities contain interaction parameters that must be obtained through correlation with binary-mixture data. However, as the number of components in a system grows, the number of parameters needed to be obtained increases exponentially. Here, a generalized procedure is proposed, as an extension of the predictive real adsorbed solution theory, for determining the parameters of any activity model, for any number of components, without correlation. This procedure is then combined with the adsorbed solution theory to predict the adsorption behavior of mixtures. As this method can be applied to any isotherm model and any activity model, it is referred to as the generalized predictive adsorbed solution theory.

  13. A generalized procedure for the prediction of multicomponent adsorption equilibria

    DOE PAGES

    Ladshaw, Austin; Yiacoumi, Sotira; Tsouris, Costas

    2015-01-01

    Prediction of multicomponent adsorption equilibria has been investigated for several decades. While there are theories available to predict the adsorption behavior of ideal mixtures, there are few purely predictive theories to account for nonidealities in real systems. Most models available for dealing with nonidealities contain interaction parameters that must be obtained through correlation with binary-mixture data. However, as the number of components in a system grows, the number of parameters needed to be obtained increases exponentially. Here, a generalized procedure is proposed, as an extension of the predictive real adsorbed solution theory, for determining the parameters of any activity model,more » for any number of components, without correlation. This procedure is then combined with the adsorbed solution theory to predict the adsorption behavior of mixtures. As this method can be applied to any isotherm model and any activity model, it is referred to as the generalized predictive adsorbed solution theory.« less

  14. SOME CONSEQUENCES OF THE THEORY OF MEMBRANE EQUILIBRIA

    PubMed Central

    Hitchcock, David I.

    1925-01-01

    In applying Donnan's theory of membrane equilibria to systems where the non-diffusible ion is furnished by a weak acid, base, or ampholyte, certain new relations have been derived. Equations have been deduced which give the ion ratio and the apparent osmotic pressure as functions of the concentration and ionization constant of the weak electrolyte, and of the hydrogen ion concentration in its solution. The conditions for maximum values of these two properties have been formulated. It is pointed out that the progressive addition of acid to a system containing a non-diffusible weak base should not cause the value of the membrane potential to rise, pass through a maximum, and fall, but should only cause it to diminish. It is shown that the theory predicts slight differences in the effect of salts on the ion ratio in such systems, the effect increasing with the valence of the cation. PMID:19872236

  15. Recent developments in Bayesian inference of tokamak plasma equilibria and high-dimensional stochastic quadratures

    NASA Astrophysics Data System (ADS)

    von Nessi, G. T.; Hole, M. J.; The MAST Team

    2014-11-01

    We present recent results and technical breakthroughs for the Bayesian inference of tokamak equilibria using force-balance as a prior constraint. Issues surrounding model parameter representation and posterior analysis are discussed and addressed. These points motivate the recent advancements embodied in the Bayesian Equilibrium Analysis and Simulation Tool (BEAST) software being presently utilized to study equilibria on the Mega-Ampere Spherical Tokamak (MAST) experiment in the UK (von Nessi et al 2012 J. Phys. A 46 185501). State-of-the-art results of using BEAST to study MAST equilibria are reviewed, with recent code advancements being systematically presented though out the manuscript.

  16. Motor Skill Learning Is Associated with Phase-Dependent Modifications in the Striatal cAMP/PKA/DARPP-32 Signaling Pathway in Rodents.

    PubMed

    Qian, Yu; Forssberg, Hans; Diaz Heijtz, Rochellys

    2015-01-01

    Abundant evidence points to a key role of dopamine in motor skill learning, although the underlying cellular and molecular mechanisms are still poorly understood. Here, we used a skilled-reaching paradigm to first examine changes in the expression of the plasticity-related gene Arc to map activity in cortico-striatal circuitry during different phases of motor skill learning in young animals. In the early phase, Arc mRNA was significantly induced in the medial prefrontal cortex (mPFC), cingulate cortex, primary motor cortex, and striatum. In the late phase, expression of Arc did not change in most regions, except in the mPFC and dorsal striatum. In the second series of experiments, we studied the learning-induced changes in the phosphorylation state of dopamine and cAMP-regulated phosphoprotein, 32k Da (DARPP-32). Western blot analysis of the phosphorylation state of DARPP-32 and its downstream target cAMP response element-binding protein (CREB) in the striatum revealed that the early, but not late, phase of motor skill learning was associated with increased levels of phospho-Thr34-DARPP-32 and phospho-Ser133-CREB. Finally, we used the DARPP-32 knock-in mice with a point mutation in the Thr34 regulatory site (i.e., protein kinase A site) to test the significance of this pathway in motor skill learning. In accordance with our hypothesis, inhibition of DARPP-32 activity at the Thr34 regulatory site strongly attenuated the motor learning rate and skilled reaching performance of mice. These findings suggest that the cAMP/PKA/DARPP-32 signaling pathway is critically involved in the acquisition of novel motor skills, and also demonstrate a dynamic shift in the contribution of cortico-striatal circuitry during different phases of motor skill learning. PMID:26488498

  17. Liquid-liquid equilibria of binary mixtures of a lipidic ionic liquid with hydrocarbons.

    PubMed

    Green, Blane D; Badini, Alexander J; O'Brien, Richard A; Davis, James H; West, Kevin N

    2016-01-28

    Although structurally diverse, many ionic liquids (ILs) are polar in nature due to the strong coulombic forces inherent in ionic compounds. However, the overall polarity of the IL can be tuned by incorporating significant nonpolar content into one or more of the constituent ions. In this work, the binary liquid-liquid equilibria of one such IL, 1-methyl-3-(Z-octadec-9-enyl)imidazolium bistriflimide, with several hydrocarbons (n-hexane, n-octane, n-decane, cyclohexane, methylcyclohexane, 1-octene) is measured over the temperature range 0-70 °C at ambient pressure using a combination of cloud point and gravimetric techniques. The phase behavior of the systems are similar in that they exhibit two phases: one that is 60-90 mole% hydrocarbon and a second phase that is nearly pure hydrocarbon. Each phase exhibits a weak dependence of composition on temperature (steep curve) above ∼10 °C, likely due to swelling and restructuring of the nonpolar nano-domains of the IL being limited by energetically unfavorable restructuring in the polar nano-domains. The solubility of the n-alkanes decreases with increasing size (molar volume), a trend that continues for the cyclic alkanes, for which upper critical solution temperatures are observed below 70 °C. 1-Octene is found to be more soluble than n-octane, attributable to a combination of its lower molar volume and slightly higher polarity. The COSMO-RS model is used to predict the T-x'-x'' diagrams and gives good qualitative agreement of the observed trends. This work presents the highest known solubility of n-alkanes in an IL to date and tuning the structure of the ionic liquid to maximize the size/shape trends observed may provide the basis for enhanced separations of nonpolar species.

  18. Phase II modification of the Water Availability Tool for Environmental Resources (WATER) for Kentucky: The sinkhole-drainage process, point-and-click basin delineation, and results of karst test-basin simulations

    USGS Publications Warehouse

    Taylor, Charles J.; Williamson, Tanja N.; Newson, Jeremy K.; Ulery, Randy L.; Nelson, Hugh L.; Cinotto, Peter J.

    2012-01-01

    This report describes Phase II modifications made to the Water Availability Tool for Environmental Resources (WATER), which applies the process-based TOPMODEL approach to simulate or predict stream discharge in surface basins in the Commonwealth of Kentucky. The previous (Phase I) version of WATER did not provide a means of identifying sinkhole catchments or accounting for the effects of karst (internal) drainage in a TOPMODEL-simulated basin. In the Phase II version of WATER, sinkhole catchments are automatically identified and delineated as internally drained subbasins, and a modified TOPMODEL approach (called the sinkhole drainage process, or SDP-TOPMODEL) is applied that calculates mean daily discharges for the basin based on summed area-weighted contributions from sinkhole drain-age (SD) areas and non-karstic topographically drained (TD) areas. Results obtained using the SDP-TOPMODEL approach were evaluated for 12 karst test basins located in each of the major karst terrains in Kentucky. Visual comparison of simulated hydrographs and flow-duration curves, along with statistical measures applied to the simulated discharge data (bias, correlation, root mean square error, and Nash-Sutcliffe efficiency coefficients), indicate that the SDPOPMODEL approach provides acceptably accurate estimates of discharge for most flow conditions and typically provides more accurate simulation of stream discharge in karstic basins compared to the standard TOPMODEL approach. Additional programming modifications made to the Phase II version of WATER included implementation of a point-and-click graphical user interface (GUI), which fully automates the delineation of simulation-basin boundaries and improves the speed of input-data processing. The Phase II version of WATER enables the user to select a pour point anywhere on a stream reach of interest, and the program will automatically delineate all upstream areas that contribute drainage to that point. This capability enables

  19. A Multistep Equilibria-Redox-Complexation Demonstration to Illustrate Le Chatelier's Principle.

    ERIC Educational Resources Information Center

    Berger, Tomas G.; Mellon, Edward K.

    1996-01-01

    Describes a process that can be used to illustrate a number of chemical principles including Le Chatelier's principle, redox chemistry, equilibria versus steady state situations, and solubility of species. (JRH)

  20. Origin and use of crystallization phase diagrams.

    PubMed

    Rupp, Bernhard

    2015-03-01

    Crystallization phase diagrams are frequently used to conceptualize the phase relations and also the processes taking place during the crystallization of macromolecules. While a great deal of freedom is given in crystallization phase diagrams owing to a lack of specific knowledge about the actual phase boundaries and phase equilibria, crucial fundamental features of phase diagrams can be derived from thermodynamic first principles. Consequently, there are limits to what can be reasonably displayed in a phase diagram, and imagination may start to conflict with thermodynamic realities. Here, the commonly used `crystallization phase diagrams' are derived from thermodynamic excess properties and their limitations and appropriate use is discussed.

  1. Experimental and molecular modeling study of the three-phase behavior of (n-decane + carbon dioxide + water) at reservoir conditions.

    PubMed

    Forte, Esther; Galindo, Amparo; Trusler, J P Martin

    2011-12-15

    Knowledge of the phase behavior of mixtures of oil with carbon dioxide and water is essential for reservoir engineering, especially in the processes of enhanced oil recovery and geological storage of carbon dioxide. However, for a comprehensive understanding, the study of simpler systems needs to be completed. In this work the system (n-decane + carbon dioxide + water) was studied as a model (oil + carbon dioxide + water) mixture. To accomplish our aim, a new analytical apparatus to measure phase equilibria at high pressure was designed with maximum operating temperature and pressure of 423 K and 45 MPa, respectively. The equipment relies on recirculation of two coexisting phases using a two-channel magnetically operated micropump designed during this work, with sampling and online compositional analysis by gas chromatography. The apparatus has been validated by comparison with published isothermal vapor-liquid equilibrium data for the binary system (n-decane + carbon dioxide). New experimental data have been measured for the system (n-decane + carbon dioxide + water) under conditions of three-phase equilibria. Data for the three coexisting phases have been obtained on five isotherms at temperatures from 323 to 413 K and at pressures up to the point at which two of the phases become critical. The experimental work is complemented here with a theoretical effort in which we developed models for these molecules within the framework of the statistical associating fluid theory for potentials of variable range (SAFT-VR). The phase behavior of the three binary subsystems was calculated using this theory, and where applicable, a modification of the Hudson and McCoubrey combining rules was used to treat the systems predictively. The experimental data obtained for the ternary mixture are compared to the predictions of the theory. Furthermore, a detailed analysis of the ternary mixture is carried out based on comparison with available data for the constituent binary

  2. Experimental and molecular modeling study of the three-phase behavior of (n-decane + carbon dioxide + water) at reservoir conditions.

    PubMed

    Forte, Esther; Galindo, Amparo; Trusler, J P Martin

    2011-12-15

    Knowledge of the phase behavior of mixtures of oil with carbon dioxide and water is essential for reservoir engineering, especially in the processes of enhanced oil recovery and geological storage of carbon dioxide. However, for a comprehensive understanding, the study of simpler systems needs to be completed. In this work the system (n-decane + carbon dioxide + water) was studied as a model (oil + carbon dioxide + water) mixture. To accomplish our aim, a new analytical apparatus to measure phase equilibria at high pressure was designed with maximum operating temperature and pressure of 423 K and 45 MPa, respectively. The equipment relies on recirculation of two coexisting phases using a two-channel magnetically operated micropump designed during this work, with sampling and online compositional analysis by gas chromatography. The apparatus has been validated by comparison with published isothermal vapor-liquid equilibrium data for the binary system (n-decane + carbon dioxide). New experimental data have been measured for the system (n-decane + carbon dioxide + water) under conditions of three-phase equilibria. Data for the three coexisting phases have been obtained on five isotherms at temperatures from 323 to 413 K and at pressures up to the point at which two of the phases become critical. The experimental work is complemented here with a theoretical effort in which we developed models for these molecules within the framework of the statistical associating fluid theory for potentials of variable range (SAFT-VR). The phase behavior of the three binary subsystems was calculated using this theory, and where applicable, a modification of the Hudson and McCoubrey combining rules was used to treat the systems predictively. The experimental data obtained for the ternary mixture are compared to the predictions of the theory. Furthermore, a detailed analysis of the ternary mixture is carried out based on comparison with available data for the constituent binary

  3. Liquid phase methanol LaPorte PDU [process development unit]: Modification, operation, and support studies; Quarterly technical progress report No. 7, 1 January--31 March 1989

    SciTech Connect

    1989-07-20

    The work under this contract will be to implement and test certain process improvements identified through the engineering studies completed to demonstrate the capability of long-term catalyst activity maintenance, and to perform process and design engineering work that is generic to a scaled-up Liquid Phase Methanol (LPMEOH) facility. A series of process development unit (PDU) runs will be performed to extend the testing of the process improvements. A parallel research program will be conducted to enhance the LPMEOH technical data base to improve the likelihood of commercialization of the LPMEOH process. Research is briefly discussed on catalyst activation. 5 figs.

  4. DETERMINATION OF SOLID-LIQUID EQUILIBRIA DATA FOR MIXTURES OF HEAVY HYDROCARBONS IN A LIGHT SOLVENT

    SciTech Connect

    F.V. Hanson; J.V. Fletcher; Karthik R.

    2003-06-01

    A methodology was developed using an FT-IR spectroscopic technique to obtain solid-liquid equilibria (SLE) data for mixtures of heavy hydrocarbons in significantly lighter hydrocarbon diluents. SLE was examined in multiple Model Oils that were assembled to simulate waxes. The various Model oils were comprised of C-30 to C-44 hydrocarbons in decane. The FT-IR technique was used to identify the wax precipitation temperature (WPT). The DSC technique was also used in the identification of the onset of the two-phase equilibrium in this work. An additional Model oil made up of C-20 to C-30 hydrocarbons in decane was studied using the DSC experiment. The weight percent solid below the WPT was calculated using the FT-IR experimental results. The WPT and the weight percent solid below the WPT were predicted using an activity coefficient based thermodynamic model. The FT-IR spectroscopy method is found to successfully provide SLE data and also has several advantages over other laboratory-based methods.

  5. Complex equilibria, speciation, and heteroprotein coacervation of lactoferrin and β-lactoglobulin.

    PubMed

    Flanagan, Sean E; Malanowski, Alexander J; Kizilay, Ebru; Seeman, Daniel; Dubin, Paul L; Donato-Capel, Laurence; Bovetto, Lionel; Schmitt, Christophe

    2015-02-10

    There has been a resurgence of interest in complex coacervation, a form of liquid-liquid phase separation (LLPS) in systems of oppositely charged macroions, but very few reports describe the somewhat anomalous coacervation between acidic and basic proteins, which occurs under very narrow ranges of conditions. We sought to identify the roles of equilibrium interprotein complexes during the coacervation of β-lactoglobulin dimer (BLG2) with lactoferrin (LF) and found that this LLPS arises specifically from LF(BLG2)2. We followed the progress of complexation and coacervation as a function of r, the LF/BLG molar ratio, using turbidity to monitor the degree of coacervation and proton release and dynamic light scattering (DLS) to assess the stoichiometry and abundance of complexes. Isothermal titration calorimetry (ITC) showed that initial complex formation is endothermic, but a large exotherm related to coacervate formation obscured other regions. On the basis of turbidimetry, proton release, and DLS, we propose a speciation diagram that presents the abundance of various complexes as a function of r. Although multiple species could be simultaneously present, distinct regions could be identified corresponding to equilibria among particular protein pairs. PMID:25565379

  6. Visualization of the solid-liquid equilibria for non-flammable mixed refrigerants

    NASA Astrophysics Data System (ADS)

    Lee, Cheonkyu; Yoo, Junghyun; Lee, Jisung; Jeong, Sangkwon

    2016-04-01

    Non-flammable mixed refrigerant (NF-MR) Joule Thomson (J-T) refrigerators have desirable characteristics and wide cooling temperature range compared to those of pure J-T refrigerators. However, the operating challenge due to freezing is a critical issue to realize this type of refrigerator. In this paper, the solid-liquid phase equilibria (i.e. freezing point) of the NF-MR which is composed of Argon (Ar), R14 (CF4), and R218 (C3F8), has been experimentally investigated by a visualized apparatus. The accuracy of the apparatus is experimentally verified with pure refrigerants and selected binary mixed refrigerants. Freezing points of the ternary NF-MRs have been measured with the molar compositions from 0.1 to 0.8 for each component. Each test result is simultaneously acquired by a camcorder for visual inspection and temperature measurement during a warming process. Experimental results reveal that the specific MR, with R14 molar composition higher than 0.4, can achieve remarkably low freezing temperature even below 77 K. These unusual freezing point depression characteristics of the MR can be a useful information for designing a cryogenic MR J-T refrigerator to reach temperatures less than 77 K.

  7. Effects of plasma rotation in reconstructed 3-D equilibria for DIII-D

    NASA Astrophysics Data System (ADS)

    Wingen, A.; Shafer, M. W.; Unterberg, E. A.; Wilcox, R. S.; Cianciosa, M. R.; Hirshman, S. P.; Hillis, D. L.; Lao, L.; Paz-Soldan, C.

    2015-11-01

    A technique for tokamak equilibrium reconstructions when weakly 3-D fields (δB/B ~ 10-3) are applied is used for inner-wall-limited DIII-D discharges. The technique couples diagnostics to the non-linear, ideal MHD equilibrium solver VMEC, using the V3FIT code, to find the most likely 3-D equilibrium based on a suite of measurements. Observations at DIII-D show that plasma rotation larger than 20 krad/s changes the relative phase between the applied 3-D fields and the measured plasma response. Numerical simulations of linear, resistive, 2-fluid MHD show, that large plasma rotation increases flux surface corrugations1. Discharges with low averaged (~10 krad/s) and peaked rotation profiles (~40 krad/s) are reconstructed. Similarities and differences to forward modeled VMEC equilibria, which do not include rotational effects, are shown. The resulting significance of including rotational effects in VMEC is discussed. Supported by US DOE DE-AC05-00OR22725, DE-FC02-04ER54698.

  8. Isomolar semigrand ensemble molecular dynamics: development and application to liquid-liquid equilibria.

    PubMed

    Morrow, Timothy I; Maginn, Edward J

    2005-02-01

    An extended system molecular dynamics method for the isomolar semigrand ensemble (fixed number of particles, pressure, temperature, and fugacity fraction) is developed and applied to the calculation of liquid-liquid equilibria (LLE) for two Lennard-Jones mixtures. The method utilizes an extended system variable to dynamically control the fugacity fraction xi of the mixture by gradually transforming the identity of particles in the system. Two approaches are used to compute coexistence points. The first approach uses multiple-histogram reweighting techniques to determine the coexistence xi and compositions of each phase at temperatures near the upper critical solution temperature. The second approach, useful for cases in which there is no critical solution temperature, is based on principles of small system thermodynamics. In this case a coexistence point is found by running N-P-T-xi simulations at a common temperature and pressure and varying the fugacity fraction to map out the difference in chemical potential between the two species A and B (mu(A)-mu(B)) as a function of composition. Once this curve is known the equal-distance/equal-area criterion is used to determine the coexistence point. Both approaches give results that are comparable to those of previous Monte Carlo (MC) simulations. By formulating this approach in a molecular dynamics framework, it should be easier to compute the LLE of complex molecules whose intramolecular degrees of freedom are often difficult to properly sample with MC techniques.

  9. Measurements of solid-liquid equilibria in the ternary system NaCl-NaBr-H2O at 373 K

    NASA Astrophysics Data System (ADS)

    Sang, Shihua; Hu, Yongxia; Cui, Ruizhi; Hu, Juanxin; Wang, Yuan

    2015-07-01

    Solid-liquid equilibria in the ternary system NaCl-NaBr-H2O at 373 K were measured by the isothermal dissolution equilibrium method. The solubilities of salts and densities of saturated solutions in the ternary system were determined experimentally. The equilibrium solid phases were also determined by chemical analysis and X-ray powder diffraction. Using the experimental data, the phase diagram of the ternary system was obtained, which comprise one univariant curve and one stationary phase in crystallization filed of Na (Cl, Br). The ternary system was solid solution type. Density values in the equilibrium solution increase with an increase of the sodium bromide concentration while decrease with an increase of the sodium chloride concentration. The relationship equation of equilibrium liquid phase and the solid phase composition data were fitted with a regression equation.

  10. Dynamical Behaviors of Multiple Equilibria in Competitive Neural Networks With Discontinuous Nonmonotonic Piecewise Linear Activation Functions.

    PubMed

    Nie, Xiaobing; Zheng, Wei Xing

    2016-03-01

    This paper addresses the problem of coexistence and dynamical behaviors of multiple equilibria for competitive neural networks. First, a general class of discontinuous nonmonotonic piecewise linear activation functions is introduced for competitive neural networks. Then based on the fixed point theorem and theory of strict diagonal dominance matrix, it is shown that under some conditions, such n -neuron competitive neural networks can have 5(n) equilibria, among which 3(n) equilibria are locally stable and the others are unstable. More importantly, it is revealed that the neural networks with the discontinuous activation functions introduced in this paper can have both more total equilibria and locally stable equilibria than the ones with other activation functions, such as the continuous Mexican-hat-type activation function and discontinuous two-level activation function. Furthermore, the 3(n) locally stable equilibria given in this paper are located in not only saturated regions, but also unsaturated regions, which is different from the existing results on multistability of neural networks with multiple level activation functions. A simulation example is provided to illustrate and validate the theoretical findings.

  11. Electrochemical measurements and thermodynamic calculations of redox equilibria in pallasite meteorites - Implications for the eucrite parent body

    NASA Technical Reports Server (NTRS)

    Righter, Kevin; Arculus, Richard J.; Paslick, Cassi; Delano, John W.

    1990-01-01

    The intrinsic oxygen fugacity (IOF) of olivine separates from the Salta, Springwater, and Eagle Station pallasites was measured between 850 and 1150 C using oxygen-specific solid zirconia electrolytes at 100,000 Pa. Thermodynamic calculations of redox equilibria involving equalibrium pallasite assemblages are in good agreement with the experimental results and provide a lower limit to pallasite redox stability; others involving disequilibrium assemblages, suggest that pallasites experienced localized, late-stage oxidation and reduction effects. Consideration of the redox buffer metal-olivine-orthopyroxene utilizing calculated Eucrite Parent Body (EPB) mantle phase compositions indicates that small redox gradients may have existed in the EPB. Such gradients may have produced strong compositional variation within the EPB. In addition, there is apparently significant redox heterogeneity in the source area of Eagle Station Trio pallasites and Bocaiuva iron meteorites.

  12. Oxygen potentials and phase equilibria in the system Ca–Co–O and thermodynamic properties of Ca{sub 3}Co{sub 2}O{sub 6} and Ca{sub 3}Co{sub 4}O{sub 9.163}

    SciTech Connect

    Jacob, K.T. Gupta, Preeti

    2015-01-15

    Oxygen potentials established by the equilibrium between three condensed phases, CaO{sub ss}+CoO{sub ss}+Ca{sub 3}Co{sub 2}O{sub 6} and CoO{sub ss}+Ca{sub 3}Co{sub 2}O{sub 6}+Ca{sub 3}Co{sub 3.93+α}O{sub 9.36−δ}, are measured as a function of temperature using solid-state electrochemical cells incorporating yttria-stabilized zirconia as the electrolyte and pure oxygen as the reference electrode. Cation non-stoichiometry and oxygen non-stoichiometry in Ca{sub 3}Co{sub 3.93+α}O{sub 9.36−δ} are determined using different techniques under defined conditions. Decomposition temperatures and thermodynamic properties of Ca{sub 3}Co{sub 2}O{sub 6} and Ca{sub 3}Co{sub 4}O{sub 9.163} are calculated from the results. The standard entropy and enthalpy of formation of Ca{sub 3}Co{sub 2}O{sub 6} at 298.15 K are evaluated. Using thermodynamic data from this study and auxiliary information from the literature, phase diagram for the ternary system Ca–Co–O is computed. Isothermal sections at representative temperatures are displayed to demonstrate the evolution of phase relations with temperature. - Graphical abstract: Isothermal section of the phase diagram of the system Ca–Co–O at 1250 K. - Highlights: • Improved definition of cation and oxygen nonstoichiometry of Ca{sub 3}Co{sub 3.93+α}O{sub 9.36−δ}. • Measurement of Δμ{sub O{sub 2}} associated with two 3-phase fields as a function of temperature. • Use of solid-state electrochemical cells for accurate measurement of Δμ{sub O{sub 2}}. • Decomposition temperatures and thermodynamic properties for ternary oxides. • Characterization of ternary phase diagram of the system Ca–Co–O.

  13. Study of monoprotic acid-base equilibria in aqueous micellar solutions of nonionic surfactants using spectrophotometry and chemometrics.

    PubMed

    Babamoradi, Hamid; Abdollahi, Hamid

    2015-10-01

    Many studies have shown the distribution of solutes between aqueous phase and micellar pseudo-phase in aqueous micellar solutions. However, spectrophotometric studies of acid-base equilibria in these media do not confirm such distribution because of the collinearity between concentrations of chemical species in the two phases. The collinearity causes the number of detected species to be equal to the number of species in a homogenous solution that automatically misinterpreted as homogeneity of micellar solutions, therefore the collinearity is often neglected. This interpretation is in contradiction to the distribution theory in micellar media that must be avoided. Acid-base equilibrium of an indicator was studied in aqueous micellar solutions of a nonionic surfactant to address the collinearity using UV/Visible spectrophotometry. Simultaneous analysis (matrix augmentation) of the equilibrium and solvation data was applied to eliminate the collinearity from the equilibrium data. A model was then suggested for the equilibrium that was fitted to the augmented data to estimate distribution coefficients of the species between the two phases. Moreover, complete resolution of concentration and spectral profiles of species in each phase was achieved.

  14. Modification of Ni-Rich FCG NMC and NCA Cathodes by Atomic Layer Deposition: Preventing Surface Phase Transitions for High-Voltage Lithium-Ion Batteries

    DOE PAGES

    Mohanty, Debasish; Dahlberg, Kevin; King, David M.; David, Lamuel A.; Sefat, Athena S.; Wood, David L.; Daniel, Claus; Dhar, Subhash; Mahajan, Vishal; Lee, Myongjai; et al

    2016-05-26

    The energy density of current lithium-ion batteries (LIBs) based on layered LiMO2 cathodes (M=Ni, Mn, Co: NMC; M=Ni, Co, Al: NCA) needs to be improved significantly in order to compete with internal combustion engines and allow for widespread implementation of electric vehicles (EVs). In this report, we show that atomic layer deposition (ALD) of titania (TiO2) and alumina (Al2O3) on Ni-rich FCG NMC and NCA active material particles could substantially improve LIB performance and allow for increased upper cutoff voltage (UCV) during charging, which delivers significantly increased specific energy utilization. Our results show that Al2O3 coating improved the NMC cyclingmore » performance by 40% and the NCA cycling performance by 34% at 1C/₋1C with respectively 4.35V and 4.4V UCV in 2Ah pouch cells. High resolution TEM/SAED structural characterization revealed that Al2O3 coatings prevented surface-initiated layered-to-spinel phase transitions in coated materials which were prevalent in uncoated materials. Lastly, EIS confirmed that Al2O3-coated materials had significantly lower increase in the charge transfer component of impedance during cycling. In conclusion, the ability to mitigate degradation mechanisms for Ni-rich NMC and NCA illustrated in this report provides insight into a method to enable the performance of high-voltage LIBs.« less

  15. Modification of Ni-Rich FCG NMC and NCA Cathodes by Atomic Layer Deposition: Preventing Surface Phase Transitions for High-Voltage Lithium-Ion Batteries.

    PubMed

    Mohanty, Debasish; Dahlberg, Kevin; King, David M; David, Lamuel A; Sefat, Athena S; Wood, David L; Daniel, Claus; Dhar, Subhash; Mahajan, Vishal; Lee, Myongjai; Albano, Fabio

    2016-01-01

    The energy density of current lithium-ion batteries (LIBs) based on layered LiMO2 cathodes (M = Ni, Mn, Co: NMC; M = Ni, Co, Al: NCA) needs to be improved significantly in order to compete with internal combustion engines and allow for widespread implementation of electric vehicles (EVs). In this report, we show that atomic layer deposition (ALD) of titania (TiO2) and alumina (Al2O3) on Ni-rich FCG NMC and NCA active material particles could substantially improve LIB performance and allow for increased upper cutoff voltage (UCV) during charging, which delivers significantly increased specific energy utilization. Our results show that Al2O3 coating improved the NMC cycling performance by 40% and the NCA cycling performance by 34% at 1 C/-1 C with respectively 4.35 V and 4.4 V UCV in 2 Ah pouch cells. High resolution TEM/SAED structural characterization revealed that Al2O3 coatings prevented surface-initiated layered-to-spinel phase transitions in coated materials which were prevalent in uncoated materials. EIS confirmed that Al2O3-coated materials had significantly lower increase in the charge transfer component of impedance during cycling. The ability to mitigate degradation mechanisms for Ni-rich NMC and NCA illustrated in this report provides insight into a method to enable the performance of high-voltage LIBs. PMID:27226071

  16. Modification of the activity of Mg{sub 3}(PO{sub 4}){sub 2} in the gas-phase conversion of cyclohexanol by addition of sodium carbonate

    SciTech Connect

    Aramendia, M.A.; Borau, V.; Jimenez, C.

    1995-11-01

    This paper reports the synthesis and characterization of solid NaMgPO{sub 4}, obtained by adding Na{sub 2}CO{sub 3} to freshly formed Mg{sub 3}(PO{sub 4}){sub 2}{center_dot}22H{sub 2}O. The magnesium orthophosphate was prepared by gelling an aqueous solution of MgCl{sub 2} and Na{sub 2}HPO{sub 4} with 3 N NaOH. The solid products thus obtained were characterized by using various structural (XRD), surface (XPS, DRIFT,BET), and morphological (SEM) elucidation techniques. The results show that the NaMgPO{sub 4} surface also contains Na{sub 2}CO{sub 3}, NaCl, and MgO, which endow it with increased activity and selectivity. Thus, Mg{sub 3}(PO{sub 4}){sub 2} yields cyclohexene (CHE) preferentially, and some cyclohexanone (CHONE), in the gas-phase conversion of cyclohexanol. On the other hand, NaMgPO{sub 4} produces CHONE selectively under the same reaction conditions. 61 refs., 9 figs., 4 tabs.

  17. Modification of Ni-Rich FCG NMC and NCA Cathodes by Atomic Layer Deposition: Preventing Surface Phase Transitions for High-Voltage Lithium-Ion Batteries

    NASA Astrophysics Data System (ADS)

    Mohanty, Debasish; Dahlberg, Kevin; King, David M.; David, Lamuel A.; Sefat, Athena S.; Wood, David L.; Daniel, Claus; Dhar, Subhash; Mahajan, Vishal; Lee, Myongjai; Albano, Fabio

    2016-05-01

    The energy density of current lithium-ion batteries (LIBs) based on layered LiMO2 cathodes (M = Ni, Mn, Co: NMC; M = Ni, Co, Al: NCA) needs to be improved significantly in order to compete with internal combustion engines and allow for widespread implementation of electric vehicles (EVs). In this report, we show that atomic layer deposition (ALD) of titania (TiO2) and alumina (Al2O3) on Ni-rich FCG NMC and NCA active material particles could substantially improve LIB performance and allow for increased upper cutoff voltage (UCV) during charging, which delivers significantly increased specific energy utilization. Our results show that Al2O3 coating improved the NMC cycling performance by 40% and the NCA cycling performance by 34% at 1 C/‑1 C with respectively 4.35 V and 4.4 V UCV in 2 Ah pouch cells. High resolution TEM/SAED structural characterization revealed that Al2O3 coatings prevented surface-initiated layered-to-spinel phase transitions in coated materials which were prevalent in uncoated materials. EIS confirmed that Al2O3-coated materials had significantly lower increase in the charge transfer component of impedance during cycling. The ability to mitigate degradation mechanisms for Ni-rich NMC and NCA illustrated in this report provides insight into a method to enable the performance of high-voltage LIBs.

  18. Modification of Ni-Rich FCG NMC and NCA Cathodes by Atomic Layer Deposition: Preventing Surface Phase Transitions for High-Voltage Lithium-Ion Batteries

    PubMed Central

    Mohanty, Debasish; Dahlberg, Kevin; King, David M.; David, Lamuel A.; Sefat, Athena S.; Wood, David L.; Daniel, Claus; Dhar, Subhash; Mahajan, Vishal; Lee, Myongjai; Albano, Fabio

    2016-01-01

    The energy density of current lithium-ion batteries (LIBs) based on layered LiMO2 cathodes (M = Ni, Mn, Co: NMC; M = Ni, Co, Al: NCA) needs to be improved significantly in order to compete with internal combustion engines and allow for widespread implementation of electric vehicles (EVs). In this report, we show that atomic layer deposition (ALD) of titania (TiO2) and alumina (Al2O3) on Ni-rich FCG NMC and NCA active material particles could substantially improve LIB performance and allow for increased upper cutoff voltage (UCV) during charging, which delivers significantly increased specific energy utilization. Our results show that Al2O3 coating improved the NMC cycling performance by 40% and the NCA cycling performance by 34% at 1 C/−1 C with respectively 4.35 V and 4.4 V UCV in 2 Ah pouch cells. High resolution TEM/SAED structural characterization revealed that Al2O3 coatings prevented surface-initiated layered-to-spinel phase transitions in coated materials which were prevalent in uncoated materials. EIS confirmed that Al2O3-coated materials had significantly lower increase in the charge transfer component of impedance during cycling. The ability to mitigate degradation mechanisms for Ni-rich NMC and NCA illustrated in this report provides insight into a method to enable the performance of high-voltage LIBs. PMID:27226071

  19. Headspace-Solid-Phase Microextraction-Gas Chromatography as Analytical Methodology for the Determination of Volatiles in Wild Mushrooms and Evaluation of Modifications Occurring during Storage

    PubMed Central

    Costa, Rosaria; De Grazia, Selenia; Grasso, Elisa; Trozzi, Alessandra

    2015-01-01

    Mushrooms are sources of food, medicines, and agricultural means. Not much is reported in the literature about wild species of the Mediterranean flora, although many of them are traditionally collected for human consumption. The knowledge of their chemical constituents could represent a valid tool for both taxonomic and physiological characterizations. In this work, a headspace-solid-phase microextraction (HS-SPME) method coupled with GC-MS and GC-FID was developed to evaluate the volatile profiles of ten wild mushroom species collected in South Italy. In addition, in order to evaluate the potential of this analytical methodology for true quantitation of volatiles, samples of the cultivated species Agaricus bisporus were analyzed. The choice of this mushroom was dictated by its ease of availability in the food market, due to the consistent amounts required for SPME method development. For calibration of the main volatile compounds, the standard addition method was chosen. Finally, the assessed volatile composition of A. bisporus was monitored in order to evaluate compositional changes occurring during storage, which represents a relevant issue for such a wide consumption edible product. PMID:25945282

  20. Modification of Mott phase transition characteristics in VO2@TiO2 core/shell nanostructures by misfit-strained heteroepitaxy.

    PubMed

    Li, Yamei; Ji, Shidong; Gao, Yanfeng; Luo, Hongjie; Jin, Ping

    2013-07-24

    Vanadium dioxide (VO2) is a key material for thermochromic smart windows that can respond to environmental temperature and modulate near-infrared irradiation by changing from a transparent state at low temperature to a more reflective state at high temperature, while maintaining visible transmittance. Here, we demonstrate for the first time that the Mott phase transition characteristics in VO2 nanoparticles can be remarkably modified by misfit strains occurring at the epitaxial interface between VO2 and the anatase TiO2 of VO2/TiO2 core-shell particles. The heteroepitaxial growth of the as-synthesized particles followed an unprecedented orientation relationship, and an epitaxial growth mechanism is proposed to explain this behavior. A relatively small theoretical coherent misfit (3-11%) and a moderate heating rate (20 °C·min(-1)) in the preparation of the core-shell structure were critically important from the thermodynamic and kinetic perspectives, respectively. The misfit-induced interfacial strain along the uniaxial cR axis increased the transition temperatures, especially on the cooling portion of the heating-cooling cycle, leading to a notably reduced transition hysteresis loop width (from 23.5 to 12.0 °C). Moreover, the optical band gap was also engineered by the interfacial effect. Such a reduced hysteresis showed a benefit for enhancing a rapid response for energy saving thermochromic smart windows. PMID:23777607