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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. Binary Solid-Liquid Phase Equilibria

    ERIC Educational Resources Information Center

    Ellison, Herbert R.

    1978-01-01

    Indicates some of the information that may be obtained from a binary solid-liquid phase equilibria experiment and a method to write a computer program that will plot an ideal phase diagram to which the experimental results may be compared. (Author/CP)

  3. 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

  4. Phase Equilibria and Crystallography of Ceramic Oxides.

    PubMed

    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.

  5. Thermodynamics and Phase Equilibria in the Vandium-Silicon System.

    DTIC Science & Technology

    1984-09-01

    and Phase Equilibria in July 1, 1982-June 30, 1985 the Vandium-Silicon System 6. PERFORMING ORG. REPORT NUMBER 7. AUTHOR(a) S. CONTRACT OR GRANT...e) Effusion, Mass Spectrometry, Vanadium Silicides, Phase Equilibria , Range of Homogeneity, Thermodynamics Activities, Free Energies of Formation...DD Form 1473. Copies of form available from cognizant contract administrator. THERMODYNAMICS AND PHASE EQUILIBRIA IN THE VANDIUM-SILICON SYSTEM

  6. 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.

  7. Nanoscale effects on thermodynamics and phase equilibria in oxide systems.

    PubMed

    Navrotsky, Alexandra

    2011-08-22

    Because different solid materials (phases) have different surface energies, equilibria among them will be significantly affected by particle size. This Minireview summarizes experimental (calorimetric) data for the surface energies of oxides and discusses shifts in the stability of polymorphs, the thermodynamics of hydration, and oxidation-reduction reactions in nanoscale oxide systems.

  8. 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.

  9. Phase equilibria study of pseudobrookite type minerals

    NASA Technical Reports Server (NTRS)

    Friel, J. J.

    1974-01-01

    Pseudobrookite, is found in volcanic rocks, and the mineral armalcolite ((Fe,Mg)Ti2O5) found in the Apollo 11 and subsequent lunar samples seems to be unique to the moon. In plutonic rocks on the earth, ilmenite and rutile were found with what appears to be an equilibrium liquidus texture, while on the moon armalcolite often appears to be the primary liquidus phase among Ti-oxides. This suggests that total pressure may be a factor in the formation of these minerals, and a knowledge of the phase relations in this system yields information about the pressure under which a given magma crystallized.

  10. 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.

  11. Phase equilibria in model surfactants forming Langmuir monolayers.

    PubMed

    Ramírez, E; Santana, A; Cruz, A; López, G E

    2007-12-14

    The study of Langmuir monolayers has generated the attention of researchers because of their unique properties and their not well understood phase equilibrium. These monolayers exhibit interesting phase diagrams where the unusual liquid-liquid equilibrium can be observed for a single component monolayer. Monte Carlo computer simulations in the virtual Gibbs ensemble were used to obtain the phase diagram of Langmuir monolayers. The liquid-vapor and liquid-liquid phase equilibria were considered by constructing the Cailletet-Mathias phase diagrams. By using the Ising model and the rectilinear approximations the identification of the critical properties for both equilibria was determined. These critical parameters were calculated as a function of the strength of the interaction between the surfactant molecules and the aqueous subphase. As a result, we have identified the coexistence between a liquid expanded state (LES)-vapor and the liquid condensed state-LES, in agreement with experimental and theoretical evidence in the literature. We obtained a clear separation of phases and a strong dependence on the strength of the solvent used. Namely, as the interaction between the solvent and the head of the surfactant increases, the critical properties also increase. Equilibrium states were characterized by computing thermodynamic quantities as a function of temperature and solvent strength.

  12. Refractory and Hard Materials in the Ti-Si-B-C-N System - Phase Equilibria, Phase Reactions and Thermal Stabilities

    DTIC Science & Technology

    2004-12-01

    1 REFRACTORY AND HARD MATERIALS IN THE Ti-Si-B-C-N SYSTEM – PHASE EQUILIBRIA , PHASE REACTIONS AND THERMAL STABILITIES Hans Jürgen Seifert...the underlying phase equilibria and reactions have to be known in detail. The main goal of this work was to study the thermal stability with...respect to the phase equilibria and the phase reactions of ceramics and refractory and hard materials in the Ti-Si-B-C-N system by means of CALPHAD

  13. Phase equilibria in polydisperse nonadditive hard-sphere systems.

    PubMed

    Paricaud, Patrice

    2008-08-01

    Colloidal particles naturally exhibit a size polydispersity that can greatly influence their phase behavior in solution. Nonadditive hard-sphere (NAHS) mixtures are simple and well-suited model systems to represent phase transitions in colloid systems. Here, we propose an analytical equation of state (EOS) for NAHS fluid mixtures, which can be straightforwardly applied to polydisperse systems. For positive values of the nonadditivity parameter Delta the model gives accurate predictions of the simulated fluid-fluid coexistence curves and compressibility factors. NPT Monte Carlo simulations of the mixing properties of the NAHS symmetric binary mixture with Delta>0 are reported. It is shown that the enthalpy of mixing is largely positive and overcomes the positive entropy of mixing when the pressure is increased, leading to a fluid-fluid phase transition with a lower critical solution pressure. Phase equilibria in polydisperse systems are predicted with the model by using the density moment formalism [P. Sollich, Adv. Chem. Phys. 116, 265 (2001)]. We present predictions of the cloud and shadow curves for polydisperse NAHS systems composed of monodisperse spheres and polydisperse colloid particles. A fixed nonadditivity parameter Delta > 0 is assumed between the monodisperse and polydisperse spheres, and a Schulz distribution is used to represent the size polydispersity. Polydispersity is found to increase the extent of the immiscibility region. The predicted cloud and shadow curves depend dramatically on the upper cutoff diameter sigmac of the Schulz distribution, and three-phase equilibria can occur for large values of sigmac.

  14. 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

  15. PHASE EQUILIBRIA INVESTIGATION OF BINARY, TERNARY, AND HIGHER ORDER SYSTEMS. PART 9. CALCULATION OF THERMODYNAMIC QUANTITIES FROM PHASE DIAGRAMS

    DTIC Science & Technology

    The thermodynamic fundamentals relating phase equilibria in binary and ternary systems to the thermodynamic properties of the phases are reviewed and...system demonstrate the application of the equations for extracting thermodynamic data from phase diagrams and also for the prediction of phase equilibria .

  16. 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}.

  17. Nematogenic Aromatic Block Copolymers of Rigid and Flexible Units. II. Phase Equilibria.

    DTIC Science & Technology

    1986-11-06

    Phase Equilibria 12 PERSONAL AUTHOR(S) -W_ R_ Krinhaum- 7- Shuf~in-. Prpdnn- A (’ifiarri anri r. rnnin 13a 1,TAPOF -EPORT 113b TIME COVERED 14. DATE...and Flexible Units. II. Phase Equilibria by W. R. Krigbaum, Z. Shufan, Jack Preston, A. Ciferri and G. Conio q Prepared for Publication in the

  18. Solid-State Phase Equilibria in the ZnS-Ga2S3 System

    DTIC Science & Technology

    1989-10-01

    S!PC FE.Wpy OFFICE OF NAVAL RESEARCH Contract N00014-87-K-0531 R&TCode 431a016 " ITECHNICAL REPORT NO. 4SSolid-State Phase Equilibria in the ZnS...FUNDING NUMBERS PROGRAM IPROJECT ITASK WORK UNIT ELEMENT NO. I(NO. (NO. (NO. 11. TITLE (include Security Classification) Soltd-State Phase Equilibria in...pure components. The identification of the phases was determined by x-ray diffraction methods. Ile principal feature of the phase equilibria is the

  19. Phase Equilibria and Transition in Mixtures of a Homopolymer and a Block Copolymer. II.

    DTIC Science & Technology

    1983-01-26

    AD-A124 929 PHASE EQUILIBRIA AND TRANSITION IN MIXTURES OF A In- NOMOPOLYMER AND’A BLOCK..(U) CINCINNATI UNJY ON DEPT OF MATERIALS SCIENCE AND...REPORT NO. 7 v2 L Phase Equilibria and Transition in Mixtures of a Homopolymer and a Block Copolymer II. The Phase Diagram by R. J. Roe and W. C. Zin...homopolymers as in our systems. The phase equilibria at temperatures above the "pseudo-triple point" BCD can be interpreted in terms of the free energy of

  20. 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

  1. Solid-State Phase Equilibria in the ZnS-CdS System

    DTIC Science & Technology

    1988-09-01

    OFFICE OF NAVAL RESEARCH !iTIB - K Contract N00014-87-K-0531 R&TCode 431a016 TECHNICAL REPORT NO. I Solid-State Phase Equilibria in the ZnS-CdS...PROGRAM PROJECT TASK VVORK j*JT ELEMENT NO NO NO % Q I rTi (Incluc e Security Classitication) Solid-State Phase Equilibria in the ZnS-CdS System 12 PERSONAL...are obsolete Accesslon For NTI& GRA&1 SOLD-STATE PHASE EQUILIBRIA IN THE ZnS-CdS SYSTEM DTIC TAB 3 W. W. Chen, J. M. Zhang, A. J. Ardell, and B. Dunn

  2. Solid-Phase Equilibria for Metal-Silicon-Oxygen Ternary Systems. II. Sc, Y, and La

    DTIC Science & Technology

    1991-02-28

    Organization: Regents of the University of California TECHNICAL REPORT No. 9 SOLID- PHASE EQUILIBRIA FOR METAL-SILICON-OXYGEN TERNARY SYSTEMS: 11: Sc, Y, AND La...34’ SOLID- PHASE EQUILIBRIA FOR METAL-SILICON-OXYGEN TERNARY SYSTEMS: 11: Sc, Y, AND 1a 13 0911OtiA AUTHORCS) Haojie Yuan and R. Stanley Williams lI" TV...0660te tCLhSSWI=) Solid phase equilibria for metal-silicon-oxygen ternary systems I1: Sc, Y and La Haojie Yuan and R. Stanley Williams Department of

  3. Model for phase equilibria in micellar solutions of nonionic surfactants

    NASA Astrophysics Data System (ADS)

    Goldstein, Raymond E.

    1986-03-01

    The formation of spherical micelles in aqueous solutions of nonionic surfactants and the equilibria between two such micellar phases are studied with a phenomenological model incorporating hydrophobic interactions and the configurational entropy of the amphiphiles. The distribution of micelle sizes is determined over the entire temperature-composition phase diagram, and moments of that distribution function determine the consolute point parameters. In a generalization of an analysis given by Stillinger and Ben-Naim, the mathematical properties of various thermodynamic functions in the neighborhood of the critical micelle concentration are related to the location of branch points of the osmotic pressure in the complex concentration plane. The model attributes the experimentally observed lower critical solution points in these systems to surfactant-water hydrogen bonding, whose temperature dependence is described with a mean field approximation. Calculated phase diagrams are in qualitative agreement with those from experiments, in particular, exhibiting closed solubility loops with quite distinct upper and lower critical compositions, and values for the lower critical composition on the order of several percent volume fraction. The relevance of certain aspects of the model to the understanding of microemulsions is discussed.

  4. Solid Phase Equilibria in the Pi-Ga-As and Pt-Ga-Sb Systems

    DTIC Science & Technology

    1988-07-22

    OFFICE OF NAVAL RESEARCH Research Contract N00014-87-K-0014 R&T Code 413E026---01 AD-A 198 654 TECHNICAL REPORT No. 9 SOLID PHASE EQUILIBRIA IN THE...Classtcation) UNCLASSLFIED: Tech.Rept.#9 SOLID PHASE EQUILIBRIA IN T11: Pt-Ga-As AND Pt-Ga-Sb SYST’IS 12 PERSONAL AuTiOR(S) C.T. Tsai and R.S. Williats 13a TYPE

  5. 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

    2016-08-03

    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.

  6. Densities, Electrical Conductivities, Viscosities and Phase Equilibria of 1,3-Dialkylimidazolium Chloride - Aluminum Chloride Binary and Ternary Melts.

    DTIC Science & Technology

    1982-07-01

    FRANK J. SELLER RESEARCH LABORATORY FJSRL-TR-82-0006 JULY 1982 DENSITIES, ELEC’TRICAL CONDUCTIVITIES, VISCOSITIES AND PHASE EQUILIBRIA OF 1,3...Conductivities, Viscosities and Phase Equilibria of 1,3- Interim 6/81-7/82 Dialkylimidazolium Chloride-Aluminum Chloride 6. PERFORMING ORG. REPORT NUMBER...Entered) FJSRL-TR-82-0006 DENSITIES, ELECTRICAL CONDUCTIVITIES, VISCOSITIES AND PHASE EQUILIBRIA OF 1,3-DIALKYLIMIDAZOLIUM CHLORIDE- ALUMINUM CHLORIDE

  7. Exact calculations of phase and membrane equilibria for complex fluids by Monte Carlo simulation. Progress report

    SciTech Connect

    Panagiotopoulos, A.Z.

    1992-06-08

    Objective is to develop molecular simulation techniques for phase equilibria in complex systems. The Gibbs ensemble Monte Carlo method was extended to obtain phase diagrams for highly asymmetric and ionic fluids. The modified Widom test particle technique was developed for chemical potentials of long polymeric molecules, and preliminary calculations of phase behavior of simple model homopolymers were performed.

  8. Exact calculations of phase and membrane equilibria for complex fluids by Monte Carlo simulation

    SciTech Connect

    Panagiotopoulos, A.Z.

    1992-06-08

    Objective is to develop molecular simulation techniques for phase equilibria in complex systems. The Gibbs ensemble Monte Carlo method was extended to obtain phase diagrams for highly asymmetric and ionic fluids. The modified Widom test particle technique was developed for chemical potentials of long polymeric molecules, and preliminary calculations of phase behavior of simple model homopolymers were performed.

  9. 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.

  10. Phase transformations and phase equilibria in the Co-Sn-Ti system in the crystallization interval

    NASA Astrophysics Data System (ADS)

    Fartushna, Iu.; Bulanova, M.; Ayral, R. M.; Tedenac, J. C.; Meleshevich, K.

    2016-12-01

    The Co-Sn-Ti system was studied in the crystallization interval (below 50 at% Sn) by the methods of Scanning Electron Microscopy, microprobe analysis, Differential Thermal Analysis, X-ray diffraction. The liquidus and solidus projections and the melting diagram were constructed. Only Co2TiSn(τ1) ternary compound (Heusler phase-L12) was found in equilibria with the liquid in the concentration interval studied. Taking into account our recent data, the liquidus projection is characterized by the fields of primary crystallization of (βTi), (Co), binary-based phases Ti3Sn, Ti2Sn, Ti5Sn3, Ti6Sn5, Ti2Co, TiCo, TiCo2 (c), TiCo2 (h), TiCo3, βCo3Sn2, CoSn and ternary τ1. The solidus projection is characterized by thirteen three-phase fields, which result from invariant four-phase equilibria, five are of eutectic type (E) and eight of transition type (U) and the existence of one more region Ti2Sn3+βCoSn3+(Sn) in the solidus projection is discussed.

  11. 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)

  12. New investigation of phase equilibria in the system Al-Cu-Si.

    PubMed

    Ponweiser, Norbert; Richter, Klaus W

    2012-01-25

    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)-γ(1) 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.

  13. 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

  14. Transport and phase equilibria of benzene in FAU type zeolites

    NASA Astrophysics Data System (ADS)

    Saravanan, Chandra

    We have studied lattice models for self-diffusion of benzene in FAU type zeolites, to explore the effect of the thermodynamics of confined fluids on the transport properties of molecules in zeolites. Our model assumes that benzene molecules are located near Na+ ions in supercages, and in 12-ring windows separating adjacent supercages, respectively. The study was performed in three stages. First, to disentangle the effect of a vapor-liquid phase equilibria on diffusion in zeolites, the transport of benzene in Na-Y is modeled in the absence of attractive guest-guest interactions. The loading dependence of diffusion coefficient, Dtheta, at a constant temperature, referred to as a diffusion isotherm, is modeled with site-blocking effects using a mean field theory (MFT) that yields, Dq=16kq a2q, where atheta ≅ 11 A is the mean intercage jump length and 1/ktheta is the mean supercage residence time. A completely analytical expression is derived to calculate ktheta. The MFT is tested using a mean field approximation (MFA) where ktheta and atheta are calculated from kinetic Monte Carlo simulations yielding excellent qualitative agreement. Further calculations are performed to test MFA by calculating "exact" diffusion coefficients from mean square displacement (MSD) calculations also yielding excellent qualitative agreement. Next, by including guest-guest attractive interactions, we have performed lattice grand canonical Monte Carlo simulations of benzene adsorption in Na-X zeolite to determine whether strongly confined benzene molecules exhibit subcritical properties. We observe a phase transition from low to high density of adsorbed benzene, analogous to vapor-liquid equilibrium, at temperatures as high as 300 K and above. By performing thermodynamic integration to construct the coexistence curve, we obtain a critical point for benzene in Na-X at Tc = 370 +/- 20 K, thetac = 0.45 +/- 0.05 fractional coverage. We suggest that careful adsorption experiments should be

  15. Leveraging Gibbs Ensemble Molecular Dynamics and Hybrid Monte Carlo/Molecular Dynamics for Efficient Study of Phase Equilibria.

    PubMed

    Gartner, Thomas E; Epps, Thomas H; Jayaraman, Arthi

    2016-11-08

    We describe an extension of the Gibbs ensemble molecular dynamics (GEMD) method for studying phase equilibria. Our modifications to GEMD allow for direct control over particle transfer between phases and improve the method's numerical stability. Additionally, we found that the modified GEMD approach had advantages in computational efficiency in comparison to a hybrid Monte Carlo (MC)/MD Gibbs ensemble scheme in the context of the single component Lennard-Jones fluid. We note that this increase in computational efficiency does not compromise the close agreement of phase equilibrium results between the two methods. However, numerical instabilities in the GEMD scheme hamper GEMD's use near the critical point. We propose that the computationally efficient GEMD simulations can be used to map out the majority of the phase window, with hybrid MC/MD used as a follow up for conditions under which GEMD may be unstable (e.g., near-critical behavior). In this manner, we can capitalize on the contrasting strengths of these two methods to enable the efficient study of phase equilibria for systems that present challenges for a purely stochastic GEMC method, such as dense or low temperature systems, and/or those with complex molecular topologies.

  16. Investigation of Phase Equilibria and Some Properties of Alloys of Ti-Al-Fe and Ti-Al-V Systems,

    DTIC Science & Technology

    Some data on the structure and properties of Ti-Al-Fe alloys are presented. The phase equilibria in alloys in the system Ti-Al-V were studies...However, the data available in the literature on phase equilibria in the systems Ti-Al-Fe and Ti-Al-V require refinement, as they are insufficiently

  17. The nucleation rate surfaces design over diagram of phase equilibria and their applications for computational chemistry

    NASA Astrophysics Data System (ADS)

    Anisimov, M. P.

    2016-12-01

    One can find in scientific literature a pretty fresh idea of the nucleation rate surfaces design over the diagrams of phase equilibria. That idea looks like profitable for the nucleation theory development and for various practical applications where predictions of theory have no high enough accuracy for today. The common thermodynamics has no real ability to predict parameters of the first order phase transition. Nucleation experiment can be provided in very local nucleation conditions even the nucleation takes place from the critical line (in two-component case) down to the absolute zero temperature limit and from zero nucleation rates at phase equilibria up to the spinodal conditions. Theory predictions have low reliability as a rule. The computational chemistry has chance to make solution of that problem easier when a set of the used axiomatic statements will adapt enough progressive assumptions [1]. Semiempirical design of the nucleation rate surfaces over diagrams of phase equilibria have a potential ability to provide a reasonable quality information on nucleation rate for each channel of nucleation. Consideration and using of the nucleation rate surface topologies to optimize synthesis of a given phase of the target material can be available when data base on nucleation rates over diagrams of phase equilibria will be created.

  18. 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

  19. Phase equilibria in the neodymium-cadmium binary system.

    PubMed

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

    2014-09-05

    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.

  20. TERNARY PHASE EQUILIBRIA IN TRANSITION METAL-BORON-CARBON-SILICON SYSTEMS. PART 4. THERMOCHEMICAL CALCULATIONS, VOLUME 3. COMPUTATIONAL APPROACH TO THE CALCULATION OF TERNARY PHASE DIAGRAMS

    DTIC Science & Technology

    The general conditional equations which govern the phase equilibria in three-component systems are presented. Using the general conditional equations...a general method has been developed to precalculate the phase equilibria in three-component systems from first principle using computer technique...The method developed has been applied to several model examples and the system Ta-Hf-C. The phase equilibria in three-component systems calculated

  1. 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.

  2. Phase equilibria in the Ag-Au-In system at 500°C

    NASA Astrophysics Data System (ADS)

    Ptashkina, E. A.; Romanova, A. G.; Pavlenko, A. S.; Kabanova, E. G.; Kuznetsov, V. N.

    2017-02-01

    Phase equilibria in Ag-Au-In system at 500°C are investigated by means of electron microscopy, electron probe microanalysis, and X-ray powder diffraction. The part of the system's isothermal cross section with an indium content of up to 50 at % is constructed.

  3. EXPERIMENTAL PHASE EQUILIBRIA OF SELECTED BINARY, TERNARY, AND HIGHER ORDER SYSTEMS. PART 4. THE PHASE DIAGRAM W-B-C

    DTIC Science & Technology

    system and the mutual solubilities between carbide and boride phases are small. The solid state sections (򒾐C) are characterized by two- phase ... equilibria existing between the phase pairs W2B + W2C, W2B + WC, WC + WB, WB + C, W2B5 + C, W2B5 + B4C, and WB approximately 4 + B4C. The two-phase

  4. Fast Method for Computing Chemical Potentials and Liquid-Liquid Phase Equilibria of Macromolecular Solutions.

    PubMed

    Qin, Sanbo; Zhou, Huan-Xiang

    2016-08-25

    Chemical potential is a fundamental property for determining thermodynamic equilibria involving exchange of molecules, such as between two phases of molecular systems. Previously, we developed the fast Fourier transform (FFT)-based method for Modeling Atomistic Protein-crowder interactions (FMAP) to calculate excess chemical potentials according to the Widom insertion. Intermolecular interaction energies were expressed as correlation functions and evaluated via FFT. Here, we extend this method to calculate liquid-liquid phase equilibria of macromolecular solutions. Chemical potentials are calculated by FMAP over a wide range of molecular densities, and the condition for coexistence of low- and high-density phases is determined by the Maxwell equal-area rule. When benchmarked on Lennard-Jones fluids, our method produces an accurate phase diagram at 18% of the computational cost of the current best method. Importantly, the gain in computational speed increases dramatically as the molecules become more complex, leading to many orders of magnitude in speed up for atomistically represented proteins. We demonstrate the power of FMAP by reporting the first results for the liquid-liquid coexistence curve of γII-crystallin represented at the all-atom level. Our method may thus open the door to accurate determination of phase equilibria for macromolecular mixtures such as protein-protein mixtures and protein-RNA mixtures, that are known to undergo liquid-liquid phase separation, both in vitro and in vivo.

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

    PubMed

    Circone, Susan; Kirby, Stephen H; Stern, Laura A

    2006-04-27

    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-H2O. 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/nCH4.H2O, 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.

  6. 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.

  7. 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.

  8. 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.

  9. 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.

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

    NASA Technical Reports Server (NTRS)

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

    1972-01-01

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

  11. Phase equilibria in DOPC/DPPC-d62/cholesterol mixtures.

    PubMed

    Davis, James H; Clair, Jesse James; Juhasz, Janos

    2009-01-01

    There is broad interest in the question of fluid-fluid phase coexistence in membranes, in particular, whether evidence for liquid-disordered (l(d))-liquid-ordered (l(o)) two-phase regions or membrane "rafts" can be found in natural membranes. In model membrane systems, such phase behavior is observed, and we have used deuterium nuclear magnetic resonance spectroscopy to map the phase boundaries of ternary mixtures containing 1,2-dioleoyl-sn-glycero-3-phosphocholine (DOPC), chain-perdeuterated 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC-d(62)), and cholesterol. For both this ternary model system and the binary DPPC-d(62)/cholesterol system, we present clear evidence for l(d)-l(o) two-phase coexistence. We have selected sample compositions to focus on this region of fluid-fluid phase coexistence and to determine its temperature and composition ranges. The deuterium nuclear magnetic resonance spectra for compositions near the l(d)-l(o) phase boundary at high cholesterol concentrations show evidence of exchange broadening or critical fluctuations in composition, similar to that reported by Vist and Davis. There appears to be a line of critical compositions ranging from 48 degrees C for a DOPC/DPPC-d(62)/cholesterol composition of 0:75:25, to approximately -8 degrees C for the composition 57:14:29. At temperatures below this two-phase region, there is a region of three-phase coexistence (l(d)-l(o)-gel). These results are collected and presented in terms of a partial ternary phase diagram that is consistent with previously reported results of Vist and Davis.

  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. 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.

  14. 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.

  15. Phase equilibria and modeling of pyridinium-based ionic liquid solutions.

    PubMed

    Domańska, Urszula; Królikowski, Marek; Ramjugernath, Deresh; Letcher, Trevor M; Tumba, Kaniki

    2010-11-25

    The phase diagrams of the ionic liquid (IL) N-butyl-4-methylpyridinium bis{(trifluoromethyl)sulfonyl}imide ([BM(4)Py][NTf(2)]) with water, an alcohol (1-butanol, 1-hexanol, 1-octanol, 1-decanol), an aromatic hydrocarbon (benzene, toluene, ethylbenzene, n-propylbenzene), an alkane (n-hexane, n-heptane, n-octane), or cyclohexane have been measured at atmospheric pressure using a dynamic method. This work includes the characterization of the synthesized compound by water content and also by differential scanning calorimetry. Phase diagrams for the binary systems of [BM(4)Py][NTf(2)] with all solvents reveal eutectic systems with regards to (solid-liquid) phase equilibria and show immiscibility in the liquid phase region with an upper critical solution temperature (UCST) in most of the mixtures. The phase equilibria (solid, or liquid-liquid) for the binary systems containing aliphatic hydrocarbons reported here exhibit the lowest solubility and the highest immiscibility gap, a trend which has been observed for all ILs. The reduction of experimental data has been carried out using the nonrandom two-liquid (NRTL) correlation equation. The phase diagrams reported here have been compared with analogous phase diagrams reported previously for systems containing the IL N-butyl-4-methylpyridinium tosylate and other pyridinium-based ILs. The influence of the anion of the IL on the phase behavior has been discussed.

  16. Phase equilibria in carbon dioxide expanded solvents: Experiments and molecular simulations.

    PubMed

    Houndonougbo, Yao; Jin, Hong; Rajagopalan, Bhuma; Wong, Kean; Kuczera, Krzysztof; Subramaniam, Bala; Laird, Brian

    2006-07-06

    We present complementary molecular simulations and experimental results of phase equilibria for carbon dioxide expanded acetonitrile, methanol, ethanol, acetone, acetic acid, toluene, and 1-octene. The volume expansion measurements were done using a high-pressure Jerguson view cell. Molecular simulations were performed using the Gibbs ensemble Monte Carlo method. Calculations in the canonical ensemble (NVT) were performed to determine the coexistence curve of the pure solvent systems. Binary mixtures were simulated in the isobaric-isothermal distribution (NPT). Predictions of vapor-liquid equilibria of the pure components agree well with experimental data. The simulations accurately reproduced experimental data on saturated liquid and vapor densities for carbon dioxide, methanol, ethanol, acetone, acetic acid, toluene, and 1-octene. In all carbon dioxide expanded liquids (CXL's) studied, the molecular simulation results for the volume expansion of these binary mixtures were found to be as good as, and in many cases superior to, predictions based on the Peng-Robinson equation of state, demonstrating the utility of molecular simulation in the prediction of CXL phase equilibria.

  17. Pressure and phase equilibria in interacting active brownian spheres.

    PubMed

    Solon, Alexandre P; Stenhammar, Joakim; Wittkowski, Raphael; Kardar, Mehran; Kafri, Yariv; Cates, Michael E; Tailleur, Julien

    2015-05-15

    We derive a microscopic expression for the mechanical pressure P in a system of spherical active Brownian particles at density ρ. Our exact result relates P, defined as the force per unit area on a bounding wall, to bulk correlation functions evaluated far away from the wall. It shows that (i) P(ρ) is a state function, independent of the particle-wall interaction; (ii) interactions contribute two terms to P, one encoding the slow-down that drives motility-induced phase separation, and the other a direct contribution well known for passive systems; and (iii) P is equal in coexisting phases. We discuss the consequences of these results for the motility-induced phase separation of active Brownian particles and show that the densities at coexistence do not satisfy a Maxwell construction on P.

  18. Phase equilibria in polymer blend thin films: a Hamiltonian approach.

    PubMed

    Souche, M; Clarke, N

    2009-12-28

    We propose a Hamiltonian formulation of the Flory-Huggins-de Gennes theory describing a polymer blend thin film. We then focus on the case of 50:50 polymer blends confined between antisymmetric walls. The different phases of the system and the transitions between them, including finite-size effects, are systematically studied through their relation with the geometry of the Hamiltonian flow in phase space. This method provides an easy and efficient way, with strong graphical insight, to infer the qualitative physical behavior of polymer blend thin films.

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

    NASA Technical Reports Server (NTRS)

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

    1972-01-01

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

  20. 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.

  1. 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.

  2. Ab Initio Study of Phase Equilibria in TiCx

    NASA Astrophysics Data System (ADS)

    Korzhavyi, P. A.; Pourovskii, L. V.; Hugosson, H. W.; Ruban, A. V.; Johansson, B.

    2002-01-01

    The phase diagram for the vacancy-ordered structures in the substoichiometric TiCx ( x = 0.5-1.0) has been established from Monte Carlo simulations with the long-range pair and multisite effective interactions obtained from ab initio calculations. Three ordered superstructures of vacancies ( Ti2C, Ti3C2, and Ti6C5) are found to be ground state configurations. Their stability has been verified by full-potential total energy calculations of the fully relaxed structures.

  3. TERNARY PHASE EQUILIBRIA IN TRANSITION METAL-BORON-CARBON-SILICON SYSTEMS. PART II. TERNARY SYSTEMS. VOLUME XVI. V-NB-C SYSTEM,

    DTIC Science & Technology

    Phase equilibria in the ternary system vanadium-niobium-carbon from 800C through the melting ranges of the cubic monocarbide solid solutions were...established on the basis of X-ray, melting point and metallographic studies. The phase equilibria above 1400C are presented in a three-dimensional...temperature-composition constitutional diagram, since the phase equilibria below 1400C were not thoroughly investigated due to kinetic problems. Vanadium

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

    NASA Astrophysics Data System (ADS)

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

    1989-02-01

    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.

  5. 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.

  6. 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.

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

    PubMed

    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.

  8. 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.

  9. Modeling the Thermodynamics of Mixed Organic-Inorganic Aerosols to Predict Water Activities and Phase Equilibria

    NASA Astrophysics Data System (ADS)

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

    2008-12-01

    Tropospheric aerosol particles contain mixtures of inorganic salts, acids, water, and a large variety of organic compounds. Interactions between these substances in liquid mixtures lead to discrepancies from ideal thermodynamic behavior. While the thermodynamics of aqueous inorganic systems at atmospheric temperatures are well established, little is known about the physicochemistry of mixed organic-inorganic particles. Salting-out and salting-in effects result from organic-inorganic interactions and are used to improve industrial separation processes. In the atmosphere, they may influence the aerosol phases. 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 substances compared to a single phase estimation. Moreover, the phases present in the aerosol define the reaction medium for heterogeneous and multiphase chemistry occurring in aerosol particles. A correct description of these phases is needed when gas- or cloud-phase reaction schemes are adapted to aerosols. Non-ideal thermodynamic behavior in mixtures is usually described by an expression for the excess Gibbs energy. We present the group-contribution model AIOMFAC (Aerosol Inorganic-Organic Mixtures Functional groups Activity Coefficients), which explicitly accounts for molecular interactions between solution constituents, both organic and inorganic, to calculate activities, chemical potentials and the total Gibbs energy of mixed systems. This model allows to compute vapor-liquid (VLE), liquid-liquid (LLE) and solid-liquid (SLE) equilibria within one framework. Focusing on atmospheric applications we considered eight different cations, five anions and a wide range of alcohols/polyols as organic compounds. With AIOMFAC, the activities of the components within an aqueous electrolyte solution are very well represented up to high ionic strength. We show that the semiempirical middle

  10. Transferable potentials for phase equilibria-coarse-grain description for linear alkanes.

    PubMed

    Maerzke, Katie A; Siepmann, J Ilja

    2011-04-07

    Coarse-grain potentials allow one to extend molecular simulations to length and time scales beyond those accesssible to atomistic representations of the interacting system. Since the coarse-grain potentials remove a large number of interaction sites and, hence, a large number of degrees of freedom, it is generally assumed that coarse-grain potentials are not transferable to different systems or state points (temperature and pressure). Here we apply lessons learned from the parametrization of transferable atomistic potentials to develop a systematic procedure for the parametrization of transferable coarse-grain potentials. In particular, we apply an iterative Boltzmann optimization for the determination of the bonded interactions for coarse-grain beads belonging to the same molecule and separated by one or two coarse-grain bonds and parametrize the nonbonded interactions by fitting to the vapor-liquid coexistence curves computed for selected molecules represented by the TraPPE-UA (transferable potentials for phase equilibria-united atom) force field. This approach is tested here for linear alkanes where parameters for C(3)H(7) end segments and for C(3)H(6) middle segments of the TraPPE-CG (transferable potentials for phase equilibria-coarse grain) force field are determined and it is shown that these parameters yield quite accurate vapor-liquid equilibria for neat n-hexane to n-triacontane and for the binary mixture of n-hexane and n-hexatriacontane. In addition, the position of the first peak in various radial distribution functions and the coordination number for the first solvation shell are well reproduced by the TraPPE-CG force field, but the first peaks are too high and narrow.

  11. Phase equilibria and solid state transformations in niobium-rich niobium-titanium-aluminum intermetallic alloys

    NASA Astrophysics Data System (ADS)

    Leonard, Keith John

    The phase equilibria and solid state transformations within seven Nb-rich Nb-Ti-Al alloys were investigated. The alloys ranged in composition between 15 and 40 at.% Al with Nb:Ti ratios of 1.5:1 to 4:1. Examination of the as-cast microstructures revealed that all alloys solidified from the beta phase field, with subsequent solid-state transformations occurring within four of the alloys during cooling. The range of primary beta phase solidification was determined to extend beyond the limits of previous liquidus projections. The high temperature beta phase field was verified in each alloy through quenching experiments. The beta phase exhibited B2 ordering at room temperature with the order-disorder transition temperatures increasing with Ti concentration. The site occupancy preferences within the beta phase were evaluated through the ALCHEMI technique, which determined that Ti substitution occurred for Nb on Nb sublattice sites with the degree of sublattice partitioning found to depend upon alloy composition. The phase equilibria and transformations that occurred within the alloys were explored over a complete range of temperatures, with experimental isotherms produced at 1400, 1100, 900 and 700°C. Formation of metastable O-Ti 2AlNb plates occurred within the 15 at.% Al alloys at 700°C, instead of the delta-Nb3Al phase due to the slow diffusion growth kinetics of the delta phase below 900°C. A new phase with a body centered tetragonal structure belonging to the I41/amd space group was discovered in the Nb-24Ti-40Al alloy below 1100°C. This phase formed as lamella with the gamma-TiAl phase from the beta solid solution at 900 and 700°C, and was also present following treatments at 1100 + 900, 1100 + 700°C and within material oil quenched from elevated temperatures. No correlation existed between this phase and either the r-TiAl2 phase, which also has the I41/amd structure, or the gamma1 phase, which was not observed within this work. The formation of a metastable

  12. Phase Equilibria of Water/CO2 and Water/n-Alkane Mixtures from Polarizable Models.

    PubMed

    Jiang, Hao; Economou, Ioannis G; Panagiotopoulos, Athanassios Z

    2017-02-16

    Phase equilibria of water/CO2 and water/n-alkane mixtures over a range of temperatures and pressures were obtained from Monte Carlo simulations in the Gibbs ensemble. Three sets of Drude-type polarizable models for water, namely the BK3, GCP, and HBP models, were combined with a polarizable Gaussian charge CO2 (PGC) model to represent the water/CO2 mixture. The HBP water model describes hydrogen bonds between water and CO2 explicitly. All models underestimate CO2 solubility in water if standard combining rules are used for the dispersion interactions between water and CO2. With the dispersion parameters optimized to phase compositions, the BK3 and GCP models were able to represent the CO2 solubility in water, however, the water composition in CO2-rich phase is systematically underestimated. Accurate representation of compositions for both water- and CO2-rich phases cannot be achieved even after optimizing the cross interaction parameters. By contrast, accurate compositions for both water- and CO2-rich phases were obtained with hydrogen bonding parameters determined from the second virial coefficient for water/CO2. Phase equilibria of water/n-alkane mixtures were also studied using the HBP water and an exponenial-6 united-atom n-alkanes model. The dispersion interactions between water and n-alkanes were optimized to Henry's constants of methane and ethane in water. The HBP water and united-atom n-alkane models underestimate water content in the n-alkane-rich phase; this underestimation is likely due to the neglect of electrostatic and induction energies in the united-atom model.

  13. Three-body interactions and solid-liquid phase equilibria: application of a molecular dynamics algorithm.

    PubMed

    Wang, Liping; Sadus, Richard J

    2006-09-01

    The effect of three-body interactions on the solid-liquid phase boundaries of argon, krypton, and xenon is investigated via a novel technique that combines both nonequilibrium and equilibrium molecular dynamics. The simulations involve the evaluation of two- and three-body forces using accurate two-body and three-body intermolecular potentials. The effect of three-body interactions is to substantially increase the coexistence pressure and to lower the densities of liquid and solid phases. Comparison with experiment indicates that three-body interactions are required to accurately determine the total pressure. In contrast to vapor-liquid phase equilibria, the relative contribution of three-body interactions to the freezing pressure exceeds the contribution of two-body interactions at all temperatures.

  14. Solid-liquid phase equilibria of the Gaussian core model fluid.

    PubMed

    Mausbach, Peter; Ahmed, Alauddin; Sadus, Richard J

    2009-11-14

    The solid-liquid phase equilibria of the Gaussian core model are determined using the GWTS [J. Ge, G.-W. Wu, B. D. Todd, and R. J. Sadus, J. Chem. Phys. 119, 11017 (2003)] algorithm, which combines equilibrium and nonequilibrium molecular dynamics simulations. This is the first reported use of the GWTS algorithm for a fluid system displaying a reentrant melting scenario. Using the GWTS algorithm, the phase envelope of the Gaussian core model can be calculated more precisely than previously possible. The results for the low-density and the high-density (reentrant melting) sides of the solid state are in good agreement with those obtained by Monte Carlo simulations in conjunction with calculations of the solid free energies. The common point on the Gaussian core envelope, where equal-density solid and liquid phases are in coexistence, could be determined with high precision.

  15. Phase equilibria of the system methane-ethane from temperature scaling Gibbs Ensemble Monte Carlo simulation

    NASA Astrophysics Data System (ADS)

    Zhang, Zhigang; Duan, Zhenhao

    2002-10-01

    A new technique of temperature scaling method combined with the conventional Gibbs Ensemble Monte Carlo simulation was used to study liquid-vapor phase equilibria of the methane-ethane (CH 4-C 2H 6) system. With this efficient method, a new set of united-atom Lennard-Jones potential parameters for pure C 2H 6 was found to be more accurate than those of previous models in the prediction of phase equilibria. Using the optimized potentials for liquid simulations (OPLS) potential for CH 4 and the potential of this study for C 2H 6, together with a simple mixing rule, we simulated the equilibrium compositions and densities of the CH 4-C 2H 6 mixtures with accuracy close to experiments. The simulated data are supplements to experiments, and may cover a larger temperature-pressure-composition space than experiments. Compared with some well-established equations of state such as Peng-Robinson equation of state (PR-EQS), the simulated results are found to be closer to experiments, at least in some temperature and pressure ranges.

  16. 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.

  17. PHASE EQUILIBRIA INVESTIGATIONS OF BINARY, TERNARY, AND HIGHER ORDER SYSTEMS. PART 2. EFFECT OF RHENIUM AND ALUMINUM ADDITIONS ON THE METAL-RICH EQUILIBRIA IN THE TITANIUM-MOLYBDENIUM-CARBON AND TITANIUM-NIOBIUM-CARBON SYSTEMS

    DTIC Science & Technology

    The solid state phase equilibria of the metal-rich regions of the Titanium-Molybdenum-Carbon and Titanium-Niobium-Carbon systems with up to 12 At...Rhenium and 10 At.% Aluminum additions, respectively, have been determined on hot pressed, heat treated, and in part arc melted alloys. The phase ... equilibria in the metal-rich regions, with these additions, is practically unchanged over that of the ternary Titanium-Molybdenum-Carbon and Titanium

  18. 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).

  19. Advantages of ion-based mole fractions for describing phase equilibria in ionic liquids: application to gas solubility.

    PubMed

    Longinotti, María Paula; Alvarez, Jorge L; Japas, M Laura

    2009-03-19

    Despite the obvious ionic character of ionic liquids (ILs), previous studies of phase equilibria in these media were formulated implicitly assuming a "molecular" behavior of the ionic solvent. In this work, a more appropriate thermodynamic treatment is applied to describe the solubility of gases in ILs. According to our results, if the concentration is expressed on an ionic basis, solutions of simple gases in ILs display rather small deviations from ideal behavior in wide composition ranges, whereas deviations are larger when the solvent is considered as an anion-cation pair. The present thermodynamic formulation also accounts for the observed solid-liquid phase equilibria of molecular and IL binary mixtures.

  20. Phase Equilibria and Transition in Mixtures of a Homopolymer and a Block Copolymer. I. Small-Angle X-Ray Scattering Study.

    DTIC Science & Technology

    1983-03-08

    AA2588 PHASE EQUILIBRIA AND TRANSITION IN MIXTURES OF A I HOMOPOLYMER AND A BLOCK..(U) CINCINNATI UNIV OH DEPT OF SMATERIALS SCIENCE AND.METALLURGICA...OFFICE OF NAVAL RESEARCH Contract N00014-77-C-0376 Task No. NR 356-655 TECHNICAL REPORT NO. 8 Phase Equilibria and Transition in Mixtures of a

  1. Exact calculations of phase and membrane equilibria for complex fluids by Monte Carlo simulation

    SciTech Connect

    Panagiotopoulos, A.Z.

    1990-08-28

    The general objective of this project is the investigation of phase equilibria for complex fluids using a novel methodology, Monte Carlo simulation in the Gibbs ensemble. The methodology enables the direct determination of the properties of two coexisting fluid phases (e.g. a liquid at equilibrium with its vapor) from a single computer experiment, and is applicable to multicomponent systems with arbitrary equilibrium constraints imposed. The specific goals of this work are to adapt the Gibbs technique to (a) highly asymmetric mixtures with large differences in size and potential energies of interaction (b) chain molecules and (c) ionic systems. Significant progress has been made in all three areas. In this paper, we will briefly describe the progress made in each area, using the same numbering scheme for the tasks as in the original proposal.

  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

    2017-02-01

    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 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.

  4. Planetary phase equilibria - Application to formation of earth, Venus and Mercury

    NASA Technical Reports Server (NTRS)

    Saxena, S. K.

    1981-01-01

    Calculations of phase equilibria in a solar mixture with variable hydrogen abundance show that the major element chemical composition of the earth and Venus can be simply explained by their formation in equilibrium at 800 and 1000 K, respectively, at a pressure of 0.001 atm, provided that there is an iron loss from the region of proto-Venus relative to the solar nebula. The calculated mineralogical chemical compositions of the two planets are in excellent agreement with the available chemical and physical data. Phase equilibrium calculations at 1500 K and 0.001 atm show that nearly 96% of the silicates and 81% of metal must have been lost from the region of proto-Mercury.

  5. Hydration energies of deprotonated amino acids from gas phase equilibria measurements.

    PubMed

    Wincel, Henryk

    2008-08-01

    Singly hydrated clusters of deprotonated amino acids were studied using an electrospray high-pressure mass spectrometer equipped with a pulsed ion-beam reaction chamber. Thermochemical data, DeltaH(o), DeltaS(o), and DeltaG(o), for the hydration reaction [AA - H](-) + H(2)O = [AA - H](-).(H(2)O) were obtained from gas-phase equilibria determinations for AA = Gly, Ala, Val, Pro, Phe, Lys, Met, Trp, Gln, Arg, and Asp. The hydration free-energy changes are found to depend significantly on the side-chain substituents. The water binding energy in [AA - H](-).(H(2)O) increases with the gas-phase acidity of AA. The anionic hydrogen bond strengths in [AA - H](-).(H(2)O) are compared with those of the cationic bonds in the corresponding AAH(+).(H(2)O) systems.

  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. 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.

  8. Exploring fluctuations and phase equilibria in fluid mixtures via Monte Carlo simulation

    NASA Astrophysics Data System (ADS)

    Denton, Alan R.; Schmidt, Michael P.

    2013-03-01

    Monte Carlo simulation provides a powerful tool for understanding and exploring thermodynamic phase equilibria in many-particle interacting systems. Among the most physically intuitive simulation methods is Gibbs ensemble Monte Carlo (GEMC), which allows direct computation of phase coexistence curves of model fluids by assigning each phase to its own simulation cell. When one or both of the phases can be modelled virtually via an analytic free energy function (Mehta and Kofke 1993 Mol. Phys. 79 39), the GEMC method takes on new pedagogical significance as an efficient means of analysing fluctuations and illuminating the statistical foundation of phase behaviour in finite systems. Here we extend this virtual GEMC method to binary fluid mixtures and demonstrate its implementation and instructional value with two applications: (1) a lattice model of simple mixtures and polymer blends and (2) a free-volume model of a complex mixture of colloids and polymers. We present algorithms for performing Monte Carlo trial moves in the virtual Gibbs ensemble, validate the method by computing fluid demixing phase diagrams, and analyse the dependence of fluctuations on system size. Our open-source simulation programs, coded in the platform-independent Java language, are suitable for use in classroom, tutorial, or computational laboratory settings.

  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. 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).

  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. 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.

  14. Phase equilibria in the ternary In–Ni–Sn system at 700 °C

    PubMed Central

    Schmetterer, C.; Zemanova, A.; Flandorfer, H.; Kroupa, A.; Ipser, H.

    2013-01-01

    The phase equilibria of the ternary system In–Ni–Sn were investigated experimentally at 700 °C using X-ray diffraction (XRD) and scanning electron microscopy (SEM) including electron micro probe analysis (EMPA) and energy dispersive X-ray spectroscopy (EDX). A corresponding isothermal section was established based on these results. This particular temperature was chosen because it allowed obtaining reliable results within reasonable time. The existence of the ternary phase InNi6Sn5 was confirmed whereas the ternary compound In2NiSn, reported earlier in literature, was found to be part of a large solid solution field based on binary InNi. The ternary solubility of the binary phases was established, and continuous solid solutions were found between the isostructural phases Ni3Sn LT and InNi3 as well as between Ni3Sn2 HT and InNi2. In addition, this isothermal section could be well reproduced by CALPHAD modelling. The resulting calculated isotherm at 700 °C is presented, too, and compared with the experimental results. PMID:27087756

  15. Monte Carlo calculation of phase equilibria for a bead-spring polymeric model

    SciTech Connect

    Sheng, Y.J.; Panagiotopoulos, A.Z. . School of Chemical Engineering); Kumar, S.K. . Dept. of Materials Science and Engineering); Szleifer, I. )

    1994-01-17

    Vapor-liquid phase diagrams for a bead-spring polymeric model have been calculated for chain lengths of 20, 50, and 100 from Monte Carlo simulations using the recently proposed chain increment method to determine the chain chemical potentials. Densities of both phases at coexistence and vapor pressures were obtained directly for a range of temperatures from highly subcritical to the vicinity of the critical point, and the critical temperature and density for each chain length were obtained by extrapolation. They also calculated the second virial coefficients for chain-chain interactions of the model and found that the temperature at which the second virial coefficients for chain-chain interactions of the model and found that the temperature at which the second virial coefficient vanishes for long chains coincides, within computational uncertainty, with the infinite chain length critical point from the phase equilibrium results. At the critical points of the finite length chains the second virial coefficient assume negative values, indicating attractive interchain interactions. The radius of gyration of chains of varying length was also determined and the [theta] temperature obtained from the radii of gyration found to coincide, within computational uncertainty, with the critical point for an infinite chain length polymer. The computational methodology they utilize can be extended to the calculation of phase equilibria in multicomponent polymer/solvent systems.

  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 in the ternary In-Ni-Sn system at 700 °C.

    PubMed

    Schmetterer, C; Zemanova, A; Flandorfer, H; Kroupa, A; Ipser, H

    2013-04-01

    The phase equilibria of the ternary system In-Ni-Sn were investigated experimentally at 700 °C using X-ray diffraction (XRD) and scanning electron microscopy (SEM) including electron micro probe analysis (EMPA) and energy dispersive X-ray spectroscopy (EDX). A corresponding isothermal section was established based on these results. This particular temperature was chosen because it allowed obtaining reliable results within reasonable time. The existence of the ternary phase InNi6Sn5 was confirmed whereas the ternary compound In2NiSn, reported earlier in literature, was found to be part of a large solid solution field based on binary InNi. The ternary solubility of the binary phases was established, and continuous solid solutions were found between the isostructural phases Ni3Sn LT and InNi3 as well as between Ni3Sn2 HT and InNi2. In addition, this isothermal section could be well reproduced by CALPHAD modelling. The resulting calculated isotherm at 700 °C is presented, too, and compared with the experimental results.

  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

    2010-05-06

    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. 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

    2016-12-01

    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.

  20. 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

  1. Phase equilibria and liquid phase epitaxy growth of PbSnSeTe lattice matched to PbSe

    NASA Technical Reports Server (NTRS)

    Mccann, Patrick J.; Fonstad, Clifton G.; Fuchs, Jacob; Feit, Ze'ev

    1987-01-01

    The necessary phase diagram data for growing lattice-matched layers of PbSnSeTe on PbSe are presented. Solid compounds of Pb(1-x)Sn(x)Se(1-y)Te(y) lattice-matched to PbSe were grown from liquid melts consisting of (Pb/1-x/Sn/x/)(1-z)(Se/1-y/Te/y/)(z); phase equilibria data were determined together with liquidus data for values of x(liquid) from 0 to 40 percent and y(liquid) from 0 to 40 percent for temperatures between 450 and 540 C. It was found that relatively large amounts of Te must be added to the melt to achieve lattice matching because of its low segregation coefficient relative to Se. A significant lattice-pulling effect was discovered for the 5-percent Sn case, and a similar effect is expected for the 10- and 20-percent Sn cases.

  2. 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

  3. Solid-Phase Equilibria in the Au-As, Au-Ga-Sb, Au-In-As, and Au-In-Sb Ternaries.

    DTIC Science & Technology

    1986-02-28

    AD6i5 469 SOLID- PHASE EQUILIBRIA IN THE Ru-As AU-GA-SB AU-IN-AS- 1/17 AND AU-IN-SB TERNAR (U) CALIFORNIA UNIV LOS ANGELES DEPT OF CHEMISTRY AND...REPORT & PERIOD COVERED SOLID- PHASE EQUILIBRIA IN THE Au-Ga-As, Au-Ga-Sb Thchnical Report Au-In-As, and Au-In-Sb TEARIEIS S. PERFORMING ORG. REPORT NUMBER...CLASSIFICATION OF THIS PAGEMI*n Does Entepd) 4./ lie- . .- - - - - -- -- Solid Phase Equilibria in the Au-Ga-As, Au-Ga-Sb, Au-In-As, and Au-In-Sb Ternaries C

  4. 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.

  5. Phase Equilibria of Sn-Sb-Ag Ternary System (II): Calculation

    NASA Astrophysics Data System (ADS)

    Gierlotka, Wojcieh; Huang, Yu-Chih; Chen, Sinn-Wen

    2008-12-01

    Knowledge of the phase equilibria of the Sn-Sb-Ag ternary system is of fundamental importance in Sn-Sb-based solder applications. Thermodynamic models of the ternary Sn-Sb-Ag system and the binary Sb-Ag and Sn-Ag systems are developed using the calculation of phase diagrams (CALPHAD) method. The calculated 250 °C isothermal section, liquidus projection, and thermodynamic properties are in good agreement with the experimental results. There are two continuous solid solutions formed between the ɛ-Ag3Sn and ɛ-Ag3Sb, and ζ-Ag17Sb3 and ζ-Ag5Sn phases, but there is no ternary compound. There are three class II ternary invariant reactions, L + Sb ↔ ɛ + β-SnSb, L + β-SnSb ↔ Sn3Sb2 + ɛ, and L + Sn3Sb2 ↔ Sn + ɛ. Their reaction temperatures are 379 °C, 313 °C, and 231 °C, respectively.

  6. In y Co4Sb12 Skutterudite: Phase Equilibria and Crystal Structure

    NASA Astrophysics Data System (ADS)

    Grytsiv, A.; Rogl, P.; Michor, H.; Bauer, E.; Giester, G.

    2013-10-01

    Phase relations were investigated for the In-Co-Sb system in the temperature range from 375°C to 800°C using as-cast and annealed alloys. Phase equilibria in the CoSb-InSb-(Sb) composition triangle are presented by a series of isothermal sections and solidus and liquidus surfaces, accompanied by a Schulz-Scheil reaction scheme. The indium-filled skutterudite In y Co4Sb12 already forms an equilibrium with liquid at 484°C, which might limit high-temperature applications of In-Co-Sb-based skutterudites. The maximal solubility of indium in In y Co4Sb12 ( y = 0.22) remains almost constant in the temperature range from 475°C to 700°C and corresponds to the equilibrium with CoSb2 and InSb. The solubility of indium in the skutterudite phase is reduced to y = 0.09 when it coexists in equilibrium with InSb and (Sb), and this decrease of the solubility might be responsible for the formation of InSb precipitates. Temperature-dependent x-ray single-crystal and specific heat data for In y Co4Sb12 were employed to determine the rattling behavior of In atoms in the skutterudite lattice.

  7. Processing, phase equilibria and environmental degradation of molybdenum (silicom,aluminum)(2) intermetallic compound

    NASA Astrophysics Data System (ADS)

    Eason, Paul Duane

    The Mo(Si,Al)2 C40 compound was chosen for investigation as a possible high temperature structural material. To produce the C40 phase, several processing routes were explored with emphasis on obtaining microstructure/property relationships (i.e. control of grain size and minimization of secondary phases). To facilitate processing of single phase material, the phase equilibria of the Mo-Si-Al ternary system were reevaluated with respect to the phases adjacent to the C40 compound. An anomalous environmental degradation appeared to be the primary obstacle to further study of the compound and was investigated accordingly. Several processing routes were assessed for the production of dense, nearly single-phase Mo(Si,Al)2. Hot powder compaction was chosen as the method of sample production as is the case with many refractory silicide based materials. Therefore, variations in the processing techniques came from the choice of precursor materials and methods of powder production. Mechanical alloying, arc-melting and comminution, and blending of both elemental and compound powders were all employed to produce charges for hot uniaxial pressing. The final compacts were compared on the basis of density, grain size and presence of secondary phases. Establishment of a Mo-Si-Al ternary isothermal phase diagram at 1400°C was performed. Multiphase alloy compositions were selected to identify the phase boundaries of the C40, C54, T1 and Mo3Al8 phase fields, as well as to verify the existence of the C54 phase at 1400°C. The alloys were equilibrated by heat treatment and analyzed for phase identification and quantitative compositional information. The environmental degradation phenomenon was approached as a classical "pest" with an emphasis of study on grain boundary chemistry and atmospheric dependence of attack. Both Auger spectroscopy and electron microscopy revealed carbon-impurity-induced grain boundary segregation responsible for the embrittlement and material loss. Means of

  8. Isotropic-nematic phase equilibria of hard-sphere chain fluids-Pure components and binary mixtures.

    PubMed

    Oyarzún, Bernardo; van Westen, Thijs; Vlugt, Thijs J H

    2015-02-14

    The isotropic-nematic phase equilibria of linear hard-sphere chains and binary mixtures of them are obtained from Monte Carlo simulations. In addition, the infinite dilution solubility of hard spheres in the coexisting isotropic and nematic phases is determined. Phase equilibria calculations are performed in an expanded formulation of the Gibbs ensemble. This method allows us to carry out an extensive simulation study on the phase equilibria of pure linear chains with a length of 7 to 20 beads (7-mer to 20-mer), and binary mixtures of an 8-mer with a 14-, a 16-, and a 19-mer. The effect of molecular flexibility on the isotropic-nematic phase equilibria is assessed on the 8-mer+19-mer mixture by allowing one and two fully flexible beads at the end of the longest molecule. Results for binary mixtures are compared with the theoretical predictions of van Westen et al. [J. Chem. Phys. 140, 034504 (2014)]. Excellent agreement between theory and simulations is observed. The infinite dilution solubility of hard spheres in the hard-sphere fluids is obtained by the Widom test-particle insertion method. As in our previous work, on pure linear hard-sphere chains [B. Oyarzún, T. van Westen, and T. J. H. Vlugt, J. Chem. Phys. 138, 204905 (2013)], a linear relationship between relative infinite dilution solubility (relative to that of hard spheres in a hard-sphere fluid) and packing fraction is found. It is observed that binary mixtures greatly increase the solubility difference between coexisting isotropic and nematic phases compared to pure components.

  9. Isotropic-nematic phase equilibria of hard-sphere chain fluids—Pure components and binary mixtures

    NASA Astrophysics Data System (ADS)

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

    2015-02-01

    The isotropic-nematic phase equilibria of linear hard-sphere chains and binary mixtures of them are obtained from Monte Carlo simulations. In addition, the infinite dilution solubility of hard spheres in the coexisting isotropic and nematic phases is determined. Phase equilibria calculations are performed in an expanded formulation of the Gibbs ensemble. This method allows us to carry out an extensive simulation study on the phase equilibria of pure linear chains with a length of 7 to 20 beads (7-mer to 20-mer), and binary mixtures of an 8-mer with a 14-, a 16-, and a 19-mer. The effect of molecular flexibility on the isotropic-nematic phase equilibria is assessed on the 8-mer+19-mer mixture by allowing one and two fully flexible beads at the end of the longest molecule. Results for binary mixtures are compared with the theoretical predictions of van Westen et al. [J. Chem. Phys. 140, 034504 (2014)]. Excellent agreement between theory and simulations is observed. The infinite dilution solubility of hard spheres in the hard-sphere fluids is obtained by the Widom test-particle insertion method. As in our previous work, on pure linear hard-sphere chains [B. Oyarzún, T. van Westen, and T. J. H. Vlugt, J. Chem. Phys. 138, 204905 (2013)], a linear relationship between relative infinite dilution solubility (relative to that of hard spheres in a hard-sphere fluid) and packing fraction is found. It is observed that binary mixtures greatly increase the solubility difference between coexisting isotropic and nematic phases compared to pure components.

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

    PubMed

    Tsuchiya, Jun; Tsuchiya, Taku

    2008-12-09

    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.

  11. New Computational Approach to Determine Liquid-Solid Phase Equilibria of Water Confined to Slit Nanopores.

    PubMed

    Kaneko, Toshihiro; Bai, Jaeil; Yasuoka, Kenji; Mitsutake, Ayori; Zeng, Xiao Cheng

    2013-08-13

    We devise a new computational approach to compute solid-liquid phase equilibria of confined fluids. Specifically, we extend the multibaric-multithermal ensemble method with an anisotropic pressure control to achieve the solid-liquid phase equilibrium for confined water inside slit nanopores (with slit width h ranging from 5.4 Å to 7.2 Å). A unique feature of this multibaric-multithermal ensemble is that the freezing points of confined water can be determined from the heat-capacity peaks. The new approach has been applied to compute the freezing point of two monolayer ices, namely, a high-density flat rhombic monolayer ice (HD-fRMI) and a high-density puckered rhombic monolayer ice (HD-pRMI) observed in our simulation. We find that the liquid-to-solid transition temperature (or the freezing point) of HD-pRMI is dependent on the slit width h, whereas that of HD-fRMI is nearly independent of the h.

  12. Phase equilibria and modeling of ammonium ionic liquid, C2NTf2, solutions.

    PubMed

    Domańska, Urszula; Marciniak, Andrzej; Królikowski, Marek

    2008-01-31

    Novel quaternary ammonium ionic liquid, ethyl(2-hydroxyethyl)dimethylammonium bis(trifluomethylsulfonyl)imide (C2NTf2), has been prepared from N,N-dimethylethanolamine as a substrate. The paper includes a specific basic characterization of the synthesized compound by NMR and the basic thermophysical properties: the melting point, enthalpy of fusion, enthalpy of solid-solid phase transition, glass transition determined by the differential scanning calorimetry (DSC), temperature of decomposition, and water content. The density of the new compound was measured. The solid-liquid or liquid-liquid phase equilibria of binary mixtures containing {C2NTf2+water or an alcohol (propan-1-ol, butan-1-ol, hexan-1-ol, octan-1-ol, decan-1-ol), aromatic hydrocarbons (benzene, toluene), aliphatic hydrocarbons (n-hexane, n-octane), dimethylsulfoxide (DMSO), or tetrahydrofuran (THF)} have been measured by a dynamic method in a wide range of temperatures from 230 to 430 K. These data were correlated by means of the nonrandom two-liquid (NRTL) equation utilizing temperature-dependent parameters derived from the solid-liquid or liquid-liquid equilibrium. From the solubility results, the negative value of the partition coefficient of ionic liquid in binary system octan-1-ol/water (log P) at 298.15 K has been calculated.

  13. 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

  14. 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.

  15. Phase equilibria of molecular fluids via hybrid Monte Carlo Wang-Landau simulations: applications to benzene and n-alkanes.

    PubMed

    Desgranges, Caroline; Delhommelle, Jerome

    2009-06-28

    In recent years, powerful and accurate methods, based on a Wang-Landau sampling, have been developed to determine phase equilibria. However, while these methods have been extensively applied to study the phase behavior of model fluids, they have yet to be applied to molecular systems. In this work, we show how, by combining hybrid Monte Carlo simulations in the isothermal-isobaric ensemble with the Wang-Landau sampling method, we determine the vapor-liquid equilibria of various molecular fluids. More specifically, we present results obtained on rigid molecules, such as benzene, as well as on flexible chains of n-alkanes. The reliability of the method introduced in this work is assessed by demonstrating that our results are in excellent agreement with the results obtained in previous work on simple fluids, using either transition matrix or conventional Monte Carlo simulations with a Wang-Landau sampling, and on molecular fluids, using histogram reweighting or Gibbs ensemble Monte Carlo simulations.

  16. First-order mean-spherical approximation for interfacial phenomena: a unified method from bulk-phase equilibria study.

    PubMed

    Tang, Yiping

    2005-11-22

    The recently proposed first-order mean-spherical approximation (FMSA) [Y. Tang, J. Chem. Phys. 121, 10605 (2004)] for inhomogeneous fluids is extended to the study of interfacial phenomena. Computation is performed for the Lennard-Jones fluid, in which all phase equilibria properties and direct correlation function for density-functional theory are developed consistently and systematically from FMSA. Three functional methods, including fundamental measure theory for the repulsive force, local-density approximation, and square-gradient approximation, are applied in this interfacial investigation. Comparisons with the latest computer simulation data indicate that FMSA is satisfactory in predicting surface tension, density profile, as well as relevant phase equilibria. Furthermore, this work strongly suggests that FMSA is very capable of unifying homogeneous and inhomogeneous fluids, as well as those behaviors outside and inside the critical region within one framework.

  17. 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.

  18. Clathrate formation and phase equilibria in the thiourea-bromoform system

    NASA Astrophysics Data System (ADS)

    Chekhova, G. N.; Shubin, Yu. V.; Pinakov, D. V.; Alferova, N. I.

    2008-07-01

    Phase equilibria in the thiourea (host)-bromoform (guest) binary system were studied by physicochemical analysis methods over the temperature range 270 455 K. The stoichiometry and stability region were determined for the channel-type compound CHBr3 · 2.40(2)(NH2)2CS; the compound was observed for the first time. When heated, the clathrate incongruently decomposed at 424.0 ± 0.8 K to rhombic thiourea and the guest component. The solubility isotherm of the thiourea-bromoform-acetic acid system was studied to find that the compound was thermodynamically stable at 293 K over the range of guest component concentrations 100 35 wt %. A decrease in its content in an equilibrium mother liquor resulted in the appearance of X-ray diffraction reflections of the initial host α polymorph. Rhombohedral cell parameters were determined (space group R-3 c, a = 15.89(1) Å, c = 12.40(1) Å, V = 2711(6) Å3, d calcd = 2.000 g/cm3, and d expt = 1.98(2) g/cm3). The mode of packing of bromoform molecules was compared with the organization of the guest subsystem in inclusion compounds formed by the substances studied.

  19. Phase equilibria of haloalkanes dissolved in ethylsulfate- or ethylsulfonate-based ionic liquids.

    PubMed

    Deive, Francisco J; Rodríguez, Ana; Pereiro, Ana B; Shimizu, Karina; Forte, Paulo A S; Romão, Carlos C; Canongia Lopes, José N; Esperança, José M S S; Rebelo, Luís P N

    2010-06-03

    The temperature-composition phase diagrams of 40 binary mixtures composed of a haloalkane dissolved in either 1-ethyl-3-methylimidazolium ethylsulfate or 1-ethyl-3-methylimidazolium ethylsulfonate were measured from ambient temperature to the boiling point temperature of the solute. The coexistence curves corresponding to liquid-liquid equilibria (LLE) boundaries were visually determined and the experimental results have been correlated using either the nonrandom two-liquid (NRTL) model or a set of empirical equations capable of describing the corresponding upper critical solution temperatures (UCSTs) loci. The different types of LLE behavior were discussed in terms of the type of ionic liquid solvent, the alkyl-chain length of the solute, and the type and pattern of halogen substitution present in the haloalkane. Auxiliary simulation data (obtained by ab initio or by molecular dynamics methods) were used to corroborate some of the experimental findings. Also, they correlate in a semiquantitative way the observed LLE behavior with the dipole moments of the different solutes.

  20. 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.

  1. Mussel bed boundaries as dynamic equilibria: thresholds, phase shifts, and alternative states.

    PubMed

    Donahue, Megan J; Desharnais, Robert A; Robles, Carlos D; Arriola, Patricia

    2011-11-01

    Ecological thresholds are manifested as a sudden shift in state of community composition. Recent reviews emphasize the distinction between thresholds due to phase shifts-a shift in the location of an equilibrium-and those due to alternative states-a switch between two equilibria. Here, we consider the boundary of intertidal mussel beds as an ecological threshold and demonstrate that both types of thresholds may exist simultaneously and in close proximity on the landscape. The discrete lower boundary of intertidal mussel beds was long considered a fixed spatial refuge from sea star predators; that is, the upper limit of sea star predation, determined by desiccation tolerance, fixed the lower boundary of the mussel bed. However, recent field experiments have revealed the operation of equilibrium processes that maintain the vertical position of these boundaries. Here, we cast analytical and simulation models in a landscape framework to show how the discrete lower boundary of the mussel bed is a dynamic predator-prey equilibrium, how the character of that boundary depends on its location in the landscape, and how boundary formation is robust to the scale of local interactions.

  2. Liquid-Liquid Phase Equilibria and Interactions between Droplets in Water-in-Oil Microemulsions.

    PubMed

    Yin, Tianxiang; Wang, Mingjie; Tao, Xiaoyi; Shen, Weiguo

    2016-12-20

    The liquid-liquid phase equilibria of [water/sodium bis(2-ethylhexyl)sulfosuccinate (AOT)/n-decane] with the molar ratio w0 of water to AOT being 37.9 and [water/AOT/ethoxylated-2,5,8,11-tetramethyl-6-dodecyne-5,8-diol(Dynol-604)/n-decane] with w0 = 37.9 and the mole fraction α of Dynol-604 in the total surfactants being 0.158 were measured in this study. From the data collected in the critical region, the critical exponent β corresponding to the width of the coexistence curve was determined, which showed good agreement with the 3D-Ising value. A thermodynamic approach based on the Carnahan-Starling-van der Waals type equation was proposed to describe the coexistence curves and to deduce the interaction properties between droplets in the microemulsions. The interaction enthalpies were found to be positive for the studied systems, which evidenced that the entropy effect dominated the phase separations as the temperature increased. The addition of Dynol-604 into the (water/AOT/n-decane) microemulsion resulted in the decrease in the critical temperature and the interaction enthalpy. Combining the liquid-liquid equilibrium data for (water/AOT/n-decane) microemulsions with various w0 values determined previously, it was shown that the interaction enthalpy decreased with w0 and tended to change its sign at low w0, which coincided with the results from the isothermal titration calorimetry investigation. All of these behaviors were interpreted by the effects of entropy and enthalpy and their competition, which resulted from the release of solvent molecules entrapped in the interface of microemulsion droplets and were dependent on the rigidity of the surfactant layers and the size of the droplet.

  3. 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 Bi2Sr2CaCu2O8 (Bi2212) melt and the details of the peritectic decomposition pathway of Bi2212 as a function on Ag content and oxygen partial pressure (PO2). 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 PO2 range studied. The stability of these solid phases were found to be highly sensitive to PO2, 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 (Al2O3) and time resolved phase transformation studies (SrCO3). Finally, the Bi2212

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

    PubMed

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

    2011-11-01

    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.

  5. 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

  6. Olivine-wadsleyite-ringwoodite phase equilibria in (Mg,Fe)2SiO4 from first-principles calculations

    NASA Astrophysics Data System (ADS)

    Yu, Y. G.; Vinograd, V. L.; Winkler, B.; Wentzcovitch, R. M.

    2012-12-01

    Phase equilibria of α , β , and γ (Mg,Fe)2SiO4 are important to understanding the mineralogy of the Earth's upper mantle. Here using the first principles approach, we studied thermodynamic properties and phase stability fields of Fe2SiO4. We show that the correct phase transition sequence in Fe2SiO4 (α -> γ ) can be obtained with the DFT + self-consistent Hubbard U method, while standard DFT methods (LSDA and σ -GGA) as well as the DFT + constant U method fail the task. The vibrational virtual crystal approximation was used to derive the phonon density of state of the Fe2SiO4 polymorphs. High-pressures thermodynamic properties of Fe2SiO4 are then derived with the aid of the quasi-harmonic approximation. They are in very good agreement with experiments. The phase diagram of (Mg,Fe)2SiO4 system is calculated under the assumption of ideal mixing within α , β , and γ solid solutions. The model permits the investigation of the temperature and pressure effects on the phase boundaries. The widths of the divariant α -β and β -γ loops are barely sensitive to the temperature changes within the range of 1473--1873 K. This study shows the promise of applying the DFT + self-consistent Hubbard U method to study phase equilibria of iron-bearing Earth minerals.

  7. Phase equilibria and structural investigations in the system Al-Fe-Si.

    PubMed

    Marker, Martin C J; Skolyszewska-Kühberger, Barbara; Effenberger, Herta S; Schmetterer, Clemens; Richter, Klaus W

    2011-12-01

    The Al-Fe-Si system was studied for an isothermal section at 800 °C in the Al-rich part and at 900 °C in the Fe-rich part, and for half a dozen vertical sections at 27, 35, 40, 50 and 60 at.% Fe and 5 at.% Al. Optical microscopy and powder X-ray diffraction (XRD) was used for initial sample characterization, and Electron Probe Microanalysis (EPMA) and Scanning Electron Microscopy (SEM) of the annealed samples was used to determine the exact phase compositions. Thermal reactions were studied by Differential Thermal Analysis (DTA). Our experimental results are generally in good agreement with the most recent phase diagram versions of the system Al-Fe-Si. A new ternary high-temperature phase τ12 (cF96, NiTi2-type) with the composition Al48Fe36Si16 was discovered and was structurally characterized by means of single-crystal and powder XRD. The variation of the lattice parameters of the triclinic phase τ1 with the composition Al2+x Fe3Si3-x (-0.3 < x < 1.3) was studied in detail. For the binary phase FeSi2 only small solubility of Al was found in the low-temperature modification LT-FeSi2 (ζβ ) but significant solubility in the high-temperature modification HT-FeSi2 (ζα ) (8.5 at.% Al). It was found that the high-temperature modification of FeSi2 is stabilized down to much lower temperature in the ternary, confirming earlier literature suggestions on this issue. DTA results in four selected vertical sections were compared with calculated sections based on a recent CALPHAD assessment. The deviations of liquidus values are significant suggesting the need for improvement of the thermodynamic models.

  8. Thermodynamics and phase equilibria involving nano phases in the Cu-Ag system.

    PubMed

    Hajra, J P; Acharya, S

    2004-09-01

    The surface tensions of the Cu-Ag system have been evaluated using Butler's equations. Since the evaluation is dependent on the thermodynamic properties of the surface phases, they are calculated based on the first and second order differentials of the surface tension at infinite dilution. The present study establishes significant differences in the properties between the surface phase and bulk phases of the system. The study of the adsorption behaviour finds silver to be surface active relative to copper, which results in the preferential adsorption of silver in the alloys. Furthermore, in view of the differences in terms of fundamental thermodynamic properties between the two phases coupled with the volume-to-radius ratio as depicted by the Thomson-Freundlich concept, the nano phases of the system exhibit a pronounced increase in the adsorption behaviour relative to that of the planar interface of the system. As expected based on the above combined effect of the surface properties, present research shows a considerable decrease in the melting points of the metals, solid-solid, solid-liquid transition and eutectic temperature with a consequent increase in the solubilities of the terminal phases of the system.

  9. 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.

  10. 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

  11. 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.

  12. 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.

  13. 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.

  14. Thermodynamic modeling of phase equilibria in magmatic systems: Progress and future directions (Robert Wilhelm Bunsen Medal Lecture)

    NASA Astrophysics Data System (ADS)

    Ghiorso, Mark S.

    2010-05-01

    Research over the past thirty years has established that thermodynamic modeling is extremely useful for illuminating the production, transport, chemical differentiation, and eruptive potential of magmas. The key to successful modeling of this kind is the formulation of an internally consistent thermodynamic database that includes properties of liquid and solid endmember components, and - most importantly - a cohesive set of models that describe the thermodynamics of mixing of both liquid (± fluid) and mineral solid solutions. Despite numerous successes in the application of thermodynamic modeling to liquid-solid phase equilibria under crustal and upper mantle pressure-temperature conditions, there are critical and relevant areas of application where the models fail to generate useful results. Importantly, these applications include phase equilibria in hornblende- and biotite-bearing magmas and the melting relations of silicate mantle-like bulk compositions at pressures above 3 GPa. Research is underway to address many of these modeling deficiencies. Approaches include (1) the development of new solution models for igneous pyroxenes and garnets, including majoritic garnet components, (2) the reformulation of thermodynamic models for liquid solution properties in order to implement non-deal associative solutions and a more robust equation of state that allows extrapolation of liquid density and free energy to high-pressures, (3) the creation of an experimental program to generate data necessary for the calibration of solution theory for igneous hornblendes and mica, and (4) the use of molecular dynamics simulations to facilitate the creation of a data base of liquid thermochemical properties at high-pressures that will serve as a basis for the calibration of phase equilibria models under Earth-like lower mantle conditions. All of these approaches give hope that in the future it will be possible to compute melting and melt-rock reaction over a much broader range of

  15. Adiabatic invariants and phase equilibria for first-order orbital resonances. [solar mass change effect on asteroid orbits

    NASA Technical Reports Server (NTRS)

    Heppenheimer, T. A.

    1975-01-01

    In the planar circular restricted three-body problem, the evolution of near-commensurable orbits is studied under change in the mass ratio, mu. The evolution involves preservation of two adiabatic invariants. Transition from circulation to libration may occur; such transitions are of two types. Type I transition occurs when the evolutionary track in phase space passes through near-zero eccentricity; as in the ordinary case (no transition), pre- and post-evolutionary states are linked by solution of a two-point boundary-value problem. Type II transition occurs when the evolutionary track encounters an unstable phase equilibrium or periodic orbit. There is then a discontinuous change in one adiabatic invariant, and pre- and post-evolutionary states are linked by solution of a three-point boundary-value problem. No evolutionary track can encounter a stable phase equilibrium, but the class of all stable phase equilibria is mapped into itself under mu change.

  16. Scale bridging description of coherent phase equilibria in the presence of surfaces and interfaces

    NASA Astrophysics Data System (ADS)

    Spatschek, R.; Gobbi, G.; Hüter, C.; Chakrabarty, A.; Aydin, U.; Brinckmann, S.; Neugebauer, J.

    2016-10-01

    We investigate phase separation including elastic coherency effects in the bulk and at surfaces and find a reduction of the solubility limit in the presence of free surfaces. This mechanism favors phase separation near free surfaces even in the absence of external stresses. We apply the theory to hydride formation in nickel, iron, and niobium and obtain a reduction of the solubility limit by up to two orders of magnitude at room temperature in the presence of free surfaces. We develop in particular a scale bridging description of the solubility limit in the low-temperature regime, where the long-ranged elastic effects are expressed through a geometrical solubility modification factor, which expresses the difference to bulk systems. This expression allows to include elastic coherency effects near surfaces, e.g., in ab initio simulations.

  17. 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.

  18. 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.

  19. Liquid/gas and liquid/liquid phase equilibria of the system water/bovine serum albumin.

    PubMed

    Antonov, Yurij; Eckelt, John; Sugaya, Rei; Wolf, Bernhard A

    2013-05-09

    The thermodynamic behavior of the system H2O/BSA was studied at 25 °C within the entire composition range: vapor pressure measurements via head space sampling gas chromatography demonstrate that the attainment of equilibria takes more than one week. A miscibility gap was detected via turbidity and the coexisting phases were analyzed. At 6 °C the two phase region extends from ca. 34 to 40 wt % BSA; it shrinks upon heating. The polymer rich phase is locally ordered, as can be seen under the optical microscope using crossed polarizers. The Flory-Huggins theory turns out to be inappropriate for the modeling of experimental results. A phenomenological expression is employed which uses three adjustable parameters and describes the vapor pressures quantitatively; it also forecasts the existence of a miscibility gap.

  20. Effect of three-body interactions on the vapor-liquid phase equilibria of binary fluid mixtures.

    PubMed

    Wang, Liping; Sadus, Richard J

    2006-08-21

    Gibbs-Duhem Monte Carlo simulations are reported for the vapor-liquid phase coexistence of binary argon+krypton mixtures at different temperatures. The calculations employ accurate two-body potentials in addition to contributions from three-body dispersion interactions resulting from third-order triple-dipole interactions. A comparison is made with experiment that illustrates the role of three-body interactions on the phase envelope. In all cases the simulations represent genuine predictions with input parameters obtained independently from sources other than phase equilibria data. Two-body interactions alone are insufficient to adequately describe vapor-liquid coexistence. In contrast, the addition of three-body interactions results in very good agreement with experiment. In addition to the exact calculation of three-body interactions, calculations are reported with an approximate formula for three-body interactions, which also yields good results.

  1. Breakup of a transient wetting layer in polymer blend thin films: unification with 1D phase equilibria.

    PubMed

    Coveney, Sam; Clarke, Nigel

    2013-09-20

    We show that lateral phase separation in polymer blend thin films can proceed via the formation of a transient wetting layer which breaks up to give a laterally segregated film. We show that the growth of lateral inhomogeneities at the walls in turn causes the distortion of the interface in the transient wetting layer. By addressing the 1D phase equilibria of a polymer blend thin film confined between selectively attracting walls, we show that the breakup of a transient wetting layer is due to wall-blend interactions; there are multiple values of the volume fraction at the walls which solve equilibrium boundary conditions. This mechanism of lateral phase separation should be general.

  2. 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.

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

    NASA Astrophysics Data System (ADS)

    Filiberto, J.; Wood, J.; Le, L.; Dasgupta, R.; Shimizu, N.; Treiman, A. H.

    2010-12-01

    Volatile species, such as H2O, CO2, F, and Cl, are important in the generation and differentiation of basaltic melts. Thus far, experimental work has focused primarily on the effects of water and carbon dioxide on basalt crystallization, liquid-line of descent, and mantle melting [e.g., 1, 2]; 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 a basalt. We have conducted nominally anhydrous piston cylinder experiments, in 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 as AgF2. Fluorine abundances in the experimental glass were measured by SIMS, and major element abundances in glass and minerals were analyzed by EPMA. Nominally volatile free experiments yield liquidus temperatures from 1330 °C at 0.8 GPa to 1400 °C at 1.6 GPa with an olivine (Fo72)-pyroxene (En68)-liquid multiple saturation at 1.25 GPa and 1375°C. The F-bearing experiments yield liquidus temperatures from 1260 °C at 0.6 GPa to 1305 °C at 1.5 GPa with an olivine (Fo66)-pyroxene (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. Mineral-melt Fe2+-Mg KD calculated for both pyroxenes and olivines 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, depresses the liquidus, and changes the composition of the crystallizing minerals. Our study demonstrates that on a weight percent basis, the effect of fluorine is similar to those of H2O [1] and Cl [3] on freezing point depression of basalts. But on an atomic percent basis, the effect of F on liquidus depression of basalts is 1.5-2 times greater than

  4. 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.

  5. 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

    2015-09-07

    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.

  6. 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.

  7. PHASE EQUILIBRIA INVESTIGATION OF BINARY, TERNARY, AND HIGHER ORDER SYSTEMS. PART IV. THE EFFECT OF MOLYBDENUM AND TUNGSTEN ON THE SUBCARBIDE SOLUTIONS IN THE VANADIUM-TANTALUM-CARBON AND NIOBIUM-TANTALUM-CARBON SYSTEMS.

    DTIC Science & Technology

    The phase equilibria investigations described in this report are in direct support of Air Force sponsored cutting tool research programs. The...the high temperature phase equilibria of possible alloy combinations is, therefore, a prerequisite for the fabrication of even test alloys. (Author)

  8. Sulfur in Hydrous, Oxidized Basaltic Magmas: Phase Equilibria and Melt Solubilities

    NASA Astrophysics Data System (ADS)

    Pichavant, M.; Scaillet, B.; di Carlo, I.; Rotolo, S.; Metrich, N.

    2006-05-01

    basalt, sulphides were found to coexist with anhydrite in a fO2 range as high as NNO+3.0. Melts at equilibrium with anhydrite have S concentrations, measured by electron microprobe, of 2070 ppm (basaltic andesite), 5600 ppm (K basalt) and 6500-6550 ppm (picritic basalt). These values reach concentrations similar to found previously for hydrous oxidized trachyandesite melts at 1000 ° C but are significantly less than recent determinations for dry basaltic melts saturated with sulfate at 1300 ° C. Two anhydrite-saturated glasses, investigated by XANES spectroscopy at the sulfur K-edge, show S to be present only as sulfate species. At lower fO2, between NNO and NNO+1, S concentrations in melts synthesized in AuPd capsules strongly decrease because most of the S present is sequestered in the Pd-rich phases. When Au capsules are used (basaltic andesite experiments), there is no marked effect of fO2 on S solubility in this fO2 range: 2250 ppm S (NNO+1.3, sulfide-saturated) vs. 2070 ppm S (NNO+4.1, anhydrite-saturated). This is consistent with the predominance of sulfate species at NNO+1.3 although sulfide species were also detected by XANES. Comparison between near-liquidus experiments with and without S shows no large influence of S on silicate phase equilibria. However, anhydrite crystallization removes a significant amount of Ca from the melt. This strongly affects melt chemistry, and induces major changes in the nature of liquidus silicate phases and in their composition.

  9. 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

  10. 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

  11. Cubical equations of state for predicting the phase equilibria of poorly studied substances

    NASA Astrophysics Data System (ADS)

    Shestova, T. D.; Markvart, A. S.; Lozovskii, T. L.; Zheleznyi, V. P.

    2013-06-01

    A new procedure for determining the coefficients of the Peng-Robinson equation of state is proposed, for which a minimum of information is required. It is shown that using the Morachevskii complexity factor of molecular interaction in the algorithm for calculating the saturation vapor pressure of substances enables us to study the parameters of the vapor-liquid equilibria of substances with various polarities. Based on our validation of the procedure for determining the coefficients of the Ping-Robinson equation, it is concluded that the values for the saturation vapor pressure of halide derivatives of hydrocarbons calculated from tabular reference data agree satisfactorily in practice.

  12. Transferable Potentials for Phase Equilibria. 4. United-Atom Description of Linear and Branched Alkenes and Alkylbenzenes

    SciTech Connect

    WICK,COLLIN D.; MARTIN,MARCUS G.; SIEPMANN,J. ILJA

    2000-07-12

    The Transferable Potentials for Phase Equilibria-United Atom (TraPPE-UA) force field for hydrocarbons is extended to alkenes and alkylbenzenes by introducing the following pseudo-atoms: CH{sub 2}(sp{sup 2}), CH(sp{sup 2}), CH(aro), R-C(aro) for the link to aliphatic side chains, and C(aro) for the link of two benzene rings. In this united-atom force field, the nonbonded interactions of the hydrocarbon pseudo-atoms are solely governed by Lennard-Jones 12-6 potentials, and the Lennard-Jones well depth and size parameters for the new pseudo-atoms were determined by fitting to the single-component vapor-liquid phase equilibria of a few selected model compounds. Configurational-bias Monte Carlo simulations in the NVT version of the Gibbs ensemble were carried out to calculate the single-component vapor-liquid coexistence curves for ethene, propene, 1-butene, trans- and cis-2-butene. 2-methylpropene, 1,5-hexadiene, 1-octene, benzene, toluene, ethylbenzene, propylbenzene, isopropylbenzene, o-, m-, and p-xylene, and naphthalene. The phase diagrams for the binary mixtures of (supercritical) ethene/n-heptane and benzene/n-pentane were determined from simulations in the NpT Gibbs ensemble. Although the TraPPE-UA force field is rather simple and makes use of relatively few different pseudo-atoms, its performance, as judged by comparisons to other popular force fields and available experimental data, is very satisfactory.

  13. Three-phase equilibria in the binary system ethylene + eicosane and the ternary system propane + ethylene + eicosane

    SciTech Connect

    Gregorowicz, J.; Loos, T.W. de; Arons, J. . Lab. of Applied Thermodyanamics and Phase Equilibria)

    1993-07-01

    The solid eicosane-liquid-vapor (SLV) phase behavior in the binary system ethylene + eicosane was investigated. It was found that the SLV curve ends at a critical end point where liquid and vapor are critical in the presence of pure solid eicosane. In this binary system liquid-liquid-vapor (LLV) equilibria are metastable with respect to solid formation. Addition of propane to mixtures of ethylene and eicosane revealed stable LLV equlibria. P-T sections for seven ternary mixtures with different propane and eicosane concentrations were determined according to the synthetic method. On the basis of the results obtained, a rough estimate of the ternary tricritical point and the metastable binary LLV curve is performed.

  14. 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.

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

    PubMed

    Potoff, Jeffrey J; Bernard-Brunel, Damien A

    2009-11-05

    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.

  16. Phase equilibria of the Sn-Ag-Cu-Ni quaternary system at the sn-rich corner

    NASA Astrophysics Data System (ADS)

    Chen, Sinn-Wen; Chang, Cheng-An

    2004-10-01

    Knowledge of phase equilibria of the Sn-Ag-Cu-Ni quaternary system at the Sn-rich corner is important for the understanding of the interfacial reactions at the Sn-Ag-Cu/Ni contacts, which are frequently encountered in recent microelectronic products. Various Sn-Ag-Cu-Ni alloys were prepared and equilibrated at 250°C. The alloys were then quenched and analyzed. The phases were determined by metallography, compositional analysis, and x-ray diffraction (XRD) analysis. No quaternary phases were found. The isoplethal sections at 60at.%Sn, 70at.%Sn, 80at.%Sn, and 90at.%Sn at 250°C are determined. The phase equilibrium relationship was proposed based on the quaternary experimental results and the 250°C isothermal sections of the four constituent ternary systems, Sn-Ag-Cu, Sn-Ag-Ni, Sn-Cu-Ni, and Cu-Ag-Ni. Because there are no ternary phases in all these three systems, all the compounds are in fact binary compounds with various solubilities of the other two elements.

  17. 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

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

    PubMed

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

    2012-09-01

    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.

  19. Effect of Alloying Additions on Phase Equilibria and Creep Resistance of Alumina-Forming Austenitic Stainless Steels

    NASA Astrophysics Data System (ADS)

    Yamamoto, Y.; Santella, M. L.; Brady, M. P.; Bei, H.; Maziasz, P. J.

    2009-08-01

    The high-temperature creep properties of a series of alumina-forming austenitic (AFA) stainless steels based on Fe-20Ni-(12-14)Cr-(2.5-4)Al-(0.2-3.3)Nb-0.1C (weight percent) were studied. Computational thermodynamics were used to aid in the interpretation of data on microstructural stability, phase equilibria, and creep resistance. Phases of MC (M: mainly Nb), M23C6 (M: mainly Cr), B2 [ β-(Ni,Fe)Al], and Laves [Fe2(Mo,Nb)] were observed after creep-rupture testing at 750 °C and 170 MPa; this was generally consistent with the thermodynamic calculations. The creep resistance increased with increasing Nb additions up to 1 wt pct in the 2.5 and 3 Al wt pct alloy series, due to the stabilization of nanoscale MC particles relative to M23C6. Additions of Nb greater than 1 wt pct decreased creep resistance in the alloy series due to stabilization of the Laves phase and increased amounts of undissolved, coarse MC, which effectively reduced the precipitation of nanoscale MC particles. The additions of Al also increased the creep resistance moderately due to the increase in the volume fraction of B2 phase precipitates. Calculations suggested that optimum creep resistance would be achieved at approximately 1.5 wt pct Nb in the 4 wt pct Al alloy series.

  20. Effect of alloying additions on phase equilibria and creep resistance of alumina-forming austenitic stainless steels

    SciTech Connect

    Yamamoto, Yukinori; Santella, Michael L; Brady, Michael P; Bei, Hongbin; Maziasz, Philip J

    2009-01-01

    The high-temperature creep properties of a series of alumina-forming austenitic (AFA) stainless steels based on Fe-20Ni-(12-14)Cr-(2.5-4)Al-(0.2-3.3)Nb-0.1C (weight percent) were studied. Computational thermodynamics were used to aid in the interpretation of data on microstructural stability, phase equilibria, and creep resistance. Phases of MC (M: mainly Nb), M{sub 23}C{sub 6} (M: mainly Cr), B2 [{beta}-(Ni,Fe)Al], and Laves [Fe{sub 2}(Mo,Nb)] were observed after creep-rupture testing at 750 C and 170 MPa; this was generally consistent with the thermodynamic calculations. The creep resistance increased with increasing Nb additions up to 1 wt pct in the 2.5 and 3 Al wt pct alloy series, due to the stabilization of nanoscale MC particles relative to M{sub 23}C{sub 6}. Additions of Nb greater than 1 wt pct decreased creep resistance in the alloy series due to stabilization of the Laves phase and increased amounts of undissolved, coarse MC, which effectively reduced the precipitation of nanoscale MC particles. The additions of Al also increased the creep resistance moderately due to the increase in the volume fraction of B2 phase precipitates. Calculations suggested that optimum creep resistance would be achieved at approximately 1.5 wt pct Nb in the 4 wt pct Al alloy series.

  1. High-Temperature Phase Equilibria of Duplex Stainless Steels Assessed with a Novel In-Situ Neutron Scattering Approach

    NASA Astrophysics Data System (ADS)

    Pettersson, Niklas; Wessman, Sten; Hertzman, Staffan; Studer, Andrew

    2017-04-01

    Duplex stainless steels are designed to solidify with ferrite as the parent phase, with subsequent austenite formation occurring in the solid state, implying that, thermodynamically, a fully ferritic range should exist at high temperatures. However, computational thermodynamic tools appear currently to overestimate the austenite stability of these systems, and contradictory data exist in the literature. In the present work, the high-temperature phase equilibria of four commercial duplex stainless steel grades, denoted 2304, 2101, 2507, and 3207, with varying alloying levels were assessed by measurements of the austenite-to-ferrite transformation at temperatures approaching 1673 K (1400 °C) using a novel in-situ neutron scattering approach. All grades became fully ferritic at some point during progressive heating. Higher austenite dissolution temperatures were measured for the higher alloyed grades, and for 3207, the temperature range for a single-phase ferritic structure approached zero. The influence of temperatures in the region of austenite dissolution was further evaluated by microstructural characterization using electron backscattered diffraction of isothermally heat-treated and quenched samples. The new experimental data are compared to thermodynamic calculations, and the precision of databases is discussed.

  2. Characterization of phase equilibria and oxidation behavior of aluminum-lithium alloys by electron, ion, and neutron beams

    SciTech Connect

    Soni, K.K.

    1991-01-01

    Secondary ion mass spectrometry (SIMS) and neutron-depth profiling (NDP) were used, in a complementary way, for the characterization of the Li distribution in Al-Li alloys in order to study their phase equilibria and oxidation behavior. SIMS compositional imaging of alloys containing T{sub 1} (Al{sub 2}LiCu), T{sub 2} (Al{sub 6}Li{sub 3}Cu), and T{sub B} (Al{sub 7.5}Cu{sub 4}Li) showed a lack of equilibrium between these phases and a non-uniform Cu distribution. Observation regarding some trace-element distributions were also made. The second-phase particles were identified by electron diffraction and x-ray microanalysis as Al{sub 3}Fe and these particles contained no Li. Oxidation of binary Al-Li alloys at high temperature produced a characteristic nodular oxide morphology. Examination of the oxide/alloy interface indicated preferential nucleation of the oxide at the grain boundaries followed by initial lateral growth. The oxide layer also exhibited surface facets due to surface reconstruction during the reaction. Oxidation of Al-Li-Mg alloys led to depletion of both Li and Mg to nearly equal extent. From these depletion profiles, the interdiffusion coefficients for the Al-Li-Mg-(Cu) alloys were calculated.

  3. High-Temperature Phase Equilibria of Duplex Stainless Steels Assessed with a Novel In-Situ Neutron Scattering Approach

    NASA Astrophysics Data System (ADS)

    Pettersson, Niklas; Wessman, Sten; Hertzman, Staffan; Studer, Andrew

    2017-01-01

    Duplex stainless steels are designed to solidify with ferrite as the parent phase, with subsequent austenite formation occurring in the solid state, implying that, thermodynamically, a fully ferritic range should exist at high temperatures. However, computational thermodynamic tools appear currently to overestimate the austenite stability of these systems, and contradictory data exist in the literature. In the present work, the high-temperature phase equilibria of four commercial duplex stainless steel grades, denoted 2304, 2101, 2507, and 3207, with varying alloying levels were assessed by measurements of the austenite-to-ferrite transformation at temperatures approaching 1673 K (1400 °C) using a novel in-situ neutron scattering approach. All grades became fully ferritic at some point during progressive heating. Higher austenite dissolution temperatures were measured for the higher alloyed grades, and for 3207, the temperature range for a single-phase ferritic structure approached zero. The influence of temperatures in the region of austenite dissolution was further evaluated by microstructural characterization using electron backscattered diffraction of isothermally heat-treated and quenched samples. The new experimental data are compared to thermodynamic calculations, and the precision of databases is discussed.

  4. 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.

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

    DOE PAGES

    Uervirojnangkoorn, Monarin; Hilgenfeld, Rolf; Terwilliger, Thomas C.; ...

    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

  6. 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.

  7. Audio steganography by amplitude or phase modification

    NASA Astrophysics Data System (ADS)

    Gopalan, Kaliappan; Wenndt, Stanley J.; Adams, Scott F.; Haddad, Darren M.

    2003-06-01

    This paper presents the results of embedding short covert message utterances on a host, or cover, utterance by modifying the phase or amplitude of perceptually masked or significant regions of the host. In the first method, the absolute phase at selected, perceptually masked frequency indices was changed to fixed, covert data-dependent values. Embedded bits were retrieved at the receiver from the phase at the selected frequency indices. Tests on embedding a GSM-coded covert utterance on clean and noisy host utterances showed no noticeable difference in the stego compared to the hosts in speech quality or spectrogram. A bit error rate of 2 out of 2800 was observed for a clean host utterance while no error occurred for a noisy host. In the second method, the absolute phase of 10 or fewer perceptually significant points in the host was set in accordance with covert data. This resulted in a stego with successful data retrieval and a slightly noticeable degradation in speech quality. Modifying the amplitude of perceptually significant points caused perceptible differences in the stego even with small changes of amplitude made at five points per frame. Finally, the stego obtained by altering the amplitude at perceptually masked points showed barely noticeable differences and excellent data recovery.

  8. Fractionation effects in phase equilibria of polydisperse hard-sphere colloids

    NASA Astrophysics Data System (ADS)

    Fasolo, Moreno; Sollich, Peter

    2004-10-01

    The equilibrium phase behavior of hard spheres with size polydispersity is studied theoretically. We solve numerically the exact phase equilibrium equations that result from accurate free energy expressions for the fluid and solid phases, while accounting fully for size fractionation between coexisting phases. Fluids up to the largest polydispersities that we can study (around 14%) can phase separate by splitting off a solid with a much narrower size distribution. This shows that experimentally observed terminal polydispersities above which phase separation no longer occurs must be due to nonequilibrium effects. We find no evidence of reentrant melting; instead, sufficiently compressed solids phase separate into two or more solid phases. Under appropriate conditions, coexistence of multiple solids with a fluid phase is also predicted. The solids have smaller polydispersities than the parent phase as expected, while the reverse is true for the fluid phase, which contains predominantly smaller particles but also residual amounts of the larger ones. The properties of the coexisting phases are studied in detail; mean diameter, polydispersity, and volume fraction of the phases all reveal marked fractionation. We also propose a method for constructing quantities that optimally distinguish between the coexisting phases, using principal component analysis in the space of density distributions. We conclude by comparing our predictions to Monte Carlo simulations at imposed chemical potential distribution, and find excellent agreement.

  9. Experimental phase equilibria of a Mount St. Helens rhyodacite: a framework for interpreting crystallization paths in degassing silicic magmas

    NASA Astrophysics Data System (ADS)

    Riker, Jenny M.; Blundy, Jonathan D.; Rust, Alison C.; Botcharnikov, Roman E.; Humphreys, Madeleine C. S.

    2015-07-01

    We present isothermal (885 °C) phase equilibrium experiments for a rhyodacite from Mount St. Helens (USA) at variable total pressure (25-457 MPa) and fluid composition (XH2Ofl = 0.6-1.0) under relatively oxidizing conditions (NNO to NNO + 3). Run products were characterized by SEM, electron microprobe, and SIMS. Experimental phase assemblages and phase chemistry are consistent with those of natural samples from Mount St. Helens from the last 4000 years. Our results emphasize the importance of pressure and melt H2O content in controlling phase proportions and compositions, showing how significant textural and compositional variability may be generated in the absence of mixing, cooling, or even decompression. Rather, variations in the bulk volatile content of magmas, and the potential for fluid migration relative to surrounding melts, mean that magmas may take varied trajectories through pressure-fluid composition space during storage, transport, and eruption. We introduce a novel method for projecting isothermal phase equilibria into CO2-H2O space (as conventionally done for melt inclusions) and use this projection to interpret petrological data from Mount St. Helens dacites. By fitting the experimental data as empirical functions of melt water content, we show how different scenarios of isothermal magma degassing (e.g., water-saturated ascent, vapor-buffered ascent, and vapor fluxing) can have quite different textural and chemical consequences. We explore how petrological data might be used to infer degassing paths of natural magmas and conclude that melt CO2 content is a much more useful parameter in this regard than melt H2O.

  10. Postperovskite phase equilibria in the MgSiO3–Al2O3 system

    PubMed Central

    Tsuchiya, Jun; Tsuchiya, Taku

    2008-01-01

    We investigate high-P,T phase equilibria of the MgSiO3–Al2O3 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 Rh2O3(II) phase, present calculations demonstrate that (i) dissolving Al2O3 tends to decrease the postperovskite transition pressure of MgSiO3 but the effect is not significant (≈-0.2 GPa/mol% Al2O3); (ii) Al2O3 produces the narrow perovskite+postperovskite coexisting P,T area (≈1 GPa) for the pyrolitic concentration (xAl2O3 ≈6 mol%), which is sufficiently responsible to the deep-mantle D″ seismic discontinuity; (iii) the transition would be smeared (≈4 GPa) for the basaltic Al-rich composition (xAl2O3 ≈20 mol%), which is still seismically visible unless iron has significant effects; and last (iv) the perovskite structure spontaneously changes to the Rh2O3(II) with increasing the Al concentration involving small displacements of the Mg-site cations. PMID:19036928

  11. 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.

  12. 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.

  13. 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

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

    PubMed

    Ranjan, V; Yu, L; Nakhmanson, Serge; Bernholc, Jerry; Nardelli, M Buongiorno

    2010-09-01

    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 (< or = 12%) undergo a transition from the alpha to the beta phase until a breakdown field of approximately 600 MV m(-1) is reached. These structural phase transitions can be exploited for efficient storage of electrical energy.

  15. Phase equilibria study of the binary systems (1-butyl-3-methylimidazolium thiocyanate ionic liquid + organic solvent or water).

    PubMed

    Domańska, Urszula; Laskowska, M; Pobudkowska, Aneta

    2009-05-07

    (Solid + liquid) phase equilibria (SLE) for the binary systems, ionic liquid (IL) 1-butyl-3-methylimidazolium thiocyanate [BMIM][SCN] with an alcohol (1-octanol, 1-nonanol, 1-decanol, 1-undecanol, or 1-dodecanol) or water, and (liquid + liquid) phase equilibria (LLE) for the binary systems of [BMIM][SCN] with an alkane (n-hexane, n-heptane, n-octane, n-nonane, or n-decane), benzene, an alkylbenzenes (toluene or ethylbenzene), tetrahydrofuran (THF), cycloalkanes (cyclohexane or cycloheptane), or ethers (di-n-propyl ether, di-n-butyl ether, di-n-pentyl ether, n-butylmethyl ether, tert-butylmethyl ether (MTBE), or tert-butylethyl ether (ETBE)) have been determined at ambient pressure. A dynamic method was used over a broad range of mole fractions and temperatures from 250 to 430 K. In the case of systems IL + alkane, cycloalkane, or ether, the mutual immiscibility with an upper critical solution temperature (UCST) was detected, and in the systems of IL + benzene, alkylbenzene, or THF, the mutual immiscibility with a lower critical solution temperature (LCST) was observed. UV-vis spectroscopy was used to determine the very small compositions of the IL in the n-hexane (about 2 x 10(-5) IL mole fraction), benzene (about 2 x 10(-3) IL mole fraction), cyclohexane (about 2 x 10(-5) IL mole fraction), and THF (about 1.2 x 10(-2) IL mole fraction). For the binary systems containing alcohol, it was noticed that with increasing chain length of an alcohol, the solubility decreases. The basic thermal properties of the pure IL, that is, the glass-transition temperature as well as the heat capacity at the glass-transition temperature, have been measured using a differential scanning microcalorimetry technique (DSC). Decomposition of the IL was detected by the simultaneous TG/DTA experiments. Well-known UNIQUAC, Wilson, and NRTL equations have been used to correlate the experimental SLE data sets for alcohols and water. For the systems containing immiscibility gaps {IL + alkane

  16. Phase equilibria, fluid structure, and diffusivity of a discotic liquid crystal.

    PubMed

    Cienega-Cacerez, Octavio; Moreno-Razo, José Antonio; Díaz-Herrera, Enrique; Sambriski, Edward John

    2014-05-14

    Molecular Dynamics simulations were performed for the Gay-Berne discotic fluid parameterized by GB(0.345, 0.2, 1.0, 2.0). The volumetric phase diagram exhibits isotropic (IL), nematic (ND), and two columnar phases characterized by radial distribution functions: the transversal fluid structure varies between a hexagonal columnar (CD) phase (at higher temperatures and pressures) and a rectangular columnar (CO) phase (at lower temperatures and pressures). The slab-wise analysis of fluid dynamics suggests the formation of grain-boundary defects in the CO phase. Longitudinal fluid structure is highly periodic with narrow peaks for the CO phase, suggestive of a near-crystalline (yet diffusive) system, but is only short-ranged for the CD phase. The IL phase does not exhibit anisotropic diffusion. Transversal diffusion is more favorable in the ND phase at all times, but only favorable at short times for the columnar phases. In the columnar phases, a crossover occurs where longitudinal diffusion is favored over transversal diffusion at intermediate-to-long timescales. The anomalous diffusivity is pronounced in both columnar phases, with three identifiable contributions: (a) the rattling of discogens within a transient "interdigitation" cage, (b) the hopping of discogens across columns, and (c) the drifting motion of discogens along the orientation of the director.

  17. Phase equilibria in DOPC/DPPC: Conversion from gel to subgel in two component mixtures.

    PubMed

    Schmidt, Miranda L; Ziani, Latifa; Boudreau, Michelle; Davis, James H

    2009-11-07

    Biological membranes contain a mixture of phospholipids with varying degrees of hydrocarbon chain unsaturation. Mixtures of long chain saturated and unsaturated lipids with cholesterol have attracted a lot of attention because of the formation of two coexisting fluid bilayer phases in such systems over a broad range of temperature and composition. Interpretation of the phase behavior of such ternary mixtures must be based on a thorough understanding of the phase behavior of the binary mixtures formed with the same components. This article describes the phase behavior of mixtures of 1,2-dioleoyl-sn-glycero-3-phosphocholine (DOPC) with 1,2-di-d(31)-palmitoyl-sn-glycero-3-phosphocholine (DPPC) between -20 and 50 degrees C. Particular attention has been paid to the phase coexistence below about 16 degrees C where the subgel phase appears. The changes in the shape of the spectrum (and its spectral moments) during the slow transformation process leads to the conclusion that below 16 degrees C the gel phase is metastable and the gel component of the two-phase mixture slowly transforms to the subgel phase with a slightly different composition. This results in a line of three-phase coexistence near 16 degrees C. Analysis of the transformation of the metastable gel domains into the subgel phase using the nucleation and growth model shows that the subgel domain growth is a two dimensional process.

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

    NASA Technical Reports Server (NTRS)

    Streett, W. B.

    1973-01-01

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

  19. Phase equilibria in the system CO 2-H 2O I: New equilibrium relations at low temperatures

    NASA Astrophysics Data System (ADS)

    Longhi, John

    2005-02-01

    Graphical analysis of free-energy relationships involving binary quadruple points and their associated univariant equilibria in the system CO 2-H 2O suggests the presence of at least 2 previously unrecognized quadruple points and a degenerate binary invariant point involving an azeotrope between CO 2-rich gas and liquid. Thermodynamic data extracted from the equilibrium involving clathrate (hydrate), gas, and ice (H = G+I) are employed along with published data to calculate the P-T range of the 3-ice equilibrium curve, S+I = H, where S is solid CO 2. This equilibrium curve intersects the H = G+I curve approximately where the latter curve intersects the S+H = G curve, thus confirming the existence of one of the inferred quadruple points involving the phases S, G, H, and I. Recognition of some binary equilibria probably have been hampered by extremely low mutual solubilities of CO 2 and H 2O in the fluids phases which, for example, render the S+H = G virtually indistinguishable from the CO 2-sublimation curve. To make the published portion of the L(liquid CO 2)-G-H equilibrium "connect" with the other new quadruple point involving S, L, G, and H, it is necessary to change the sense of the equilibrium from L = G+H at higher pressures to L+H = G at lower pressures by positing a L = G azeotrope at very low concentrations of H 2O. At the low-pressure origin of the azeotrope, which is only a few bars above the CO 2-triple point, the azeotrope curve intersects the 3-phase curve tangentially, creating a degenerate invariant point at which the 3-phase equilibrium changes from L+H = G at lower pressures to L = G+H at higher pressures. The azeotrope curve is offset at slightly lower temperature from the L = G+H curve until the 3-phase equilibrium terminates at the quadruple point involving G, L, H, and W (water). With further increase in pressure the azeotrope curve tracks the L = G+W equilibrium and apparently terminates at a critical end point in close proximity to critical

  20. 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.

  1. New insight into phase equilibria involving imidazolium bistriflamide ionic liquids and their mixtures with alcohols and water.

    PubMed

    Pereiro, Ana B; Deive, Francisco J; Rodríguez, Ana; Ruivo, Diana; Canongia Lopes, José N; Esperança, José M S S; Rebelo, Luís P N

    2010-07-15

    The fluid phase equilibria (liquid-liquid demixing behavior (LLE)) of mixtures of ionic liquids of the 1-alkyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide family, [C(n)mim][NTf(2)], with 2-methylpropanol or n-octanol were investigated. Binary mixtures of [C(4)mim][NTf(2)] + alcohol and [C(6)mim][NTf(2)] + alcohol were compared to pseudobinary mixtures of (0.5[C(2)mim] + 0.5[C(6)mim])[NTf(2)] + alcohol and (0.5[C(2)mim] + 0.5[C(10)mim])[NTf(2)] + alcohol, respectively. Additionally, the presence of water in the studied alcohols or as a third component in the system was analyzed in order to check any possible deviation from the LLE observed for the anhydrous systems. Systems containing small fractions of ionic liquid show similar LLE between the corresponding binary and pseudobinary systems; however, large differences are observed in the presence of water when the IL mass fraction is increased.

  2. Standard state Gibbs energies of hydration of hydrocarbons at elevated temperatures as evaluated from experimental phase equilibria studies

    NASA Astrophysics Data System (ADS)

    Plyasunov, Andrey V.; Shock, Everett L.

    2000-08-01

    Experimental results of phase equilibria studies at elevated temperatures for more than twenty hydrocarbon-water systems were uniformly correlated within the framework of the Peng-Robinson-Stryjek-Vera equation of state in combination with simple mixing rules. This treatment allows evaluation of the Gibbs energy of hydration for many alkanes, 1-alkenes, cycloalkanes (derivatives of cyclohexane) and alkylbenzenes up to 623 K at saturated water vapor pressure and up to 573 K at 50 MPa. Results for homologous series show regular changes with increasing carbon number, and confirm the applicability of the group contribution approach to the Gibbs energy of hydration of hydrocarbons at elevated temperatures. The temperature dependence of group contributions to the Gibbs energy of hydration were determined for CH 3, CH 2, and CH in aliphatic hydrocarbons; C=C and H for alkenes; c-CH 2 and c-CH in cycloalkanes; and CH ar and C ar in alkylbenzenes (or aromatic hydrocarbons). Close agreement between calculated and experimental results suggests that this approach provides reasonable estimates of Gibbs energy of hydration for many alkanes, 1-alkenes, alkyl cyclohexanes and alkylbenzenes at temperatures up to 623 K and pressures up to 50 MPa.

  3. Structure and phase equilibria of the soybean lecithin/PEG 40 monostearate/water system.

    PubMed

    Montalvo, G; Pons, R; Zhang, G; Díaz, M; Valiente, M

    2013-11-26

    PEG stearates are extensively used as emulsifiers in many lipid-based formulations. However, the scheme of the principles of the lipid-surfactant polymer interactions are still poorly understood and need more studies. A new phase diagram of a lecithin/PEG 40 monostearate/water system at 30 °C is reported. First, we have characterized the binary PEG 40 monostearate/water system by the determination of the critical micelle concentration value and the viscous properties. Then, the ternary phase behavior and the influence of phase structure on their macroscopic properties are studied by a combination of different techniques, namely, optical microscopy, small-angle X-ray scattering, differential scanning calorimetry, and rheology. The phase behavior is complex, and some samples evolve even at long times. The single monophasic regions correspond to micellar, swollen lamellar, and lamellar gel phases. The existence of extended areas of phase coexistence (hexagonal, cubic, and lamellar liquid crystalline phases) may be a consequence of the low miscibility of S40P in the lecithin bilayer as well as of the segregation of the phospholipid polydisperse hydrophobic chains. The presence of the PEG 40 monostearate has less effect in the transformation to the cubic phase for lecithin than that found in other systems with simple glycerol-based lipids.

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

    PubMed Central

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

    2014-01-01

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

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

    PubMed

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

    2014-01-24

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

  6. Solid-State Phase Equilibria and Intermetallic Compounds of the Si-V-Zr Ternary System

    NASA Astrophysics Data System (ADS)

    Pan, Yanfang; Ye, Haimei; Chen, Xiaoxian; Jiang, Wenping; Yang, Wenchao; Zhan, Yongzhong

    2016-12-01

    Phase relations in the Si-V-Zr ternary system at 973 K (700 °C) were experimentally investigated using X-ray powder diffraction and scanning electron microscopy coupled with energy-dispersive X-ray spectroscopy. The isothermal section at 973 K (700 °C) is governed by seventeen three-phase regions, thirty-two two-phase regions, and sixteen single-phase regions. Ten binary compounds and one ternary compound (SiVZr) were confirmed. There are two new ternary compounds found in this work for the first time. One of them (Si4V3Zr2) was found in the stoichiometric composition around V 38 pct, Si 50 pct, and Zr 12 pct. The existence of another one (V17Si12Zr3) was observed while analyzing the XRD results of large quantities of equilibrated samples in the region around 54 at. pct V, 33 at. pct Si, and 13 at. pct Zr.

  7. 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.

  8. Phase equilibria and crystal chemistry of the R-Cu-Ti-O systems (R=lanthanides and Y)

    SciTech Connect

    Yang, Z.; Wong-Ng, W.; Kaduk, J.A.; Jang, M.; Liu, G.

    2009-05-15

    As part of the study of interaction of the Ba{sub 2}RCu{sub 3}O{sub 6+z} (R=lanthanides and Y) superconductor with SrTiO{sub 3} buffer, phase equilibria of the subsystem, R{sub 2}O{sub 3}-TiO{sub 2}-CuO (R=Nd, Y, and Yb), have been investigated in air at 960 deg. C. While the phase relationships of the two phase diagrams with smaller R (Y and Yb) are similar, substantial differences were found in the Nd{sub 2}O{sub 3}-TiO{sub 2}-CuO system, partly due to different phase formation in the binary R{sub 2}O{sub 3}-TiO{sub 2} and R{sub 2}O{sub 3}-CuO systems. R{sub 2}CuTiO{sub 6} and R{sub 2}Cu{sub 9}Ti{sub 12}O{sub 36} were the only ternary phases established in all the three diagrams. R{sub 2}Cu{sub 9}Ti{sub 12}O{sub 36} belongs to the perovskite-related [AC{sub 3}](B{sub 4})O{sub 12} family which is cubic Im3. Depending on the size of R{sup 3+}, R{sub 2}CuTiO{sub 6} crystallizes in two crystal systems: Pnma (R=La-Gd), and P6{sub 3}cm (R=Dy-Lu). The structure and crystal chemistry of the Pnma series of R{sub 2}CuTiO{sub 6} (R=La, Nd, Sm, Eu, and Gd) are discussed in detail in this paper. Patterns for selected members of R{sub 2}CuTiO{sub 6} have also been prepared and submitted for inclusion in the Powder Diffraction File (PDF). - Graphical abstract: Phase diagram of the Y{sub 2}O{sub 3}-CuO-TiO{sub 2} system prepared in air at 960 deg. C

  9. Phase equilibria study of the binary systems (N-hexylisoquinolinium thiocyanate ionic liquid + organic solvent or water).

    PubMed

    Królikowska, Marta; Karpińska, Monika; Zawadzki, Maciej

    2012-04-12

    Liquid-liquid phase equilibria (LLE) of binary mixtures containing a room-temperature ionic liquid N-hexylisoquinolinium thiocyanate, [HiQuin][SCN] with an aliphatic hydrocarbon (n-hexane, n-heptane), aromatic hydrocarbon (benzene, toluene, ethylbenzene, n-propylbenzene), cyclohexane, thiophene, water, and 1-alcohol (1-ethanol, 1-butanol, 1-hexanol, 1-octanol, 1-decanol) have been determined using a dynamic method from room temperature to the boiling-point of the solvent at ambient pressure. N-hexylisoquinolinium thiocyanate, [HiQuin][SCN] has been synthesized from N-hexyl-isoquinolinium bromide as a substrate. Specific basic characterization of the new compound including NMR spectra, elementary analysis, and water content have been done. The density and viscosity of pure ionic liquid were determined over a wide temperature range from 298.15 to 348.15 K. The mutual immiscibility with an upper critical solution temperature (UCST) for the binary systems {IL + aliphatic hydrocarbon, cyclohexane, or water} was detected. In the systems of {IL + aromatic hydrocarbon or thiophene} an immiscibility gap with a lower critical solution temperature (LCST) was observed. Complete miscibility in the liquid phase, over a whole range of ionic liquid mole fraction, was observed for the binary mixtures containing IL and an 1-alcohol. For the tested binary systems with immiscibility gap {IL + aliphatic hydrocarbon, aromatic hydrocarbon, cyclohexane, thiophene, or water}, the parameters of the LLE correlation have been derived using the NRTL equation. The basic thermal properties of the pure IL, that is, the glass-transition temperature as well as the heat capacity at the glass-transition temperature, have been measured using a differential scanning microcalorimetry technique (DSC). Decomposition of the IL was detected by simultaneous thermogravimetric/differential thermal analysis (TG/DTA) experiments.

  10. 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.

  11. Determination of thermodynamic parameters of tautomerization in gas phase by mass spectrometry and DFT calculations: Keto-enol versus nitrile-ketenimine equilibria.

    PubMed

    Giussi, Juan M; Gastaca, Belen; Albesa, Alberto; Cortizo, M Susana; Allegretti, Patricia E

    2011-02-01

    The study of tautomerics equilibria is really important because the reactivity of each compound with tautomeric capacity can be determined from the proportion of each tautomer. In the present work the tautomeric equilibria in some γ,δ-unsaturated β-hydroxynitriles and γ,δ-unsaturated β-ketonitriles were studied. The first family of compounds presents two possible theoretical tautomers, nitrile and ketenimine, while the second one presents four possible theoretical tautomers, keto-nitrile, enol (E and Z)-nitrile and keto-ketenimine. The equilibrium in gas phase was studied by gas chromatography-mass spectrometry (GC-MS). Tautomerization enthalpies were calculated by this methodology, and results were compared with those obtained by density functional theory (DFT) calculations, observing a good agreement between them. Nitrile tautomers were favored within the first family of compounds, while keto-nitrile tautomers were favored in the second family.

  12. Confinement-Induced Supercriticality and Phase Equilibria of Hydrocarbons in Nanopores.

    PubMed

    Luo, Sheng; Lutkenhaus, Jodie L; Nasrabadi, Hadi

    2016-11-08

    For over a century, the phase behavior of bulk fluids has been described as PVT (pressure-volume-temperature) three-dimensional properties, but it has become increasingly clear that the liquid-vapor phase behavior in confined geometries is significantly altered from the bulk. Efforts have been devoted to accessing confined phase transitions using sorption, molecular simulations, and theoretical methods. However, a comprehensive picture of PVT relationships for confined hydrocarbons remains uncertain. Herein, we introduce d (confining pore diameter) as a fourth dimension, and we present PVT-d behavior of confined fluids in nanopores. For the first time, a T-d phase diagram is presented for n-hexane, n-octane, and n-decane under multiple confinement scales (37.9, 14.8, 9.8, 6.0, 4.1, 3.3, and 2.2 nm cylindrical pore diameter) using experimental differential scanning calorimetry and PVT-d equation of state theory at atmospheric pressure. As pore diameter decreases from 37.9 to 4.1 nm, the bubble point increases by as much as 15 K above bulk, until we observe behavior consistent with a supercritical state, pointing to confinement-induced supercriticality. Remarkably, experimental and theoretical findings overlap very well, showing that this approach effectively captures the phase boundaries between the liquid, vapor, and supercritical fluid regions. The model and completed EOS are additionally extended to calculation of isothermal capillary adsorption, and its validity is discussed.

  13. Theorization on ion-exchange equilibria: activity of species in 2-D phases.

    PubMed

    Tamura, Hiroki

    2004-11-01

    Ion-exchange reactions are naturally occurring at soil and sediment/water interphases, determining soil fertility and water quality. These ion-exchange reactions with inorganic and organic exchangers are applied to chemical analysis, recovery of useful ions from low-grade ores (potentially from sea water), water purification including the preparation of "ultrapure" water, production of foods and medicines, therapy, and other uses. It is important to theorize about or to model ion-exchange reactions for quantitative explanations of ion-exchange phenomena and for efficient operation of ion-exchange processes. This paper describes the modeling of ion-exchange equilibria for hydroxyl sites on metal oxides and carboxyl sites in resins with monovalent cations (alkali metal ions), a monovalent anion (nitrate ion), and divalent heavy metal ions. The procedure of modeling is as follows: the stoichiometry and material balance equations of the respective ion-exchange reactions were established based on findings here and by others. The equilibrium conditions were given by the Frumkin equation, where the mass-action relation is modified with lateral interactions between species at the interphase. The model equations were fitted to the measured data and model parameter values were determined by nonlinear regression analysis. The formation of bonds between ions and exchanger sites was evaluated by the equilibrium constant and the suppression of bond formation by electrostatic, geometric, and other lateral interactions was evaluated by the interaction constant. It was established that the properties of ions are determined by the valence, size, and hydration state of the ions. Monovalent ions (anions and cations) react with oxide surface hydroxyl and resin carboxyl sites as hydrated ions and form loose ion-site pairs by a weak electrostatic bond (nonspecific adsorption). However, the lateral interactions are large because of a large polarization of the ion-site pairs. When the

  14. Influence of gas phase equilibria on the chemical vapor deposition of graphene.

    PubMed

    Lewis, Amanda M; Derby, Brian; Kinloch, Ian A

    2013-04-23

    We have investigated the influence of gas phase chemistry on the chemical vapor deposition of graphene in a hot wall reactor. A new extended parameter space for graphene growth was defined through literature review and experimentation at low pressures (≥0.001 mbar). The deposited films were characterized by scanning electron microscopy, Raman spectroscopy, and dark field optical microscopy, with the latter showing promise as a rapid and nondestructive characterization technique for graphene films. The equilibrium gas compositions have been calculated across this parameter space. Correlations between the graphene films grown and prevalent species in the equilibrium gas phase revealed that deposition conditions associated with a high acetylene equilibrium concentration lead to good quality graphene deposition, and conditions that stabilize large hydrocarbon molecules in the gas phase result in films with multiple defects. The transition between lobed and hexagonal graphene islands was found to be linked to the concentration of the monatomic hydrogen radical, with low concentrations associated with hexagonal islands.

  15. Isotropic-nematic phase equilibria in the Onsager theory of hard rods with length polydispersity.

    PubMed

    Speranza, Alessandro; Sollich, Peter

    2003-06-01

    We analyze the effect of a continuous spread of particle lengths on the phase behavior of rodlike particles, using the Onsager theory of hard rods. Our aim is to establish whether "unusual" effects such as isotropic-nematic-nematic (I-N-N) phase separation can occur even for length distributions with a single peak. We focus on the onset of I-N coexistence. For a log-normal distribution, we find that a finite upper cutoff on rod lengths is required to make this problem well posed. The cloud curve, which tracks the density at the onset of I-N coexistence as a function of the width of the length distribution, exhibits a kink; this demonstrates that the phase diagram must contain a three-phase I-N-N region. Theoretical analysis shows that in the limit of large cutoff, the cloud point density actually converges to zero, so that phase separation results at any nonzero density; this conclusion applies to all length distributions with fatter-than-exponentail tails. Finally, we consider the case of a Schulz distribution, with its exponential tail. Surprisingly, even here the long rods (and hence the cutoff) can dominate the phase behavior, and a kink in the cloud curve and I-N-N coexistence again result. Theory establishes that there is a nonzero threshold for the width of the length distribution above which these long-rod effects occur, and shows that the cloud and shadow curves approach nonzero limits for a large cutoff, both in good agreement with the numerical results.

  16. 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.

  17. Dual-wavelength Raman spectroscopy approach for studying fluid-phase equilibria using a single laser.

    PubMed

    Kiefer, Johannes

    2010-06-01

    A novel Raman spectroscopy setup for the investigation of multiphase fluid mixtures is proposed. The total output of a frequency-doubled Nd:YAG laser is separated into a strong 532 nm beam for generating Raman signals in the vapor phase and the weak residual of the fundamental 1064 nm radiation to be utilized as laser source for Raman scattering in the liquid phase. This approach will provide sufficient signal intensity from the gas (despite low density) for determination of mixture composition and at the same time it facilitates recording high-resolution spectra from the liquid in order to allow studying molecular physics phenomena together with concentration measurements.

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

    PubMed

    Marshall, Bennett D; Chapman, Walter G

    2013-08-07

    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. 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

  20. 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)

  1. Phase equilibria in ionic liquid-aromatic compound mixtures, including benzene fluorination effects.

    PubMed

    Blesic, Marijana; Lopes, José N Canongia; Pádua, Agílio A H; Shimizu, Karina; Gomes, Margarida F Costa; Rebelo, Luís Paulo N

    2009-05-28

    This work extends the scope of previous studies on the phase behavior of mixtures of ionic liquids with benzenes or its derivatives by determining the solid-liquid and liquid-liquid phase diagrams of mixtures containing an ionic liquid and a fluorinated benzene. The systems studied include 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide plus hexafluorobenzene or 1,3,5-trifluorobenzene and 1-ethyl-3-methylimidazolium triflate or N-ethyl-N-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide plus benzene. The phase diagrams exhibit different kinds of solid-liquid behavior: the (usual) occurrence of eutectic points; the (not-so-usual) presence of congruent melting points and the corresponding formation of inclusion crystals; or the observation of different ionic liquid crystalline phases (polymorphism). These different types of behavior can be controlled by temperature annealing during crystallization or by the nature of the aromatic compound and can be interpreted, at a molecular level, taking into account the structure of the crystals or liquid mixtures, together with the unique characteristics of ionic liquids, namely the dual nature of their interactions with aromatic compounds.

  2. 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).

  3. The studies of phase equilibria and efficiency assessment for self-emulsifying lipid-based formulations.

    PubMed

    Shahba, Ahmad Abdul-Wahhab; Mohsin, Kazi; Alanazi, Fars Kaed

    2012-06-01

    The study was designed to build up a database for the evaluation of the self-emulsifying lipid formulations performance. A standard assessment method was constructed to evaluate the self-emulsifying efficiency of the formulations based on five parameters including excipients miscibility, spontaneity, dispersibility, homogeneity, and physical appearance. Equilibrium phase studies were conducted to investigate the phase changes of the anhydrous formulation in response to aqueous dilution. Droplet size studies were carried out to assess the influence of lipid and surfactant portions on the resulted droplet size upon aqueous dilution. Formulations containing mixed glycerides showed enhanced self-emulsification with both lipophilic and hydrophilic surfactants. Increasing the polarity of the lipid portion in the formulation leaded to progressive water solubilization capacity. In addition, formulations containing medium chain mixed glycerides and hydrophilic surfactants showed lower droplet size compared with their long chain and lipophilic counterparts. The inclusion of mixed glycerides in the lipid formulations enormously enhances the formulation efficiency.

  4. 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.

  5. Structure and phase equilibria of mixtures of the complex salt hexadecyltrimethylammonium polymethacrylate, water and different oils.

    PubMed

    Bernardes, Juliana Silva; Loh, Watson

    2008-02-15

    This work reports on phase diagrams for mixtures of a complex salt formed by a cationic surfactant and an oppositely charged polyelectrolyte, hexadecyltrimethylammonium polymethacrylate, in binary mixtures with water and in ternary mixtures containing water and organic solvents of different polarity ('oils'): decanol, octanol, p-xylene and cyclohexane. The liquid crystalline structures formed were identified by small angle X-ray scattering measurements, which also provided information about changes in the size of the aggregates as a function of the system composition. These results are analysed in comparison with others previously reported [Bernardes et al., J. Phys. Chem. B 110 (2006) 10332-10340] for the analog complex formed with polyacrylate and, in general, reveal that the presence of an extra methylene group in the polymer chain does not produce significant changes in the complex phase diagrams nor in the structure of the liquid crystalline phases formed. Additionally, the obtained results confirm once more the approach used to analyze these kinds of systems formed by polymer and oppositely charged surfactant.

  6. 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.

  7. 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.

  8. Phase Equilibria of BaO-R2O3-CuO z Systems (R = Y and Lanthanides) under CO2-free Conditions

    NASA Astrophysics Data System (ADS)

    Wong-Ng, W.; Yang, Z.; Cook, L. P.; Frank, J.; Loung, M.; Huang, Q.

    2007-10-01

    For applications ranging from phase equilibria to the processing of second-generation high T c superconductor-coated-conductors, phase diagrams constructed under carbonate-free conditions are needed. Subsolidus phase equilibria of BaO-R2O3-CuO z (R = Ho) have been investigated at {p}_{{{{O}}_{{{2}}} }} = 100{Pa} (810°C), 21 kPa (875°C) and 0.1 MPa (850 and 930°C) by applying controlled atmosphere methods to minimize the presence of carbonate and CO2 and H2O contamination. Under carbonate-free conditions, most of these phase diagrams are different from those reported in the literature. In this paper, we also review and compare the phase diagrams of ten BaO-R2O3-CuO z systems (R = Nd, Sm, Eu, Gd, Dy, Y, Ho, Er, Tm and Yb) that were previously determined in this laboratory under {p}_{{{{O}}_{{{2}}} }} = 100{Pa}{.} Among these diagrams, a distinct trend of phase formation and tie-line relationships is observed.

  9. Phase equilibria of (Mg,Fe)2SiO4 at the Earth's upper mantle conditions from first-principles studies

    NASA Astrophysics Data System (ADS)

    Yu, Yonggang G.; Vinograd, Victor L.; Winkler, Björn; Wentzcovitch, Renata M.

    2013-04-01

    Phase equilibria of α, β, and γ (Mg,Fe)2SiO4 are important to understanding the mineralogy of the Earth's upper mantle. Using the first principles approach, we studied thermodynamic properties and phase stability fields of Fe2SiO4. We show that the correct phase transition sequence in Fe2SiO4 (α → γ) can be obtained with the DFT + self-consistent Hubbard U method, while standard DFT methods (LSDA and σ-GGA) as well as the DFT + constant U method fail the task. The vibrational virtual crystal approximation was used to derive the phonon density of state of the Fe2SiO4 polymorphs. High-pressure thermodynamic properties of Fe2SiO4 are then derived with the aid of the quasi-harmonic approximation. They are in very good agreement with experiments. The phase diagram of the (Mg,Fe)2SiO4 system is calculated under the assumption of ideal mixing within α, β, and γ solid solutions. The model permits the investigation of the temperature and pressure effects on the phase boundaries. The widths of the divariant α-β and β-γ loops are barely sensitive to temperature between 1473 and 1873 K. This study shows the promise of applying the DFT + self-consistent Hubbard U method to study phase equilibria of iron-bearing Earth minerals.

  10. Phase equilibria along a basalt-rhyolite mixing line: implications for the origin of calc-alkaline intermediate magmas

    NASA Astrophysics Data System (ADS)

    Ussler, William; Glazner, Allen F.

    1989-02-01

    One-atmosphere, anhydrous phase equilibria determined for alkali basalt/high-silica rhyolite mixtures provide a model for crystallization of natural calc-alkaline mixed magmas. The compositional trend defined by these mixtures mimics the trends of many continental calc-alkaline volcanic suites. As with many naturally occurring suites, the mixtures studied straddle the low-pressure olivine-plagioclase-augite thermal divide. Magma mixing provides a convenient method for magmas to cross this thermal divide in the absence of magnetite crystallization. For the mixtures, Mg-rich olivine (Fo82 87) coexists alone with liquid over an exceptionally large range of temperature and silica content (up to 63 wt% SiO2). This indicates that the Mg-rich olivines found in many andesites and dacites are not necessarily out of equilibrium with the host magma, as is commonly assumed. Such crystals may be either primary phenocrysts, or inherited phenocrysts derived from a mafic magma that mixed with a silicic magma. For the bulk compositions studied, the distribution of Fe and Mg between olivine and liquid ( K D ) is equal to 0.3 and is independent of temperature and composition. This result extends to silicic andesites the applicability of K D arguments for tests of equilibrium between olivine and groundmass and for modeling of fractional crystallization. In contrast, the distribution of calcium and sodium between plagioclase and liquid varies significantly with temperature and composition. Therefore, plagioclase-liquid K D s cannot be used for fractional crystallization modeling or as a test of equilibrium. Calcic plagioclase from a basalt will be close to equilibrium with andesitic mixtures, but sodic plagioclase from a rhyolite will be greatly out of equilibrium. This explains the common observation that calcic plagioclase crystals in hybrid andesites are generally close to textural equilibrium with the surrounding groundmass, but sodic plagioclase crystals generally show remelting

  11. A description of phase equilibria in nonideal systems with the use of integral equation theory

    NASA Astrophysics Data System (ADS)

    D'Yakonov, S. G.; Klinov, A. V.; D'Yakonov, G. S.

    2009-06-01

    Integral equation theory for partial distribution functions was used to consider a method for calculations of vapor-liquid phase equilibrium conditions in binary Lennard-Jones systems with substantial deviations from the Berthelot-Lorentz mixing rules. Possible sources of errors in pressure and chemical potential values and methods for refining the results were analyzed. The required accuracy of calculations can be reached using two parameters only, one in the closure to the Ornstein-Zernike equation and the other in the equation for the chemical potential. These parameters are determined independently from two thermodynamic equations.

  12. 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

  13. Solidification and phase equilibria in the Fe-C-Cr-NbC system

    NASA Astrophysics Data System (ADS)

    Gregolin, J. A. R.; Alcantara, N. G.

    1991-10-01

    A solidification model is developed and experimentally checked for Fe-C-Cr-Nb alloys in the white cast irons range. It is based on a partial quaternary Fe-C-Cr-NbC phase diagram and predicts the possible solidification paths for the alloys containing γ, with (Fe,Cr)7C3 and NbC as the microconstituents at room temperature. The dendritic γ to massive (Fe,Cr)7C3 transition in experimental alloy microstructures with NbC contents up to 22 pet is explained by this model. Thermal analysis is also used to compare the solidification paths and model approach.

  14. Direct computation of two-phase icosahedral equilibria of lipid bilayer vesicles

    NASA Astrophysics Data System (ADS)

    Zhao, Siming; Healey, Timothy; Li, Qingdu

    2017-02-01

    Correctly formulated continuum models for lipid-bilayer membranes present a significant challenge to computational mechanics. In particular, the mid-surface behavior is that of a 2-dimensional fluid, while the membrane resists bending much like an elastic shell. Here we consider a well-known Helfrich-Cahn-Hilliard model for two-phase lipid-bilayer vesicles, incorporating mid-surface fluidity, curvature elasticity and a phase field. We present a systematic approach to the direct computation of vesical configurations possessing icosahedral symmetry, which have been observed in experiment and whose mathematical existence has recently been established. We first introduce a radial-graph formulation to overcome the difficulties associated with fluidity within a conventional Lagrangian description. We use the so-called subdivision surface finite element method combined with an icosahedral-symmetric mesh. The resulting discrete equations are well-conditioned and inherit equivariance properties under a representation of the icosahedral group. We use group-theoretic methods to obtain a reduced problem that captures all icosahedral-symmetric solutions of the full problem. Finally we explore the behavior of our reduced model, varying numerous physical parameters present in the mathematical model.

  15. 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

  16. Influence of water solubility, phase equilibria, and capillary pressure on methane occurrence in sediments

    SciTech Connect

    Claypool, G.E.

    1996-12-31

    Microbial methane is generated in rapidly accumulating marine sediments (>40 m/my) where pore waters are deficient in dissolved oxygen and sulfate. Based on indirect geochemical evidence, microbial methane generation is largely confined to depths of between 10 and 1000 meters beneath the sea floor. Under shelf conditions (water depth <200 m), methane concentrations can exceed solubility in pore water and accumulate as free gas, or escape the sediment as bubbles, or be oxidized in surface sediments. Under some deeper-water conditions of continental slope and rise sediments, more of the methane can be retained and buried because of increased solubility, and because methane in excess of solubility can be stabilized as methane hydrate. Few direct measurements of methane concentration in subsurface pore waters have been made. However, methane-water phase transitions (gas-water contacts, base of gas hydrate reflector) on seismic records can be used with methane solubility relationships to estimate gas contents of sediments. Comparison of various environments shows a relatively narrow range of dissolved methane contents. In marine sediments, free gas (and methane hydrate) is stable only in contact with methane-saturated pore water. Finer-grained sediments can be supersaturated with respect to a gas (and gas hydrate?) phase because of capillary pressure inhibition of bubble (or hydrate?) formation. The amount of methane dissolved in marine sediment pore water is necessarily larger than that present as gas hydrate.

  17. Influence of water solubility, phase equilibria, and capillary pressure on methane occurrence in sediments

    SciTech Connect

    Claypool, G.E. )

    1996-01-01

    Microbial methane is generated in rapidly accumulating marine sediments (>40 m/my) where pore waters are deficient in dissolved oxygen and sulfate. Based on indirect geochemical evidence, microbial methane generation is largely confined to depths of between 10 and 1000 meters beneath the sea floor. Under shelf conditions (water depth <200 m), methane concentrations can exceed solubility in pore water and accumulate as free gas, or escape the sediment as bubbles, or be oxidized in surface sediments. Under some deeper-water conditions of continental slope and rise sediments, more of the methane can be retained and buried because of increased solubility, and because methane in excess of solubility can be stabilized as methane hydrate. Few direct measurements of methane concentration in subsurface pore waters have been made. However, methane-water phase transitions (gas-water contacts, base of gas hydrate reflector) on seismic records can be used with methane solubility relationships to estimate gas contents of sediments. Comparison of various environments shows a relatively narrow range of dissolved methane contents. In marine sediments, free gas (and methane hydrate) is stable only in contact with methane-saturated pore water. Finer-grained sediments can be supersaturated with respect to a gas (and gas hydrate ) phase because of capillary pressure inhibition of bubble (or hydrate ) formation. The amount of methane dissolved in marine sediment pore water is necessarily larger than that present as gas hydrate.

  18. Phlogopite: high temperature solution calorimetry, thermodynamic properties, Al-Si and stacking disorder, and phase equilibria

    SciTech Connect

    Clemens, J.D.; Circone, S.; Navrotsky, A.; McMillan, P.F.; Smith, B.K.; Wall, V.J.

    1987-09-01

    Two structural features complicate the thermodynamics of synthetic and natural micas. The first is a varying degree of tetrahedral Al-Si disorder. Raman spectroscopic study of phlogopite synthesized above 600/sup 0/C suggests a disordered Al-Si distribution. Calculations of the P-T locus of the geologically important equilibrium: Phl + 3Qtz = 3En + Sa + H/sub 2/O, using the authors thermochemical data, agree within experimental error with the results of calculations based on the best available phase equilibrium data only if a tetrahedrally disordered phlogopite is assumed. Such calculations are very sensitive to uncertainties in ..delta..H/sup 0/ and ..delta..HG/sup 0/, and reversed phase equilibrium experiments remain essential to obtaining reliable estimates of thermodynamic properties. In contrast to these Al-Si disordered phlogopites, some biotites of low temperature parageneses (<600/sup 0/C) may have substantial Al-Si order. A variable Al-Si distribution has a substantial effect on the configurational entropy and therefore on the free energy of the mica in question. The second structural complication is stacking disorder, which is present in phlogopite synthesized at 650/sup 0/C but not in the 850/sup 0/C sample. The enthalpy difference between these two samples, determined by solution calorimetry, is smaller than the experimental uncertainty of +/- 1.0 kcal mol/sup -1/. Thus there appears to be little driving force for ordering, and micas with disordered stacking sequences may persist in many geologic environments.

  19. Crystallization history of lunar picritic basalt sample 12002 - Phase-equilibria and cooling-rate studies

    NASA Technical Reports Server (NTRS)

    Walker, D.; Kirkpatrick, R. J.; Longhi, J.; Hays, J. F.

    1976-01-01

    Experimental crystallization of a lunar picrite composition (sample 12002) at controlled linear cooling rates produces systematic changes in the temperature at which crystalline phases appear, in the texture, and in crystal morphology as a function of cooling rate. Phases crystallize in the order olivine, chromium spinel, pyroxene, plagioclase, and ilmenite during equilibrium crystallization, but ilmenite and plagioclase reverse their order of appearance and silica crystallizes in the groundmass during controlled cooling experiments. The partition of iron and magnesium between olivine and liquid is independent of cooling rate, temperature, and pressure. Comparison of the olivine nucleation densities in the lunar sample and in the experiments indicates that the sample began cooling at about 1 deg C/hr. Pyroxene size, chemistry, and growth instability spacings, as well as groundmass coarseness, all suggest that the cooling rate subsequently decreased by as much as a factor of 10 or more. The porphyritic texture of this sample, then, is produced at a decreasing, rather than a discontinuously increasing, cooling rate.

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

    PubMed

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

    2011-10-01

    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.

  1. 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].

  2. Phase Equilibria and Kinetic Crystallization Experiments on the Inyo Domes Rhyolite

    NASA Astrophysics Data System (ADS)

    Castro, J. M.; Gardner, J. E.

    2003-12-01

    Textural characterization of volcanic materials is a common approach used to decipher the conditions of magma ascent, prior to and during eruption. Such an approach is based on the well-established link between magma devolatilization and crystallization. Understanding of the functional relations between degassing and the kinetics of feldspar crystallization has advanced through experimental decompression of natural rhyolitic materials (e.g., Hammer and Rutherford, 2002), thus allowing comparisons between natural and synthetic textures to be used as a geospeedometer. Similar parameterizations of the growth of mafic silicates in silicic melts are sparse, and kinetic information (e.g., growth and nucleation rates) on the crystallization of pyroxene in rhyolitic melts are completely lacking. In light of the common presence of clinopyroxene in groundmass glasses of intermediate volcanic rocks and the abundance of this phase in microlite populations of many pyroclastic and effusive obsidians, we investigate the kinetics of clinopyroxene crystallization in response to isothermal decompression of the Inyo rhyolite. Isothermal decompression experiments are conducted on the low-Ba member of the Inyo rhyolite at H2O-saturation, 750° C, Pi=200 MPa, and NNO+1; initial conditions are guided both by previous studies and new constraints on the H2O-saturated stability regions of the natural mineral paragenesis determined by phase equilibrium experiments run over broad ranges in P (200 to 50 MPa) and T (700-900° C). Decompression paths involve an equilibration period (4-7 days) followed by multiple-step pressure drops of equal size (16 to 30 MPa) and duration, to varying final pressures (167 to 4.4 MPa). Integrated decompression rates vary from 0.045 MPa/min to 0.004 MPa/min, corresponding to total run durations ranging from 3 to 24 days. The observed crystallization sequence is: Fe-Ti oxide, cpx, biotite, plagioclase. In 3 and 6 day runs, clinopyroxene exhibits both low number

  3. 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

  4. 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

  5. Direct calculation of liquid-vapor phase equilibria from transition matrix Monte Carlo simulation

    NASA Astrophysics Data System (ADS)

    Errington, Jeffrey R.

    2003-06-01

    An approach for directly determining the liquid-vapor phase equilibrium of a model system at any temperature along the coexistence line is described. The method relies on transition matrix Monte Carlo ideas developed by Fitzgerald, Picard, and Silver [Europhys. Lett. 46, 282 (1999)]. During a Monte Carlo simulation attempted transitions between states along the Markov chain are monitored as opposed to tracking the number of times the chain visits a given state as is done in conventional simulations. Data collection is highly efficient and very precise results are obtained. The method is implemented in both the grand canonical and isothermal-isobaric ensemble. The main result from a simulation conducted at a given temperature is a density probability distribution for a range of densities that includes both liquid and vapor states. Vapor pressures and coexisting densities are calculated in a straightforward manner from the probability distribution. The approach is demonstrated with the Lennard-Jones fluid. Coexistence properties are directly calculated at temperatures spanning from the triple point to the critical point.

  6. 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.

  7. A transferable force field to predict phase equilibria and surface tension of ethers and glycol ethers.

    PubMed

    Ferrando, Nicolas; Lachet, Véronique; Pérez-Pellitero, Javier; Mackie, Allan D; Malfreyt, Patrice; Boutin, Anne

    2011-09-15

    We propose a new transferable force field to simulate phase equilibrium and interfacial properties of systems involving ethers and glycol ethers. On the basis of the anisotropic united-atom force field, only one new group is introduced: the ether oxygen atom. The optimized Lennard-Jones (LJ) parameters of this atom are identical whatever the molecule simulated (linear ether, branched ether, cyclic ether, aromatic ether, diether, or glycol ether). Accurate predictions are achieved for pure compound saturated properties, critical properties, and surface tensions of the liquid-vapor interface, as well as for pressure-composition binary mixture diagrams. Multifunctional molecules (1,2-dimethoxyethane, 2-methoxyethanol, diethylene glycol) have also been studied using a recently proposed methodology for the calculation of the intramolecular electrostatic energy avoiding the use of additional empirical parameters. This new force field appears transferable for a wide variety of molecules and properties. It is furthermore worth noticing that binary mixtures have been simulated without introducing empirical binary parameters, highlighting also the transferability to mixtures. Hence, this new force field gives future opportunities to simulate complex systems of industrial interest involving molecules with ether functions.

  8. 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.

  9. 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.

  10. First-principles study of phase equilibria in Cu-Pt-Rh disordered alloys.

    PubMed

    Yuge, Koretaka

    2009-10-14

    Phase stability of Cu-Pt-Rh ternary disordered alloys is examined by a combination of cluster expansion techniques and Monte Carlo statistical simulation based on first-principles calculation. The sign of pseudo-binary ECIs indicates that neighboring Cu and Pt strongly prefer unlike-atom pairs, Pt and Rh weakly prefer unlike-atom pairs, and Cu and Rh atoms prefer like-atom pairs, indicating that the ternary alloy retains the ordering tendency of the constituent binary alloys. The formation energy of a random alloy at T = 1200 K exhibits a negative sign for a wide range of Pt-rich compositions, while at Pt-poor compositions of x≤0.25, the formation energy has a positive value. Calculated affinities for the random alloy show the variety of energetically favored bonds for the alloy: Cu-Pt bonds in both first-and second-nearest neighbor (1-NN and 2-NN) are energetically preferred for all the composition range, the Pt-Rh bond in 1-NN is preferred at Pt-rich compositions, the Pt-Rh in 2-NN and Rh-Cu in 1-NN bonds are unfavored for all compositions, and the Rh-Cu bond in 2-NN is unfavored for Pt-poor compositions. We elucidate that the ordering tendency of 1-NN and 2-NN Cu-Pt, 2-NN Pt-Rh and 1-NN Cu-Rh atoms in constituent binary alloys is retained for the whole composition range of Cu-Pt-Rh ternary alloys, while that of 1-NN Pt-Rh and 2-NN Cu-Rh atoms significantly depends on composition.

  11. Temperature and pressure based NMR studies of detergent micelle phase equilibria.

    PubMed

    Alvares, Rohan; Gupta, Shaan; Macdonald, Peter M; Prosser, R Scott

    2014-05-29

    Bulk thermodynamic and volumetric parameters (ΔGmic°, ΔHmic°, ΔSmic°, ΔCp,mic°, ΔVmic°, and Δκmic°) associated with the monomer–micelle equilibrium, were directly determined for a variety of common detergents [sodium n-dodecyl sulfate (SDS), n-dodecyl phosphocholine (DPC), n-dodecyl-β-d-maltoside (DDM), and 7-cyclohexyl-1-heptyl phosphocholine (CyF)] via 1H NMR spectroscopy. For each temperature and pressure point, the critical micelle concentration (cmc) was obtained from a single 1H NMR spectrum at a single intermediate concentration by referencing the observed chemical shift to those of pure monomer and pure micellar phases. This permitted rapid measurements of the cmc over a range of temperatures and pressures. In all cases, micelle formation was strongly entropically favored, while enthalpy changes were all positive, with the exception of SDS, which exhibited a modestly negative enthalpy of micellization. Heat capacity changes were also characteristically negative, while partial molar volume changes were uniformly positive, as expected for an aggregation process dictated by hydrophobic effects. Isothermal compressibility changes were found to be consistent with previous measurements using other techniques. Thermodynamic measurements were also related to spectroscopic studies of topology and micelle structure. For example, paramagnetic effects resulting from the addition of dioxygen provided microscopic topological details concerning the hydrophobicity gradient along the detergent chains within their respective micelles as detected by 1H NMR. In a second example, combined 13C and 1H NMR chemical shift changes arising from application of high pressure, or upon micellization, of CyF provided site-specific details regarding micelle topology. In this fashion, bulk thermodynamics could be related to microscopic topological details within the detergent micelle.

  12. 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

  13. Interpretation of open system petrogenetic processes: Phase equilibria constraints on magma evolution

    NASA Astrophysics Data System (ADS)

    Defant, Marc J.; Nielsen, Roger L.

    1990-01-01

    occurred. Most basaltic magmas cannot evolve to high silica compositions without magnetite fractionation. Small amounts of rhyolite assimilation (assimilation/fractionation < 0.1), however, can drive evolving basalts to more silica rich compositions. If mass balance models are used to interpret these synthetic AFC data, low residuals are obtained if magnetite is added to the crystallizing assemblage. This approach works even for cases where magnetite was not a fractionating phase. Thus, the mass balance results are mathematically correct, but are geologically irrelevant.

  14. Phase equilibria at alkali-rich early proterozoic banded iron formation, Kursk magnetic anomaly, Russia

    NASA Astrophysics Data System (ADS)

    Sayko, K. A.; Gerasimov, V. Yu.; Poskryakova, M. V.

    2003-04-01

    Banded iron formation (BIF) rocks of Kursk Magnetic anomaly (KMA) are distinguished from well known Precambrian BIF by the alkali enrichment and aluminum depletion and as a total absence of the aluminum bearing minerals. From layered silicates the maximum saturated potassium phases seladonite and tetraferribiotite are of widespread occurrence instead stilpnomelane, minnesotaite and greenalite commonplace for low grade BIF. It has been widely distribution of the seladonite with the assemblage of tetraferribiotite, magnetite, hematite, and quartz distinguish ferruginous quartzites Mikhailovsk iron deposit (KMA) from well known Precambrian BIF of the ancient shields. From Fe-Mg silicates the aegirine, ribeckite and aluminum-less chlorite are present. The hematite and magnetite stability in the ferruginous quartzites assemblages suggest the high values of the oxygen fugacity near magnetite-hematite buffer. This is confirmed by somewhat increasing XMg values for seladonite, tetraferribiotite, chlorite, and ribeckite. The minerals producing with large amounts of ferric iron (seladonite, tetraferribiotite) in the ferruginous quartzites of Mikhailovsk iron deposit is caused by the oxygen fugacity high values. For example the ferrichamosite (Fe_5Fe3+(Fe3+Si_3)O10(OH)_8) is produced in place of the commonplace for the low-grade BIF greenalite (Fe_6Si_4O10(OH)_8). As a whole chlorites are a rarity in BIFs (Laird, 1989) through low rocks aluminum content and represent by chamosite (Gole, 1981), clinochlore and ripidolite (Miyano, Beukes, 1997). Chlorite in studied ferruginous quartzites has a uncommon aluminumless composition with high Fe3+ content and corresponds hypothetical end-member of chamosite - "ferrichamosite" and "ferriclinochlore" - "ferrichamosite" series (Burt, 1989). Uncommon aluminumless chlorite composition assumes that it appears during low-grade metamorphism and possible catagenesis: Mag + Hem + Qtz rightarrow H_2O rightarrow Fe-Chm + O_2 Sid + Qtz + Mag

  15. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2004-10-01

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

  17. 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

  18. The Gibbs free energy of nukundamite (Cu3.38Fe0.62S4): A correction and implications for phase equilibria

    USGS Publications Warehouse

    Seal, R.R.; Inan, E.E.; Hemingway, B.S.

    2001-01-01

    The Gibbs free energy of formation of nukundamite (Cu3.38Fe0.62S4) was calculated from published experimental studies of the reaction 3.25 Cu3.38Fe0.62S4 + S2 = 11 CuS + 2 FeS2 in order to correct an erroneous expression in the published record. The correct expression describing the Gibbs free energy of formation (kJ???mol-1) of nukundamite relative to the elements and ideal S2 gas is ??fG?? nukundamite T(K) = -549.75 + 0.23242 T + 3.1284 T0.5, with an uncertainty of 0.6%. An evaluation of the phase equilibria of nukundamite with associated phases in the system Cu-Fe-S as a function of temperature and sulfur fugacity indicates that nukundamite is stable from 224 to 501??C at high sulfidation states. At its greatest extent, at 434??C, the stability field of nukundamite is only 0.4 log f(S2) units wide, which explains its rarity. Equilibria between nukundamite and bornite, which limit the stability of both phases, involve bornite compositions that deviate significantly from stoichiometric Cu5FeS4. Under equilibrium conditions in the system Cu-Fe-S, nukundamite + chalcopyrite is not a stable assemblage at any temperature.

  19. 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

  20. Improvement of the accuracy of phase observation by modification of phase-shifting electron holography.

    PubMed

    Suzuki, Takahiro; Aizawa, Shinji; Tanigaki, Toshiaki; Ota, Keishin; Matsuda, Tsuyoshi; Tonomura, Akira

    2012-07-01

    We found that the accuracy of the phase observation in phase-shifting electron holography is strongly restricted by time variations of mean intensity and contrast of the holograms. A modified method was developed for correcting these variations. Experimental results demonstrated that the modification enabled us to acquire a large number of holograms, and as a result, the accuracy of the phase observation has been improved by a factor of 5.

  1. The application of the Deiters equation of state to the calculations of the vapour-liquid phase equilibria in systems containing halogenhydrocarbons

    NASA Astrophysics Data System (ADS)

    Dąbrowska, Barbara

    2000-03-01

    The Deiters equation of state and the Redlich-Kwong equation of state were used for calculations of low-temperature vapour-liquid phase equilibria and related thermodynamic properties in binary systems containing halogenhydrocarbons. In all calculations, standard mixing rules for the Deiters equation of state as well as the modified mixing rules (including the repulsion function and density-dependent weight factors or the repulsion function and modified mean density approximation with density-dependent weight factors) were used. The calculations were done for the following systems: CF 4/CHF 3, CF 3Cl/CF 2Cl 2, CH 4/CHF 2Cl, CH 4/CF 2Cl 2, CHF 3/CFCl 3, N 2/CF 2Cl 2. The best results were achieved with the Deiters equation of state, especially with modified mixing rules. For higher pressures and lower temperatures the Redlich-Kwong equation of state is not able to predict the phase equilibria in halogenhydrocarbon systems accurately. It fails too in the case of strongly polar substances. The best parameter sets for the Redlich-Kwong equation of state and the Deiters equation of state for the systems investigated were collected.

  2. Phase equilibria, crystal structure and properties of complex oxides in the Nd2O3-SrO-CoO system

    NASA Astrophysics Data System (ADS)

    Aksenova, T. V.; Efimova, T. G.; Lebedev, O. I.; Elkalashy, Sh. I.; Urusova, A. S.; Cherepanov, V. A.

    2017-04-01

    The phase equilibria in the ½Nd2O3-SrO-CoO system were systematically studied at 1373 K in air. The intermediate phases formed in the ½Nd2O3-SrO-CoO system at 1373 K in air are: Nd1-xSrxCoO3-δ (0.0≤x≤0.5 with orthorhombic structure, sp. gr. Pbnm and 0.6≤x≤0.95 whose structure was detected as cubic according to XRD sp. gr. Pm3m, but shown to be tetragonal by TEM due to the oxygen vacancy ordering), Nd2-ySryCoO4-δ (0.6≤y≤1.1 with tetragonal K2NiF4-type structure, sp. gr. I4/mmm) and Nd2-zSrzO3 (0.0≤z≤0.15 with hexagonal structure, sp. gr. P-3m1). The unit cell parameters for the single phase samples were refined by the Rietveld analysis. The changes of oxygen content in Nd1-xSrxCoO3-δ (0.6≤x≤0.95) and Ruddlesden-Popper oxide Nd2-ySryCoO4-δ were examined by TGA. All were found to be oxygen deficient phases. High-temperature dilatometry allows calculating the thermal expansion coefficient and evaluating the chemical expansion coefficient at high temperature. The projection of isothermal-isobaric phase diagram for the Nd-Sr-Co-O system at 1373 K in air to the compositional triangle of metallic components has been constructed. The phase equilibria in the studied Nd-Sr-Co-O system were compared to La-Sr-Co-O and Nd-M-Co-O (M=Ca and Ba).

  3. Phase equilibria and salting-out effects in a cesium nitrate-triethylamine-water system at 5-25°C

    NASA Astrophysics Data System (ADS)

    Il'in, K. K.; Cherkasov, D. G.

    2013-04-01

    Phase equilibria and critical phenomena in a cesium nitrate-water-triethylamine system in which the constituent binary liquid system is stratified at the lower critical solution temperature (LCST) is studied in a range of 5-25°C by the visual polythermal method. It is found that introducing cesium nitrate into the water-triethylamine system leads to a slight reduction in the LCST (from 18.3 to 16.3°C) and to a decrease in the mutual solubility of the components. The distribution coefficients of triethylamine between aqueous and the organic phases of the monotectic state at different temperatures are calculated. It is found that the salting-out of triethylamine from aqueous solutions by cesium nitrate increases with rising temperature. The results of the salting-out effect of sodium, potassium, and cesium nitrates on a water-triethylamine binary system are compared.

  4. 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.

  5. Phase equilibria study in binary systems (tetra-n-butylphosphonium tosylate ionic liquid + 1-alcohol, or benzene, or n-alkylbenzene).

    PubMed

    Domańska, Urszula; Paduszyński, Kamil

    2008-09-04

    Ambient pressure (solid + liquid) equilibria (SLE) and (liquid + liquid) equilibria (LLE) of binary systems--ionic liquid (IL) tetra- n-butylphosphonium p-toluenesulfonate + 1-alcohol (1-butanol, 1-hexanol, 1-octanol, 1-decanol, or 1-dodecanol), benzene, or n-alkylbenzene (toluene, ethylbenzene, n-propylbenzene)-have been determined by using dynamic method in a broad range of mole fractions and temperatures from 250 to 335 K. For binaries containing alcohol, simple eutectic diagrams were observed with complete miscibility in the liquid phase. Only in the case of system [IL + n-propylbenzene] was mutual immiscibility with an upper critical solution temperature (UCST) with low solubility of the IL in the alcohol and high solubility of the alcohol in the IL detected. The basic thermal properties of pure IL, i.e., melting and glass-transition temperatures as well as enthalpy of melting, have been measured with differential scanning microcalorimetry technique (DSC). Well-known UNIQUAC, Wilson, NRTL, NRTL1, and NRTL2 equations have been fitted to obtain experimental data sets. For the system containing immiscibility gap [IL + n-propylbenzene], parameters of the equations have been derived only from SLE data. As a measure of goodness of correlations, root-mean square deviations of temperature have been used. These experimental results were compared to the previously measured binary systems with tetra- n-butylphosphonium methanesulfonate. Changing anion from methanesulfonate to p-toluenesulfonate decreases solubilities in systems with alcohols and increases the solubilities in binary systems with benzene and alkylbenzenes.

  6. Transferable potentials for phase equilibria. 9. Explicit hydrogen description of benzene and five-membered and six-membered heterocyclic aromatic compounds.

    PubMed

    Rai, Neeraj; Siepmann, J Ilja

    2007-09-13

    The explicit hydrogen version of the transferable potentials for phase equilibria (TraPPE-EH) force field is extended to benzene, pyridine, pyrimidine, pyrazine, pyridazine, thiophene, furan, pyrrole, thiazole, oxazole, isoxazole, imidazole, and pyrazole. While the Lennard-Jones parameters for carbon, hydrogen (two types), nitrogen (two types), oxygen, and sulfur are transferable for all 13 compounds, the partial charges are specific for each compound. The benzene dimer energies for sandwich, T-shape, and parallel-displaced configurations obtained for the TraPPE-EH force field compare favorably with high-level electronic structure calculations. Gibbs ensemble Monte Carlo simulations were carried out to compute the single-component vapor-liquid equilibria for benzene, pyridine, three diazenes, and eight five-membered heterocycles. The agreement with experimental data is excellent with the liquid densities and vapor pressures reproduced within 1 and 5%, respectively. The critical temperatures and normal boiling points are predicted with mean deviations of 0.8 and 1.6%, respectively.

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

    PubMed

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

    2015-06-28

    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

  8. 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

  9. 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.

  10. 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.

  11. 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.

  12. 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.

  13. 3-Hydroxy-4-methyl-4-pentenonitrile and 4-methyl-3-oxo-4-pentenonitrile: Study of the tautomerics equilibria in gas phase and in solution.

    PubMed

    Giussi, Juan M; Ponzinibbio, Agustín; Cortizo, M Susana; Allegretti, Patricia E

    2010-10-01

    In the present work the tautomerics equilibria in 3-hydroxy-4-methyl-4-pentenonitrile and 4-methyl-3-oxo-4-pentenonitrile have been studied. The first compound presents two possible theoretical tautomers, nitrile and ketenimine. The second compound presents four possible theoretical tautomers ketonitrile, nitrile-enol (E and Z) and keto-ketenimine. The study of the equilibrium in gas phase was performed by gas chromatography-mass spectrometry (GC-MS), and in solution by proton nuclear magnetic resonance spectrometry ((1)H NMR). In gas phase, the ketonitrile tautomer was favoured, a result which was supported by theoretical calculations by the use of AM1 semi-empiric calculation. The experimental tautomerization heat values were in good agreement with the theoretical ones. The (1)H NMR spectra gave the additional evidence for the coexistence of the tautomers ketonitrile and enolnitrile for 4-methyl-3-oxo-4-pentenonitrile. The nitrile-ketenimine equilibrium for both compounds could not be observed by (1)H NMR spectra because of the low sensibility of this method. The ketonitrile-enolnitrile tautomerization heat of 4-methyl-3-oxo-4-pentenonitrile has been calculated and compared with the corresponding one in gas phase to evaluate the solvent effect.

  14. Determining age of Pan African metamorphism using Sm-Nd garnet-whole rock geochronology and phase equilibria modeling in the Tasriwine ophiolite, Sirwa, Anti-Atlas Morocco

    NASA Astrophysics Data System (ADS)

    Inglis, Jeremy D.; Hefferan, Kevin; Samson, Scott D.; Admou, Hassan; Saquaque, Ali

    2017-03-01

    Sm-Nd garnet-whole rock geochronology and phase equilibria modeling have been used to determine the age and conditions of regional metamorphism within the Tasriwine ophiolite complex, Sirwa, Morocco. Pressure and temperature estimates obtained using a NaCaKFMASHT phase diagram (pseudosection) and garnet core and rim compositions predict that garnet growth began at ∼0.72 GPa and ∼615 °C and ended at ∼0.8 GPa and ∼640 °C. A bulk garnet Sm-Nd age of 647.2 ± 1.7 Ma, calculated from a four point isochron that combines whole rock, garnet full dissolution and two successively more aggressive partial dissolutions, provides a precise date for garnet formation and regional metamorphism. The age is over 15 million years younger than a previous age estimate of regional metamorphism of 663 ± 13 Ma based upon a SHRIMP U-Pb date from rims on zircon from the Iriri migmatite. The new data provide further constraints on the age and nature of regional metamorphism in the Anti-Atlas mountains and emphasizes that garnet growth during regional metamorphism may not necessarily coincide with magmatism/anatexis which predominate the signature witnessed by previous U-Pb studies. The ability to couple PT estimates for garnet formation with high precision Sm-Nd geochronology highlights the utility of garnet studies for uncovering the detailed metamorphic history of the Anti-Atlas mountain belt.

  15. 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.

  16. 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.

  17. High-pressure anatectic paragneisses from the Namche Barwa, Eastern Himalayan Syntaxis: Textural evidence for partial melting, phase equilibria modeling and tectonic implications

    NASA Astrophysics Data System (ADS)

    Guilmette, C.; Indares, A.; Hébert, R.

    2011-05-01

    Rare kyanite-bearing anatectic paragneisses are found as boudins within sillimanite-bearing paragneisses of the core of the Namche Barwa Antiform, Tibet. In the present study, we document an occurrence from the NW side of the Yarlung Zangbo River. These rocks mainly consist of the assemblage garnet + K-feldspar + kyanite ± biotite + quartz + rutile ± plagioclase with kyanite locally pseudomorphed by sillimanite. The documented textures are consistent with the rocks having undergone biotite-dehydration melting in the kyanite stability field, under high-P granulite facies conditions, and having experienced melt extraction. However textures related to melt crystallization are ubiquitous both in polymineralic inclusions in garnet and in the matrix, suggesting that a melt fraction had remained in these rocks. Phase equilibria modelling was undertaken in the NCKFMASTHO system with THERMOCALC. P-T pseudosections built with the bulk compositions of one aluminous and one sub-aluminous paragneiss samples predict a biotite-kyanite-garnet-quartz-plagioclase-K-feldspar-liquid-rutile ± ilmenite field, in which biotite-dehydration melting occurs, located in the P-T range of ~ 800-875 °C and ~ 10-17 kbar. In addition, the topologies of these pseudosections are consistent with substantial melt loss during prograde metamorphism. A second set of P-T pseudosections with melt-reintegrated model bulk compositions were thus constructed to evaluate the effect of melt loss. The integration of textural information, precise mineral modes, mineral chemistry, and phase equilibria modelling allowed to constrain a P-T path where the rocks are buried to lower crustal depths at peak P-T conditions higher than 14 kbar and 825 °C, possibly in the order of 15-16 kbar and 850 °C, followed by decompression and cooling to P-T conditions of around 9 kbar and 810 °C, under which the remaining melt was solidified. The implications for granite production at the NBA and for Himalayan tectonic models

  18. 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

  19. Study of phase equilibria in the CO(NH2)2-KH2PO4-K2HPO4-H2O system at 25°C using an optimized method of cross sections

    NASA Astrophysics Data System (ADS)

    Noskov, M. N.; Mazunin, S. A.

    2015-06-01

    Phase equilibria are studied in ternary contouring systems and in the CO(NH2)2-KH2PO4-K2HPO4-H2O quaternary system at 25°C using an optimized method of cross sections. It is found that an incongruent chemical compound forms between the components of a system with the composition 2KH2PO4 · K2HPO4. The compositions of eutonic and peritonic solutions and the solid phases saturating them are determined. The lines of monovariant equilibria and the crystallization surface of potassium dihydrogen phosphate are studied. The location of the eutonic and peritonic solutions and monovariant equilibrium lines near the plane are shown.

  20. Computation of liquid-liquid equilibria and phase stabilities: implications for RH-dependent gas/particle partitioning of organic-inorganic aerosols

    NASA Astrophysics Data System (ADS)

    Zuend, A.; Marcolli, C.; Peter, T.; Seinfeld, J. H.

    2010-05-01

    Semivolatile organic and inorganic aerosol species partition between the gas and aerosol particle phases to maintain thermodynamic equilibrium. Liquid-liquid phase separation into an organic-rich and an aqueous electrolyte phase can occur in the aerosol as a result of the salting-out effect. Such liquid-liquid equilibria (LLE) affect the gas/particle partitioning of the different semivolatile compounds and might significantly alter both particle mass and composition as compared to a one-phase particle. We present a new liquid-liquid equilibrium and gas/particle partitioning model, using as a basis the group-contribution model AIOMFAC (Zuend et al., 2008). This model allows the reliable computation of the liquid-liquid coexistence curve (binodal), corresponding tie-lines, the limit of stability/metastability (spinodal), and further thermodynamic properties of the phase diagram. Calculations for ternary and multicomponent alcohol/polyol-water-salt mixtures suggest that LLE are a prevalent feature of organic-inorganic aerosol systems. A six-component polyol-water-ammonium sulphate system is used to simulate effects of relative humidity (RH) and the presence of liquid-liquid phase separation on the gas/particle partitioning. RH, salt concentration, and hydrophilicity (water-solubility) are identified as key features in defining the region of a miscibility gap and govern the extent to which compound partitioning is affected by changes in RH. The model predicts that liquid-liquid phase separation can lead to either an increase or decrease in total particulate mass, depending on the overall composition of a system and the particle water content, which is related to the hydrophilicity of the different organic and inorganic compounds. Neglecting non-ideality and liquid-liquid phase separations by assuming an ideal mixture leads to an overestimation of the total particulate mass by up to 30% for the composition and RH range considered in the six-component system simulation

  1. Computation of liquid-liquid equilibria and phase stabilities: implications for RH-dependent gas/particle partitioning of organic-inorganic aerosols

    NASA Astrophysics Data System (ADS)

    Zuend, A.; Marcolli, C.; Peter, T.; Seinfeld, J. H.

    2010-08-01

    Semivolatile organic and inorganic aerosol species partition between the gas and aerosol particle phases to maintain thermodynamic equilibrium. Liquid-liquid phase separation into an organic-rich and an aqueous electrolyte phase can occur in the aerosol as a result of the salting-out effect. Such liquid-liquid equilibria (LLE) affect the gas/particle partitioning of the different semivolatile compounds and might significantly alter both particle mass and composition as compared to a one-phase particle. We present a new liquid-liquid equilibrium and gas/particle partitioning model, using as a basis the group-contribution model AIOMFAC (Zuend et al., 2008). This model allows the reliable computation of the liquid-liquid coexistence curve (binodal), corresponding tie-lines, the limit of stability/metastability (spinodal), and further thermodynamic properties of multicomponent systems. Calculations for ternary and multicomponent alcohol/polyol-water-salt mixtures suggest that LLE are a prevalent feature of organic-inorganic aerosol systems. A six-component polyol-water-ammonium sulphate system is used to simulate effects of relative humidity (RH) and the presence of liquid-liquid phase separation on the gas/particle partitioning. RH, salt concentration, and hydrophilicity (water-solubility) are identified as key features in defining the region of a miscibility gap and govern the extent to which compound partitioning is affected by changes in RH. The model predicts that liquid-liquid phase separation can lead to either an increase or decrease in total particulate mass, depending on the overall composition of a system and the particle water content, which is related to the hydrophilicity of the different organic and inorganic compounds. Neglecting non-ideality and liquid-liquid phase separations by assuming an ideal mixture leads to an overestimation of the total particulate mass by up to 30% for the composition and RH range considered in the six-component system

  2. A contribution to the understanding of phase equilibria (structure of Sr[sub 7]ZrSi[sub 6]O[sub 21])

    SciTech Connect

    Plaisier, J.R.; Graaff, R.A.G. de; Ijdo, D.J.W. . Inst. of Chemistry); Huntelaar, M.E. )

    1994-07-01

    The crystal structure of Sr[sub 7]ZrSi[sub 6]O[sub 21] is described. Sr[sub 7]ZrSi[sub 6]O[sub 21], M[sub r] = 1,209.10, triclinic, P[bar 1], a = 8.398(3)[angstrom], b = 8.435(2)[angstrom], c = 8.445(3)[angstrom], [alpha] = 106.13(3)[degree], [beta] = 106.49(3)[degree], [gamma] = 105.90(3)[degree], V = 509.0(3)[angstrom][sup 3], Z = 1, D[sub x] = 3.944(3) Mgr/m[sup 3]. [gamma](MoK[alpha]) = 0.71069[angstrom], F(000) = 558, room temperature, final R = 0.073 for 1,145 observed reflections. The structure is pseudo rhombohedral, R[bar 3], a[sub hex] = 13.474[angstrom], c[sub hex] = 9.714[angstrom], Z = 3. The crystal structure determination establishes the formula for the compound earlier described in phase equilibria studies as Sr[sub 6]ZrSi[sub 5]O[sub 18].

  3. 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.

  4. Sapphirine-bearing granulites from the Tongbai orogen, China: Petrology, phase equilibria, zircon U-Pb geochronology and implications for Paleozoic ultrahigh temperature metamorphism

    NASA Astrophysics Data System (ADS)

    Xiang, Hua; Zhong, Zeng-Qiu; Li, Ye; Qi, Min; Zhou, Han-Wen; Zhang, Li; Zhang, Ze-Ming; Santosh, M.

    2014-11-01

    We report here for the first time the occurrence of sapphirine-bearing granulites within the Qinling Group of the Qinling-Tongbai orogen and provide robust evidence for extreme crustal metamorphism at ultrahigh-temperature (UHT) conditions. We document the UHT indicator of sapphirine and spinel in a mafic granulite consisting of orthopyroxene, biotite, plagioclase, amphibole and rutile/ilmenite. The ferromagnesian minerals in the sapphirine-bearing granulite have high XMg [Mg/(Mg + Fe)] (orthopyroxene XMg = 0.84-0.95; biotite XMg = 0.81; amphibole XMg = 0.87-0.96). The phase equilibria modeling demonstrates that the early spinel-bearing assemblage is stable at 923-950 °C and 6.7-8.9 kbar, and the peak assemblage of Opx + Pl + Spr/Spl + Amp + Bt + Ilm (+ melt) defines a field at 922-947 °C and 8.4-10.2 kbar. Rutiles have variable Zr concentrations but mostly cluster at ca. 1,500 and 3400 ppm. Zr-in-rutile geothermometry yielded high temperatures of up to 890-940 °C. Zircon U-Pb dating of the granulite constrains the timing of the immediate post-peak and retrograde metamorphic stages as 429 ± 7 Ma and 412 ± 4 Ma, respectively. The UHT metamorphism, together with extensive occurrence of coeval magmatic suites suggests that the Tongbai orogen experienced a Paleozoic Andean-type orogeny probably derived from mid-oceanic ridge subduction of the Qinling Ocean.

  5. Hydrothermal phase equilibria in Ln 2O 3-H 2O-CO 2 systems . I. The lighter lanthanides

    NASA Astrophysics Data System (ADS)

    Tareen, J. A. K.; Kutty, T. R. N.

    1980-10-01

    Phase diagrams for Nd 2O 3-H 2O-CO 2 and Gd 2O 3-H 2O-CO 2 systems at 1500 atm are given along with the results of selected runs in La, Sm and Eu systems. The stable phases in systems of La and Nd, are Ln(OH)CO 3-B, Ln 2O 2CO 3-II and LnOOH, in addition to the Ln(OH) 3 phase at extremely low partial pressures of CO 2 in the system. The systems become more and more complex with decreasing ionic radi and the number of stable carbonate phases increases. Ln 2(CO 3) 3 · 3H 2O orthorhombic (tengerate-like phase) is stable from Sm to Gd in addition to the other phases. The Gd(OH)CO 3-A (ancylite-like phase) is hydrothermally stable at XCO 2 ⩾ 0.5 while its hexagonal polymorph, Gd(OH)CO 3-B is stable at low partial pressures of CO 2 in the system.

  6. High-temperature phase equilibria in the Al-rich corner of the Al-Ti-C system

    SciTech Connect

    Frage, N.; Frumin, N.; Levin, L.; Polak, M.; Dariel, M.P.

    1998-04-01

    A thermodynamic analysis of the Al-rich corner in the ternary Al-Ti-C diagram, providing phase relations and regions of phase stability, is presented. An invariant four-phase equilibrium between Al, Al{sub 4}C{sub 3}, Al{sub 3}Ti, and TiC{sub x} takes place at 0.53 at. pct Ti, 7.10{sup {minus}6} at. pct C, and TiC{sub 0.883} at 966 K. The carbon content of the TiC{sub x} phase, which extends from x = 0.48 to 0.98, exerts a significant effect on phase relationships in this ternary system. In particular, it is shown that stoichiometric TiC is not stable in the presence of liquid Al. For example, at 1,300 K, a two-phase equilibrium between Al{sub L} and TiC{sub x} exists only in the 0.91 < x < 0.82 range. Thus, the interaction of Al{sub L} with stoichiometric TiC leads to the formation of the Al{sub 4}C{sub 3} aluminum carbide phase, whereas for x < 0.82, only the intermetallic compound Al{sub 3}Ti can form at this temperature. The results of this analysis were confirmed by X-ray diffraction (XRD) measurements of relevant composites.

  7. Phase Equilibria and Crystal Chemistry in Portions of the System SrO-CaO-Bi2O3-CuO, Part IV— The System CaO-Bi2O3-CuO

    PubMed Central

    Burton, B. P.; Rawn, C. J.; Roth, R. S.; Hwang, N. M.

    1993-01-01

    New data are presented on the phase equilibria and crystal chemistry of the binary systems CaO-Bi2O3 and CaO-CuO and the ternary CaO-Bi2O3-CuO. Symmetry data and unit cell dimensions based on single crystal and powder x-ray diffraction measurements are reported for several of the binary CaO-Bi2O3 phases, including corrected compositions for Ca4Bi6O13 and Ca2Bi2O5. The ternary system contains no new ternary phases which can be formed in air at ~700–900 °C. PMID:28053484

  8. Phase equilibria in four-component system consisting of water, a nonionic surfactant mixture, and oleic acid

    SciTech Connect

    Matveenko, V.N.; Drovetskii, B.Yu.; Kirasanov, E.A.

    1994-05-01

    The phase diagram of the system consisting of water, Tween 20, Span 80, and oleic acid has been obtained; the coexisting phases have been identified; and the character of the equilibrium of microemulsion, liquid crystal, and molecular solution has been described. In the water-Tween 20-oleic acid system, the ratio of the water volume to the surfactant volume is identical in all of the coexisting phases; this proves the existence of a corresponding field variable in a system with a nonionic surfactant.

  9. Phase and Extractive Equilibria in the Water-Inorganic Salting-out Agent-Polyethyleneglycol Alkyl Ether Systems

    NASA Astrophysics Data System (ADS)

    Kudryashova, O. S.; Denisova, S. A.; Lesnov, A. E.; Popova, M. A.

    2008-04-01

    The solubility isotherms were constructed for the ternary systems H2O-DS-10 synthanol-(NH4)2SO4 and H2O—ALM-10 synthanol-KSCN at 298 K. The regions of two-phase liquid equilibrium were revealed. The interphase distribution of some metal ions was examined. It was established that cobalt(II) and zinc ions were quantitatively extracted into the phase of the surface-active substance in the system with potassium thiocyanate.

  10. 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.

  11. Phase equilibria in electrochemically oxidized La 2CuO 4δ. Transport measurements versus chemical analysis

    NASA Astrophysics Data System (ADS)

    Ondoño-Castillo, S.; Michel, C. R.; Seffar, A.; Fontcuberta, J.; Casañ-Pastor, N.

    1994-12-01

    A comparative study of physical and chemical methods for the analysis of the number and identity of holes in electrochemically oxidized La 2CuO 4+δ is reported. A combination of TGA and iodometric chemical analyses shows the existence of two species with different oxidation potentials. Susceptibility and resistivity measurements show the existence of at least two segregated superconducting phases, while Seebeck measurements shows a large change in the number of carriers for a constant value of δ; this atypical behavior is consistent though with the chemical data and implies the existence of a phase equilibrium within the oxide.

  12. Phase equilibria study of {N-hexylisoquinolinium bis{(trifluoromethyl)sulfonyl}imide + aromatic hydrocarbons or an alcohol} binary systems.

    PubMed

    Domańska, Urszula; Zawadzki, Maciej; Tshibangu, M Marc; Ramjugernath, Deresh; Letcher, Trevor M

    2011-04-14

    Isoquinolinium ionic liquid (IL) has been synthesized from N-hexylisoquinolinium bromide as a substrate. Specific basic characterization of the synthesized compound is included, which includes NMR spectra, elementary analysis, and water content. The basic thermal properties of the pure IL, that is, melting and solid-solid transition temperatures, as well as the enthalpy of fusion, or solid-solid transition have been measured using a differential scanning microcalorimetry technique. The density and viscosity as a function of temperature have been measured for the pure IL at temperatures higher than the melting temperature and were extrapolated to T = 298.15 K. The temperature-composition phase diagrams of 8 binary mixtures composed of the IL N-hexylisoquinolinium bis{(trifluoromethyl)sulfonyl}imide, ([HiQuin][NTf(2)]) and an aromatic hydrocarbon (benzene, or toluene, or ethylbenzene, n-propylbenzene) or an alcohol (1-butanol, or 1-hexanol, or 1-octanol, or 1-decanol) have been determined from ambient temperature to the boiling-point temperature of the solvent at ambient pressure. A dynamic method was used over a broad range of mole fractions and temperatures from 270 to 330 K. For the binary systems, the eutectic diagrams were observed with immiscibility in the liquid phase with an upper critical solution temperature (UCST). In the case of the mixture {IL + benzene, or alkylbenzene} the eutectic systems with mutual immiscibility in the liquid phase with very high UCSTs were observed. These points were not detectable with our method and were observed at low IL mole fraction. For mixtures with alcohols, it was observed that with an increasing chain length of an alcohol, the solubility decreases and the UCST increases. The coexistence curves corresponding to liquid-liquid phase equilibrium boundaries and the solid-liquid phase equilibrium has been correlated using the well-known nonrandom two-liquid (NRTL) model.

  13. Equation of state modeling of the phase equilibria of ionic liquid mixtures at low and high pressure.

    PubMed

    Karakatsani, Eirini K; Economou, Ioannis G; Kroon, Maaike C; Bermejo, Maria D; Peters, Cor J; Witkamp, Geert-Jan

    2008-10-28

    Accurate design of processes based on ionic liquids (ILs) requires knowledge of the phase behavior of the systems involved. In this work, the truncated perturbed chain polar statistical associating fluid theory (tPC-PSAFT) is used to correlate the phase behavior of binary and ternary IL mixtures. Both non-polar and polar solvents are examined, while methyl imidazolium ILs are used in all cases. tPC-PSAFT accounts explicitly for weak dispersion interactions, highly directive polar interactions between permanent dipolar and quadrupolar molecules and association between hydrogen bonding molecules. For mixtures of non-polar solvents, tPC-PSAFT predicts accurately the binary mixture data. For the case of polar solvents, a binary interaction parameter is fitted to the experimental data and the agreement between experiment and correlation is very good in all cases.

  14. 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.

  15. Solid-Phase Equilibria for Metal-Silicon-Oxygen Ternary Systems I: Mg, Ca, Sr and Ba

    DTIC Science & Technology

    1990-07-01

    both Sr and Ba to their respective disilicides . An intermediate situation exists for the Ca oxides and silicates, in which excess Si can react with CaO...Si depends on their structural and electrical properties , and significant amounts of research would be required to grow such films and evaluate their... properties . The phase diagrams in Figs. 2-4 can also be used to estimate whether or not various forms of the new oxide superconductors are compatible

  16. Pressure effects on phase equilibria and solid solubility in MgO-Y2O3 nanocomposites

    NASA Astrophysics Data System (ADS)

    Akdoǧan, E. K.; Şavklιyιldιz, I.; Berke, B.; Zhong, Z.; Wang, L.; Weidner, D.; Croft, M. C.; Tsakalakos, T.

    2012-03-01

    We study the temperature and pressure dependence of phase evolution in the 0.5MgO-0.5Y2O3 nanocomposite system using a diamond anvil apparatus in conjunction with in situ synchrotron energy dispersive x-ray diffraction at 7 GPa hydrostatic pressure. At (298 K, 7.0 GPa), structural transformations in the Y2O3 phase are observed, giving rise to the co-existence of its cubic, hexagonal, and monoclinic polymorphs together with cubic MgO. An increase in temperature to 1273 K causes the crystallinity of the Y2O3 hexagonal and monoclinic phases to increase. Isothermal and isobaric hold at (1273 K, 7.0 GPa) for 60 min results in yttrium dissolution in cubic MgO, causing ˜1.0% expansive volumetric lattice strain despite the large differences in the ionic radii of the cations. Cooling the nanocomposite to (298 K, 0 GPa) after a 60 min soak yields four phase co-existence among cubic MgO and cubic, hexagonal, and monoclinic Y2O3. The residual MgO unit cell volume expansion is 0.69% at 298 K, indicating solid solution formation at room temperature despite large differences in the ionic radii of Mg2+ and Y3+. The macroscopic shrinkage due to densification is 3% by volume. Thermodynamic considerations suggest that the relative molar partial volume of Y3+ in MgO is a negative quantity, indicating that the partial molar volume of Y3+ in the solid solution is smaller than its molar volume in the pure state. Aging of the nanocomposites for 240 h does not change the observed 4 phase co-existence. We propose a crystallographic model in which the observed volumetric expansion of the MgO unit cell is primarily attributed to two hydrostatic expansive strain components accompanying solid solution formation: (i) Coulomb repulsion among O2- ions in the immediate vicinity of Mg2+ vacancies, and (ii) misfit strain due to differences in ionic radii upon Y3+ substitution on Mg2+ sites.

  17. 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

  18. 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.

  19. Riemannian geometry study of vapor-liquid phase equilibria and supercritical behavior of the Lennard-Jones fluid.

    PubMed

    May, Helge-Otmar; Mausbach, Peter

    2012-03-01

    The behavior of thermodynamic response functions and the thermodynamic scalar curvature in the supercritical region have been studied for a Lennard-Jones fluid based on a revised modified Benedict-Webb-Rubin equation of state. Response function extrema are sometimes used to estimate the Widom line, which is characterized by the maxima of the correlation lengths. We calculated the Widom line for the Lennard-Jones fluid without using any response function extrema. Since the volume of the correlation length is proportional to the Riemannian thermodynamic scalar curvature, the locus of the Widom line follows the slope of maximum curvature. We show that the slope of the Widom line follows the slope of the isobaric heat capacity maximum only in the close vicinity of the critical point and that, therefore, the use of response function extrema in this context is problematic. Furthermore, we constructed the vapor-liquid coexistence line for the Lennard-Jones fluid using the fact that the correlation length, and therefore the thermodynamic scalar curvature, must be equal in the two coexisting phases. We compared the resulting phase envelope with those from simulation data where multiple histogram reweighting was used and found striking agreement between the two methods.

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

    PubMed

    Koga, K; Widom, B

    2016-06-22

    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.

  1. 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.

  2. Phase-equilibria for design of coal-gasification processes: dew points of hot gases containing condensible tars. Final report

    SciTech Connect

    Prausnitz, J.M.

    1980-05-01

    This research is concerned with the fundamental physical chemistry and thermodynamics of condensation of tars (dew points) from the vapor phase at advanced temperatures and pressures. Fundamental quantitative understanding of dew points is important for rational design of heat exchangers to recover sensible heat from hot, tar-containing gases that are produced in coal gasification. This report includes essentially six contributions toward establishing the desired understanding: (1) Characterization of Coal Tars for Dew-Point Calculations; (2) Fugacity Coefficients for Dew-Point Calculations in Coal-Gasification Process Design; (3) Vapor Pressures of High-Molecular-Weight Hydrocarbons; (4) Estimation of Vapor Pressures of High-Boiling Fractions in Liquefied Fossil Fuels Containing Heteroatoms Nitrogen or Sulfur; and (5) Vapor Pressures of Heavy Liquid Hydrocarbons by a Group-Contribution Method.

  3. 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.

  4. Phase equilibria in system LiCl-NaCl-H2O at 308 and 348 K

    NASA Astrophysics Data System (ADS)

    Wang, Shi-qiang; Guo, Ya-fei; Liu, Dong-fang; Deng, Tian-long

    2016-12-01

    The solubilities and densities of the solutions in the ternary system LiCl-NaCl-H2O at 308 and 348 K were determined by the method of isothermal dissolution equilibrium. There are one invariant point, two univariant isotherm dissolution curves, and two crystallization regions corresponding to monohydrate (LiCl · H2O) and NaCl, respectively. This system at both temperatures belongs to hydrate type I, and neither double salt nor solid solution was found. A comparison of the phase diagram for the ternary system at 273-348 K shows that the area of crystallization region of LiCl · H2O is decreased with the increasing of temperature, while that of NaCl is increased obviously. The solution density of the ternary system at two temperatures changes regularly with the increasing of LiCl concentration.

  5. Phase equilibria diagrams, crystal growth peculiarities and Raman investigations of lead and sodium-bismuth tungstate-molybdate solid solutions

    NASA Astrophysics Data System (ADS)

    Lebedev, Andrei V.; Avanesov, Samvel A.; Yunalan, Tyliay M.; Klimenko, Valeriy A.; Ignatyev, Boris V.; Isaev, Vladislav A.

    2016-02-01

    In this paper a comprehensive study of lead and sodium-bismuth tungstate-molybdate solid solutions was carried out, including the clarification of their structural peculiarities and phase diagrams of PbMoO4-PbWO4 and NaBi(MoO4)2-NaBi(WO4)2 systems, the study of spontaneous Raman spectra of these compounds, as well as preliminary experiments on single crystals growth of lead tungstate-molybdate. The linewidths, peak and integral intensities of the totally symmetric Raman vibrations of solid solutions were estimated in comparison with known SRS-active crystals. The conditions of the Czochralski growth of optically transparent lead tungstate-molybdate mixed crystals were found and SRS effect was observed in these crystals when pumping by 12 ns 1064 nm laser pulses.

  6. 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

  7. 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.

  8. Simulation of chemical potentials and phase equilibria in two- and three-dimensional square-well fluids: finite size effects.

    PubMed

    Vörtler, Horst L; Schäfer, Katja; Smith, William R

    2008-04-17

    We study the simulation cell size dependence of chemical potential isotherms in subcritical square-well fluids by means of series of canonical ensemble Monte Carlo simulations with increasing numbers of particles, for both three-dimensional bulk systems and two-dimensional planar layers, using Widom-like particle insertion methods. By estimating the corresponding vapor/liquid coexistence densities using a Maxwell-like equal area rule for the subcritical chemical potential isotherms, we are able to study the influence of system size not only on chemical potentials but also on the coexistence properties. The chemical potential versus density isotherms show van der Waals-like loops in the subcritical vapor/liquid coexistence range that exhibit distinct finite size effects for both two- and three-dimensional fluids. Generally, in agreement with recent findings for related studies of Lennard-Jones fluids, the loops shrink with increasing number of particles. In contrast to the subcritical isotherms themselves, the equilibrium vapor/liquid densities show only a weak system size dependence and agree quantitatively with the best-known literature values for three-dimensional fluids. This allows our approach to be used to accurately predict the phase coexistence properties. Our resulting phase equilibrium results for two-dimensional square-well fluids are new. Knowledge concerning finite size effects of square-well systems is important not only for the simulation of thermodynamic properties of simple fluids, but also for the simulation of models of more complex fluids (such as aqueous or polymer fluids) involving square-well interactions.

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

    PubMed

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

    2015-10-16

    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.

  10. Phase equilibria in the palladium-rich part of the Pd-Au-Cu-Sn quaternary system

    NASA Astrophysics Data System (ADS)

    Kareva, M. A.; Kabanova, E. G.; Zhmurko, G. P.; Kuznetsov, V. N.

    2017-02-01

    The solubility of tin in the phases of Pd-Au-Sn and Pd-Cu-Sn ternary systems and a Pd-Au-Cu-Sn quaternary system with a fixed Pd: Au: Cu ratio of 11.1: 1: 4.6 is studied via microstructural, X-ray diffraction, and energy dispersive analysis. It is found that a quaternary alloy in equilibrium with a solid solution based on Pd, Au, and Sn contains a τ1 compound with structure which is derivative of the In type. It contains 15 at % Sn and is a solid solution of the same compounds identified earlier in Pd-Au-Sn and Pd-Cu-Sn ternary systems. In addition, a quaternary alloy with a content of 20 at % Sn also contains a τ2 compound with the Pd2CuSn own type and can barely dissolve gold. The obtained data are used to construct a three-dimensional model of the Pd-rich part of the isothermal tetrahedron of the Pd-Au-Cu-Sn system and diagrams of the tin solubility isolines in palladium-rich alloys of the quaternary system at 500°C.

  11. 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.

  12. 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…

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

    SciTech Connect

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

    2015-12-15

    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 Tb{sub 4}Mg{sub 3}Co{sub 2} and Tb{sub 4}MgCo was confirmed. The formation of two solid solutions, Tb{sub 1−x}Mg{sub x}Co{sub 3} (0≤x≤0.4) and Tb{sub 1-−x}Mg{sub x}Co{sub 2} (0≤x≤0.6), was found for the first time. It is shown that Tb{sub 5}Mg{sub 24} also dissolves a small amount of Co. Other binary compounds do not dissolve the third component. The Tb{sub 4}MgCo and TbMgCo{sub 4} 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 Tb{sub 4}MgCoH{sub 12.7} hydride was stable up to 300 °C and disproportionated at higher temperature. Two other hydrides, Tb{sub 4}Mg{sub 3}Co{sub 2}H{sub ∼4} and Tb{sub 2}MgCo{sub 9}H{sub 12}, are unstable in air and decompose into the initial compounds. - Highlights: • The phase equilibria at 500 °°C in the Tb–Mg–Co system has been studied. • The existence of two ternary compounds, Tb{sub 4}Mg{sub 3}Co{sub 2} and Tb{sub 4}MgCo, was confirmed. • The formation of two solid solutions, Tb{sub 1−x}Mg{sub x}Co{sub 3} and Tb{sub 1−x}Mg{sub x}Co{sub 2}, was found. • Hydrogen sorption–desorption properties have been studied for the selected alloys.

  14. Effects of volatiles on phase equilibria of a basalt from Piton de la Fournaise (Réunion island): experimental results and comparison with natural products.

    NASA Astrophysics Data System (ADS)

    Brugier, Yann-Aurélien; Pichavant, Michel; di Muro, Andréa; Bourdier, Jean-Louis

    2015-04-01

    The eruptive activity of the Piton de la Fournaise (PdF) hotspot volcano is monitored by geophysical, geochemical and petrological approaches. Nevertheless, the structure of the feeding system and magma reservoirs is still debated. 4 different lava groups occur at PdF: (1) Steady State Basalts (SSB), the dominant group in the recent activity, (2) the Differentiated Lavas group, typical of the early activity, (3) the Picrites group with olivine-rich lavas (oceanites) characteristic of La Réunion volcanism and (4) the Abnormal Group (AbG) that contains lavas with mixed geochemical characteristics. To understand the petrogenetic relations between the 4 groups of lavas, constrain the structure of the feeding system and the magma storage conditions, experimental phase equilibria have been determined under fluid-present conditions, with either H2O or H2O+CO2 added, for a SSB lava from the 2009 eruption. Experiments have been performed both at high pressures (HP) and 1atm. The HP experiments were carried out in an IHPV, pressurized with Ar-H2 mixtures, at 50MPa and 400MPa. The 1atm experiments used a vertical CO-CO2 gas mixing furnace. Experimental products were analyzed by SEM, EMPA and µ-FTIR Spectroscopy. Results at 50 MPa lead to a crystallization sequence in the order olivine (ol, + spinel), clinopyroxene (cpx), plagioclase (plag). Volatile concentrations in experimental glasses range from 0.5 to 1 wt% for H2O and 30 to 180 ppm for CO2, within the range of glass inclusions in olivine phenocrysts. Fo contents in ol, Mg# in cpx and An contents in plag are in agreement with compositions of natural phenocrysts, suggesting that our experiments closely approach the shallow magmatic evolution at PdF. Preliminary experiments at 400 MPa indicate a change in the crystallization sequence, olivine being replaced by cpx as the liquidus phase. Our data are in marked contrast with previous experimental results under volatile-free conditions. Experiments at 1 atm are in progress

  15. 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.

  16. 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.

  17. 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.

  18. 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.

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

    PubMed

    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.

  20. Synthesis, Phase Transfer and Surface Modification of Hydrophobic Quantum Dots for Bioapplications

    NASA Astrophysics Data System (ADS)

    Zhang, Ruili; Zhang, Xiao; Li, Xiaoyu; Yang, Ping

    2013-04-01

    We review the preparation, phase transfer, surface modification and possible bioapplications of hydrophobic CdSe based quantum dots (QDs). CdSe cores with rod and spherical morphologies were prepared through adjusting preparation conditions. The photoluminescence (PL) of the QDs depended strongly on preparation conditions. The QDs were coated with semiconductor shells to improve their PL properties. Anisotropic growth occurred during shell coating. Core/shell QDs revealed tunable PL and high PL efficiencies up to 90%. The phase transfer of QDs from oil phase to water phase was carried out via polymer or a sol-gel process. The silanization of the QDs plays an important role for the sol-gel process. Because of a SiO2 coating, the surface modification of the QDs for bioapplications became easy. After transferring into water phase, the QDs still retained high PL efficiency. Because of their high PL, these biofunctional materials could provide a platform for various applications.

  1. 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

  2. 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).

  3. 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).

  4. Investigation of the Phase Equilibria and Phase Transformations Associated with the BISMUTH(2) STRONTIUM(2) Calcium COPPER(2) Oxygen(y) Superconductor

    NASA Astrophysics Data System (ADS)

    Holesinger, Terry George

    Compositional measurements of the Bi_2Sr_2CaCu_2O_{y} (2212) solid solution region were performed in the TEM in order to separate intergrowth and solid solubility effects. Most of the solid solubility is accounted for by changes in the Sr and Ca concentrations. Changes in the Bi concentration account for the rest. Based on these results, two substitution schemes were determined to occur. The first is just the interchange between Sr and Ca. The second involves the substitution of Bi for Sr or Ca. It appears to be unfavorable for Sr or Ca to substitute for Bi. The Cu content of the 2212 phase was found to be nearly constant. The 2212 phase was found with 12 other phases in this work, most of which were also solid solutions. Hence variations in the overall cation stoichiometry and oxygen partial pressure are accommodated by changes in (1) the amount, types, and composition of the secondary phases, (2) the number of intergrowths within the 2212 phase (apparent composition), and/or (3) the solid solution composition of the 2212 phase (actual composition). Crystallization of nominal 2212 glasses was found to proceed in two steps with the formation of Bi_2Sr_{2-x}Ca_ {x}CuO_{y} (2201) and Cu_2O followed by Bi_2Sr_{3-x}Ca_{x}O _{y}, CaO, and SrO. The 2212 phase converts from the 2201 phase with increasing temperatures and was kinetically limited by diffusion below 800 ^circC. At 800^circ 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. From the results of the solidification study, an eutectic was determined to separate the 2212/2201 phases that are stable at high oxygen partial pressures from the Bi_2Sr_{3-x}Ca _{x}O_{y} (23x) and rm Bi_2Sr_{2-x}Ca _{x}O_{y} (22x) phases present at low oxygen partial pressures. At high oxygen partial pressures, it was found that the separation of CaO in the melt and the initial crystallization of alkaline

  5. Phase equilibria of a low S and C lunar core: Implications for an early lunar dynamo and physical state of the current core

    NASA Astrophysics Data System (ADS)

    Righter, K.; Go, B. M.; Pando, K. A.; Danielson, L.; Ross, D. K.; Rahman, Z.; Keller, L. P.

    2017-04-01

    Multiple lines of geochemical and geophysical evidence suggest the Moon has a small metallic core, yet the composition of the core is poorly constrained. The physical state of the core (now or in the past) depends on detailed knowledge of its composition, and unfortunately, there is little available data on relevant multicomponent systems (i.e., Fe-Ni-S-C) at lunar interior conditions. In particular, there is a dearth of phase equilibrium data to elucidate whether a specific core composition could help to explain an early lunar geodynamo and magnetic field intensities, or current solid inner core/liquid outer core states. We utilize geochemical information to estimate the Ni, S and C contents of the lunar core, and then carry out phase equilibria experiments on several possible core compositions at the pressure and temperature conditions relevant to the lunar interior. The first composition is 0.5 wt% S and 0.375 wt% C, based on S and C contents of Apollo glasses. A second composition contains 1 wt% each of S and C, and assumes that the lunar mantle experienced degassing of up to 50% of its S and C. Finally a third composition contains C as the dominant light element. Phase equilibrium experiments were completed at 1, 3 and 5 GPa, using piston cylinder and multi-anvil techniques. The first composition has a liquidus near 1550 °C and solidus near 1250 °C. The second composition has a narrower liquidus and solidus temperatures of 1400 and 1270 °C, respectively, while the third composition is molten down to 1150 °C. As the composition crystallizes, the residual liquid becomes enriched in S and C, but S enrichment is greater due to the incorporation of C (but not S) into solid metallic FeNi. Comparison of these results to thermal models for the Moon allow an evaluation of which composition is consistent with the geophysical data of an early dynamo and a currently solid inner and liquid outer core. Composition 1 has a high enough liquidus to start crystallizing

  6. Correction of magnetooptic device phase errors in optical correlators through filter design modifications

    NASA Technical Reports Server (NTRS)

    Downie, John D.; Reid, Max B.; Hine, Butler P.

    1991-01-01

    We address the problem of optical phase errors in an optical correlator introduced by the input and filter plane spatial light modulators. Specifically, we study a laboratory correlator with magnetooptic spatial light modulator (MOSLM) devices. We measure and characterize the phase errors, analyze their effects on the correlation process, and discuss a means of correction through a design modification of the binary phase-only optical filter function. The phase correction technique is found to produce correlation results close to those of an error-free correlator.

  7. 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).

  8. Monte Carlo simulations of 1,3,5-triamino-2,4,6-trinitrobenzene (TATB): Pressure and temperature effects for the solid phase and vapor-liquid phase equilibria.

    PubMed

    Rai, Neeraj; Bhatt, Divesh; Siepmann, J Ilja; Fried, Laurence E

    2008-11-21

    The transferable potentials for phase equilibria (TraPPE) force field was extended to nitro and amino substituents for aromatic rings via parametrization to the vapor-liquid coexistence curves of nitrobenzene and aniline, respectively. These groups were then transferred to model 1,3,5-triamino-2,4,6-trinitrobenzene (TATB). Without any further parametrization to solid state data, the TraPPE force field is able to predict TATB's unit cell lengths and angles at 295 K with mean unsigned percentage errors of 0.3% and 1.8% and the specific density within 0.5%. These predictions are comparable in accuracy to the GRBF model [Gee et al., J. Chem. Phys. 120, 7059 (2004)] that was parametrized directly to TATB's solid state properties. Both force fields are able to reproduce the pressure dependence of TATB's unit cell volume, but they underestimate its thermal expansion. Due to its energetic nature and unusually large cohesive energy, TATB is not chemically stable at temperature in its liquid range. Gibbs ensemble simulations allow one to determine TATB's vapor-liquid coexistence curve at elevated temperatures and the predicted critical temperature and density for the TraPPE and GRBF model are 937+/-8 and 1034+/-8 K, and 0.52+/-0.02 and 0.50+/-0.02 gcm(3), respectively.

  9. Effect of silica gel modification with cyclofructans on properties of hydrophilic interaction liquid chromatography stationary phases.

    PubMed

    Kozlík, Petr; Símová, Veronika; Kalíková, Květa; Bosáková, Zuzana; Armstrong, Daniel W; Tesařová, Eva

    2012-09-28

    Hydrophilic interaction liquid chromatography (HILIC) offers very good possibilities for separation of polar compounds as an alternative to reversed phase HPLC where polar compounds are not sufficiently retained. HILIC is becoming more popular for the analysis of biologically interesting (active) analytes. Various stationary phases are commercially available however, development of new materials (sorbents) suitable for HILIC systems still continues. Silica gel columns can be used directly but their modification can improve separation ability of the stationary phases. Cyclofructan-based stationary phases are demonstrated as possible HILIC columns in this work. The effect of silica gel modification by cyclofructan and a derivatized cyclofructan was studied in detail. HILIC separation systems with silica gel, cyclofructan and isopropyl cyclofructan modified silica stationary phases were compared. The detailed study of chromatographic behavior of peptides revealed that multimodal retention mechanism is present in systems with these stationary phases. Mobile phase composition changes the types of interactions and their strengths. It appears that ability to donate protons and dispersion forces are the main interactions that affect retention in HILIC with cyclofructan-based columns while they are less important in separation systems with bare silica stationary phase. Suitability of cyclofructan-based stationary phases in HILIC for separation of pentapeptides and nonapeptides was demonstrated.

  10. Phase equilibria and crystal chemistry in portions of the system SrO-CaO-Bi2O3-CuO, part 2 - the system SrO-Bi2O3-CuO

    SciTech Connect

    Roth, R.S.; Rawn, C.J.; Burton, B.P.; Beech, F.

    1990-01-01

    New data are presented on the phase equilibria and crystal chemistry of the binary systems SrO-Bi2O3 and SrO-CuO and the ternary system SrO-Bi2O3-CuO. Symmetry data and unit cell dimensions based on single crystal and powder x-ray diffraction measurement are reported for all the binary SrO-Bi2O3 phases, including a new phase identified as Sr6Bi2O9. The ternary system contains at least four ternary phases which can be formed in air at about 900 C. These are identified as Sr2Bi2CuO6, Sr8Bi4Cu5O(19 + x) Sr3Bi2Cu2O8 and a solid solution (the Raveau phase) which, For equilibrium conditions at about 900 C, corresponds approximately to the formula Sr(1.8-x)Bi(22+x)Cu(1 + or - x/2)Oz(0.0 = or < about 0.15). Superconductivity in the phase apparently occurs only in compositions that correspond to negative values of x. Compositions that lie outside the equilibrium Raveau-phase field often form nearly homogenous Raveau-phase products. Typically this occurs after relatively brief heat treatments, or in crystallization of a quenched melt.

  11. Phase Equilibria and Crystal Chemistry in Portions of the System SrO-CaO-Bi2O3-CuO, Part II—The System SrO-Bi2O3-CuO

    PubMed Central

    Roth, R. S.; Rawn, C. J.; Burton, B. P.; Beech, F.

    1990-01-01

    New data are presented on the phase equilibria and crystal chemistry of the binary systems Sr0-Bi203 and SrO-CuO and the ternary system SrO-Bi2O3-CuO. Symmetry data and unit cell dimensions based on single crystal and powder x-ray diffraction measurements are reported for all the binary SrO-Bi2O3 phases, including a new phase identified as Sr6Bi2O9. The ternary system contains at least four ternary phases which can be formed in air at ~900 °C. These are identified as Sr2Bi2CuO6, Sr8Bi4Cu5O19+x, Sr3Bi2Cu2O8 and a solid solution (the Raveau phase) which, for equilibrium conditions at ~900 °C, corresponds approximately to the formula Sr1.8−xBi2.2+xCu1±x/2Oz.(0.0⩽x⩽~0.15). Superconductivity in this phase apparently occurs only in compositions that correspond to negative values of x. Compositions that lie outside the equilibrium Raveau-phase field often form nearly homogeneous Raveau-phase products. Typically this occurs after relatively brief heat treatments, or in crystallization of a quenched melt. PMID:28179779

  12. 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.

  13. Phase equilibria modeling applied to fluid inclusions: Liquid-vapor equilibria and calculation of the molar volume in the CO[sub 2]-CH[sub 4]-N[sub 2] system

    SciTech Connect

    Thiery, R.; Dubessy, J. ); Vidal, J. )

    1994-02-01

    Quantitative use of fluid inclusions requires the determination of composition and molar volume. The molar volume can be calculated in the CO[sub 2]-CH[sub 4]N[sub 2] system from both the determination of the temperature of a L + V [yields] L (or V) equilibrium if the composition is known independently, provided an equation of state (EOS) reproduces the P-V-T-X properties of each phase at equilibrium. This study is applicable to fluids for which the sequence of phase transition is S[sub CO2] + L + V [yields] L + V [yields] L (or V) at increasing temperature. The molar volume is determined by following a two-step algorithm: (1) the pressure is calculated from a two-parameter cubic EOS with interaction parameters optimized along experimental L-V isotherms (2) the molar volume is then calculated by the correlation of LEE and KESLER (1975) with the pressure calculated in the first step. Projections of polybaric L-V isotherms in [upsilon]-X diagrams of the CO[sub 2]-CH[sub 4], CO[sub 2]-N[sub 2], and CH[sub 4]-N[sub 2] systems can be directly applied to fluid inclusion studies. In addition, it is shown that the molar volume of CO[sub 2]-rich fluids (X[sub CO2] > 0.6) in the ternary system can be estimated with sufficient accuracy using empirical formulae relating to the [upsilon]-X diagrams of the CO[sub 2]-CH[sub 4] and CO[sub 2]-N[sub 2] binary systems.

  14. Shifting Phases for Patchy Particles - Effect of mutagenesis and chemical modification on the phase diagram of human gamma D crystallin

    NASA Astrophysics Data System (ADS)

    McManus, Jennifer J.; James, Susan; McNamara, Ruth; Quinn, Michelle

    2014-03-01

    Single mutations in human gamma D crystallin (HGD), a protein found in the eye lens are associated with several childhood cataracts. Phase diagrams for several of these protein mutants have been measured and reveal that phase boundaries are shifted compared with the native protein, leading to condensation of protein in a physiologically relevant regime. Using HGD as a model protein, we have constructed phase diagrams for double mutants of the protein, incorporating two single amino acid substitutions for which phase diagrams are already known. In doing so, the characteristics of each of the single mutations are maintained but both are now present in the same protein particle. While these proteins are not of interest physiologically, this strategy allows the controlled synthesis of nano-scale patchy particles in which features associated with a known phase behavior can be included. It can also provide a strategy for the controlled crystallisation of proteins. Phase boundaries also change after the chemical modification of the protein, through the covalent attachment of fluorescent labels, for example, and this will also be discussed. The authors acknowledge Science Foundation Ireland Stokes Lectureship and Grant 11/RFP.1/PHY/3165. The authors also acknowledge the Irish Research Council and the John and Pat Hume Scholarship.

  15. Strategies for the Gas Phase Modification of Cationized Arginine via Ion/ion Reactions.

    PubMed

    Prentice, Boone M; McGee, William M; Stutzman, John R; McLuckey, Scott A

    2013-11-15

    The gas phase acetylation of cationized arginine residues is demonstrated here using ion/ion reactions with sulfosuccinimidyl acetate (sulfo-NHS acetate) anions. Previous reports have demonstrated the gas phase modification of uncharged primary amine (the N-terminus and ε-amino side chain of lysine) and uncharged guanidine (the arginine side chain) functionalities via sulfo-NHS ester chemistry. Herein, charge-saturated arginine-containing peptides that contain sodium ions as the charge carriers, such as [ac-ARAAARA+2Na](2+), are shown to exhibit strong reactivity towards sulfo-NHS acetate whereas the protonated peptide analogues exhibit no such reactivity. This difference in reactivity is attributed to the lower sodium ion (as compared to proton) affinity of the arginine, which results in increased nucleophilicity of the cationized arginine guanidinium functionality. This increased nucleophilicity improves the arginine residue's reactivity towards sulfo-NHS esters and enhances the gas phase covalent modification pathway. No such dramatic increase in reactivity towards sulfo-NHS acetate has been observed upon sodium cationization of lysine amino acid residues, indicating that this behavior appears to be unique to arginine. The sodium cationization process is demonstrated in the condensed phase by simply spiking sodium chloride into the peptide sample solution and in the gas phase by a peptide-sodium cation exchange process with a sulfo-NHS acetate sodium-bound dimer cluster reagent. This methodology demonstrates several ways by which arginine can be covalently modified in the gas phase even when it is charged. Collisional activation of an acetylated arginine product can result in deguanidination of the residue, generating an ornithine. This gas phase ornithination exhibits similar site-specific fragmentation behavior to that observed with peptides ornithinated in solution and may represent a useful approach for inducing selective peptide cleavages.

  16. Reagent Cluster Anions for Multiple Gas-phase Covalent Modifications of Peptide and Protein Cations

    PubMed Central

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

    2013-01-01

    Multiple gas phase ion/ion covalent modifications of peptide and protein ions are demonstrated here using cluster-type reagent anions of N-hydroxysulfosuccinimide acetate (sulfo-NHS acetate) and 2-formyl-benzenesulfonic acid (FBMSA). These reagents are used here 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 anions which, upon collisional activation, produced fragment ions with various numbers of modifications. Data for the pentamer cluster are included here as illustrative of the results obtained for the clusters comprised of 2–6 reagent molecules. PMID:23702708

  17. 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.

  18. Phase Equilibria Studies in the System ZnO-``FeO''-Al2O3-CaO-SiO2 Relevant to Imperial Smelting Furnace Slags: Part II

    NASA Astrophysics Data System (ADS)

    Zhao, Baojun; Hayes, Peter C.; Jak, Evgueni

    2010-04-01

    The phase equilibria and the liquidus temperatures in the system ZnO-“FeO”-Al2O3-CaO-SiO2 have been determined experimentally in equilibrium with metallic iron. Specifically, the effects of Al2O3 concentrations in Imperial Smelting Furnace slags are identified, and the results are presented in the form of pseudo-ternary sections ZnO-“FeO”-(Al2O3 + CaO + SiO2) in which CaO/SiO2 = 0.93 and (CaO + SiO2)/Al2O3 = 5.0 and 3.5, respectively. It was found that, in the presence of Al2O3, the spinel phase is formed, the spinel primary phase field expands, and the wustite and melilite primary phase fields are reduced in size with an increasing Al2O3 concentration. The implications of the findings to industrial practice are discussed.

  19. 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).

  20. Inverse plasma equilibria

    SciTech Connect

    Hicks, H.R.; Dory, R.A.; Holmes, J.A.

    1983-01-01

    We illustrate in some detail a 2D inverse-equilibrium solver that was constructed to analyze tokamak configurations and stellarators (the latter in the context of the average method). To ensure that the method is suitable not only to determine equilibria, but also to provide appropriately represented data for existing stability codes, it is important to be able to control the Jacobian, tilde J is identical to delta(R,Z)/delta(rho, theta). The form chosen is tilde J = J/sub 0/(rho)R/sup l/rho where rho is a flux surface label, and l is an integer. The initial implementation is for a fixed conducting-wall boundary, but the technique can be extended to a free-boundary model.

  1. Programmed functionalization of SURMOFs via liquid phase heteroepitaxial growth and post-synthetic modification.

    PubMed

    Tu, Min; Wannapaiboon, Suttipong; Fischer, Roland A

    2013-12-07

    Heterostructured surface mounted metal-organic frameworks (SURMOFs) [Cu2(NH2-bdc)2(dabco)] (B) on top of [Cu2(bdc)2(dabco)] (A) were deposited on pyridyl-terminated Au covered QCM substrate using a step-by-step liquid phase epitaxial growth method. Sequentially, the pore size of the top layer [Cu2(NH2-bdc)2(dabco)] (B) was modified by targeting the installed amino moiety with tert-butyl isothiocyanate (tBITC). The adsorption properties of the programmed functionalized SURMOFs studied using an environment controlled quartz crystal microbalance (QCM) instrument exhibited the possibility to achieve high selectivity and capacity by heteroepitaxial growth and post-synthetic modification.

  2. Phase Equilibria in the System "FeO"-CaO-SiO2-Al2O3-MgO at Different CaO/SiO2 Ratios

    NASA Astrophysics Data System (ADS)

    Jang, Kyoung-oh; Ma, Xiaodong; Zhu, Jinming; Xu, Haifa; Wang, Geoff; Zhao, Baojun

    2017-03-01

    The "FeO"-containing slags play an important role in the operation of an ironmaking blast furnace (BF), in particular the primary slags such as the system "FeO"-CaO-SiO2-Al2O3-2 mass pct MgO with CaO/SiO2 weight ratios of 1.3, 1.5, and 1.8 saturated with metallic iron. To investigate the characteristics of such a slag system and its behavior in BF, the phase equilibria and liquidus temperatures in the slag system have been experimentally determined using the high-temperature equilibration and quenching technique followed by an electron probe X-ray microanalysis (EPMA). Isotherms between 1553 K and 1603 K (1280 °C and 1330 °C) were determined in the primary phase fields of dicalcium silicate, melilite, spinel, and monoxide [(Mg,Fe2+)O]. Pseudo-ternary phase diagrams of (CaO + SiO2)-Al2O3-"FeO" with a fixed MgO concentration at 2 mass pct and at CaO/SiO2 ratios of 1.3, 1.5, and 1.8 have been discussed, respectively, simplifying the complexity of the slag system for easy understanding and applying in BF operation. It was found that the liquidus temperatures increase in melilite and spinel primary phase fields, but decrease in dicalcium silicate and monoxide primary phase fields with increasing Al2O3/(CaO + SiO2) ratio. In addition, the liquidus temperatures decrease with increasing "FeO" concentration in dicalcium silicate and melilite primary phase fields, while showing an increasing trend in the spinel and monoxide primary phase fields. The data resulted from this study can be used to improve and optimize currently available database of thermodynamic models used in FactSage.

  3. 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

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

    PubMed

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

    2012-09-04

    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%).

  5. Global histone modification fingerprinting in human cells using epigenetic reverse phase protein array

    PubMed Central

    Partolina, Marina; Thoms, Hazel C; MacLeod, Kenneth G; Rodriguez-Blanco, Giovanny; Clarke, Matthew N; Venkatasubramani, Anuroop V; Beesoo, Rima; Larionov, Vladimir; Neergheen-Bhujun, Vidushi S; Serrels, Bryan; Kimura, Hiroshi; Carragher, Neil O; Kagansky, Alexander

    2017-01-01

    The balance between acetylation and deacetylation of histone proteins plays a critical role in the regulation of genomic functions. Aberrations in global levels of histone modifications are linked to carcinogenesis and are currently the focus of intense scrutiny and translational research investments to develop new therapies, which can modify complex disease pathophysiology through epigenetic control. However, despite significant progress in our understanding of the molecular mechanisms of epigenetic machinery in various genomic contexts and cell types, the links between epigenetic modifications and cellular phenotypes are far from being clear. For example, enzymes controlling histone modifications utilize key cellular metabolites associated with intra- and extracellular feedback loops, adding a further layer of complexity to this process. Meanwhile, it has become increasingly evident that new assay technologies which provide robust and precise measurement of global histone modifications are required, for at least two pressing reasons: firstly, many approved drugs are known to influence histone modifications and new cancer therapies are increasingly being developed towards targeting histone deacetylases (HDACs) and other epigenetic readers and writers. Therefore, robust assays for fingerprinting the global effects of such drugs on preclinical cell, organoid and in vivo models is required; and secondly, robust histone-fingerprinting assays applicable to patient samples may afford the development of next-generation diagnostic and prognostic tools. In our study, we have used a panel of monoclonal antibodies to determine the relative changes in the global abundance of post-translational modifications on histones purified from cancer cell lines treated with HDAC inhibitors using a novel technique, called epigenetic reverse phase protein array. We observed a robust increase in acetylation levels within 2–24 h after inhibition of HDACs in different cancer cell lines

  6. Code System to Model Aqueous Geochemical Equilibria.

    SciTech Connect

    PETERSON, S. R.

    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 mass 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.

  7. 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.

  8. 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.

  9. Femtosecond laser modification of an array of vertically aligned carbon nanotubes intercalated with Fe phase nanoparticles.

    PubMed

    Labunov, Vladimir; Prudnikava, Alena; Bushuk, Serguei; Filatov, Serguei; Shulitski, Boris; Tay, Beng Kang; Shaman, Yury; Basaev, Alexander

    2013-09-03

    Femtosecond lasers (FSL) are playing an increasingly important role in materials research, characterization, and modification. Due to an extremely short pulse width, interactions of FSL irradiation with solid surfaces attract special interest, and a number of unusual phenomena resulted in the formation of new materials are expected. Here, we report on a new nanostructure observed after the interaction of FSL irradiation with arrays of vertically aligned carbon nanotubes (CNTs) intercalated with iron phase catalyst nanoparticles. It was revealed that the FSL laser ablation transforms the topmost layer of CNT array into iron phase nanospheres (40 to 680 nm in diameter) located at the tip of the CNT bundles of conical shape. Besides, the smaller nanospheres (10 to 30 nm in diameter) are found to be beaded at the sides of these bundles. Some of the larger nanospheres are encapsulated into carbon shells, which sometime are found to contain CNTs. The mechanism of creation of such nanostructures is proposed.

  10. Experimental phasing with SHELXC/D/E: combining chain tracing with density modification.

    PubMed

    Sheldrick, George M

    2010-04-01

    The programs SHELXC, SHELXD and SHELXE are designed to provide simple, robust and efficient experimental phasing of macromolecules by the SAD, MAD, SIR, SIRAS and RIP methods and are particularly suitable for use in automated structure-solution pipelines. This paper gives a general account of experimental phasing using these programs and describes the extension of iterative density modification in SHELXE by the inclusion of automated protein main-chain tracing. This gives a good indication as to whether the structure has been solved and enables interpretable maps to be obtained from poorer starting phases. The autotracing algorithm starts with the location of possible seven-residue alpha-helices and common tripeptides. After extension of these fragments in both directions, various criteria are used to decide whether to accept or reject the resulting poly-Ala traces. Noncrystallographic symmetry (NCS) is applied to the traced fragments, not to the density. Further features are the use of a 'no-go' map to prevent the traces from passing through heavy atoms or symmetry elements and a splicing technique to combine the best parts of traces (including those generated by NCS) that partly overlap.

  11. Cross-phase Modification: A mechanism for the I-mode and other enhanced confinement regimes?

    NASA Astrophysics Data System (ADS)

    Newman, David; Terry, Paul; Sanchez, Raul; Bustos, A.

    2016-10-01

    New confinement regimes such as the I-mode offer good confinement properties with reduced density limit issues and better control. Previously, a number of different mechanisms have been identified for the formation and maintenance of enhanced confinement regimes. However, few if any allow enhanced confinement in one channel but not another as is seen in the I-mode. We propose modifications of cross-phases as a possible mechanism for different transport in different channels. Using simple dynamical models which have been able to capture a remarkable amount of the dynamics of the core and edge transport barriers found in many devices, we add cross phase to investigate the new mechanism. To this basic 7 field transport framework a simple model for phase effects, due to multiple instabilities, between the transported fields such as density and temperature is added with which we can investigate whether the dynamics of more continuous transitions such as the I-mode can be captured and understood. It can. This is backed up by multi-scale simulations on full gyro-kinetic codes. We then look at the question: If this mechanism is valid, what can the model tell us about control knobs for these promising regimes? Work supported by DOE Grant DE-FG02-04ER54741.

  12. Equilibria bearing on the behavior of titanate phases during crystallization of iron silicate melts under strongly reducing conditions. [in lunar rocks

    NASA Technical Reports Server (NTRS)

    Lipin, B. R.; Muan, A.

    1974-01-01

    Titanate phase relations at liquidus temperatures are determined for the CaAl2Si2O8-Fe2TiO4-FeTi2O5 system in contact with metallic iron by reflected- and transmitted-light microscopy, electron microprobe, and X-ray diffraction analyses. Results of critical equilibration runs are presented, various primary phase areas and liquidus isotherms are illustrated, and the geometry of the system is described. Three piercing points are determined, and it is noted that the compositional interrelations among coexisting crystalline and liquid phases as well as the sequence of the various titanate phases are indicative of the significant effects of the various cations on the relative stability of these phases. It is found that Al2O3 exerts a strong stabilizing effect on the phase assemblage of ulvospinel plus ferropseudobrookite relative to ilemite.

  13. Phase equilibria and molecular packing in the N,N-dimethyldodecylamine oxide/gramicidin D/water system studied by 2H nuclear magnetic resonance spectroscopy.

    PubMed Central

    Orädd, G; Lindblom, G; Arvidson, G; Gunnarsson, K

    1995-01-01

    A partial phase diagram of the system N,N-dimethyldodecylamine oxide (DDAO)/water/gramicidin D was determined by 2H-NMR. Both 2H2O and perdeuterated DDAO (DDAO-d31) were studied by solid state NMR techniques. Addition of gramicidin D to the micellar (L1), normal hexagonal (HI) and cubic (I) phases of DDAO induces phase separations, giving two-phase regions, which all contain a lamellar (L alpha) phase. The L alpha phase containing gramicidin is characterized by larger order parameters for DDAO-d31 compared with the corresponding order parameters in the L alpha and HI phases of DDAO-d31/H2O. The L alpha phase may stay in equilibrium with any other phase in the phase diagram. The DDAO exchange between the coexisting phases is slow on the NMR timescale, which is why the recorded NMR spectrum consists of superimposed spectra from the different phases occurring in the sample. Gramicidin D can be solubilized in appreciable quantities only in the lamellar phase of DDAO-d31. Increasing amounts of gramicidin in the liquid crystalline phases result in a continuous increase in the molecular ordering up to about 5 mol% gramicidin, where a plateau is reached. This is consistent with a recent theoretical model describing the influence on the ordering of lipids by a membrane protein with larger hydrophobic thickness than the lipid bilayer. The solvent used for dissolving gramicidin at the incorporation of the peptide in the lipid aggregates has no effect on the 2H-NMR lineshapes of DDAO-d31. It is concluded that gramicidin is solubilized in the L alpha phase and that it always adopts the channel conformation independent of a particular solvent. The channel conformation is also supported by CD studies. In some of the samples, macroscopic orientation of the lipid aggregates is observed. It is concluded that DDAO-d31 in the binary system favors an orientation with the long axis of the hydrocarbon chain perpendicular to the magnetic field, whereas when gramicidin D is present the

  14. 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.

  15. 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.

  16. Two- and three-phase equilibria of polydisperse Yukawa hard-sphere fluids confined in random porous media: high temperature approximation and scaled particle theory.

    PubMed

    Hvozd, Taras V; Kalyuzhnyi, Yurij V

    2017-02-15

    We have studied the phase behavior of polydisperse Yukawa hard-sphere fluid confined in random porous media using extension and combination of high temperature approximation and scaled particle theory. The porous media are represented by the matrix of randomly placed hard-sphere obstacles. Due to the confinement, polydispersity effects are substantially enhanced. At an intermediate degree of fluid polydispersity and low density of the matrix, we observe two-phase coexistence with two critical points, and cloud and shadow curves forming closed loops of ellipsoidal shape. With the increase of the matrix density and the constant degree of polydispersity, these two critical points merge and disappear, and at lower temperatures the system fractionates into three coexisting phases. A similar phase behavior was observed in the absence of the porous media caused, however, by the increase of the polydispersity.

  17. In situ high temperature X-Ray diffraction study of the phase equilibria in the UO2-PuO2-Pu2O3 system

    NASA Astrophysics Data System (ADS)

    Belin, Renaud C.; Strach, Michal; Truphémus, Thibaut; Guéneau, Christine; Richaud, Jean-Christophe; Rogez, Jacques

    2015-10-01

    The region of the U-Pu-O phase diagram delimited by the compounds UO2-PuO2-Pu2O3 is known to exhibit a miscibility gap at low temperature. Consequently, MOX fuels with a composition entering this region could decompose into two fluorite phases and thus exhibit chemical heterogeneities. The experimental data on this domain found in the literature are scarce and usually provided using DTA that is not suitable for the investigation of such decomposition phenomena. In the present work, new experimental data, i.e. crystallographic phases, lattice parameters, phase fractions and temperature of phase separation, were measured in the composition range 0.14 < Pu/(U + Pu) < 0.62 and 1.85 < O/(U + Pu) < 2 from 298 to 1750 K using a novel in situ high temperature X-ray diffraction apparatus. A very good agreement is found between the temperature of phase separation determined from our results and using the thermodynamic model of the U-Pu-O system based on the CALPHAD method. Also, the combined use of thermodynamic calculations and XRD results refinement proved helpful in the determination of the O/M ratio of the samples during cooling. The methodology used in the current work might be useful to investigate other oxides systems exhibiting a miscibility gap.

  18. 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.

  19. 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

  20. 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.

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

    DOE PAGES

    Podesta, M.; Gorelenkova, M.; Fredrickson, E. D.; ...

    2016-07-22

    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 effectivemore » 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. Furthermore, those important aspects are only qualitatively captured by simpler fast ion transport models that are based on radial diffusion of energetic ions only.« less

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

    SciTech Connect

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

    2016-07-22

    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. Furthermore, those important aspects are only qualitatively captured by simpler fast ion transport models that are based on radial diffusion of energetic ions only.

  3. Three-phase solid-liquid-vapor equilibria in the binary hydrocarbon systems methane-n-hexane and methane-benzene

    SciTech Connect

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

    1981-10-01

    Pressure, temperature, liquid-phase compositions, and liquid-phase molar volumes are presented along the solid-liquid-vapor (SLV) loci of the binary systems methane-n-hexane and methane-benzene. The data were taken by using cryoscopic techniques and are compared to the solid-liquid (SL) data at elevated pressures of Kuebler and McKinley. The standard deviations of the smoothed SLV data for liquid-phase solute composition presented herein from the raw SLV data are 3.7% for the methane-n-hexane system and 8.6% for the low-temperature branch of the methane-benzene system. The corresponding standard deviation for the high-temperature (high solute composition) branch for the system methane-benzene is less than 0.7%. 8 refs.

  4. Correct Representation of Conformational Equilibria.

    ERIC Educational Resources Information Center

    Fulop, F.; And Others

    1983-01-01

    In representing conformational equilibria of compounds having only one chiral center, erroneous formulas showing different antipodes on the two sides of the equilibrium are rare. In contrast, with compounds having two or more chiral centers especially with saturated heterocycles, this erroneous representation occurs frequently in the chemical…

  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

    DOE PAGES

    East, William E.; Zrake, Jonathan; Yuan, Yajie; ...

    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

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

    PubMed

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

    2015-05-07

    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.

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

    SciTech Connect

    Not Available

    1991-01-02

    Liquid-entrained operations at the LaPorte Liquid Phase Methanol (LPMEOH) Process Development Unit (PDU) continued during June and July 1988 under Tasks 2.1 and 2.2 of Contract No. DE-AC22-87PC90005 for the US Department of Energy. The primary focus of this PDU operating program was to prepare for a confident move to the next scale of operation with an optimized and simplified process. Several new design options had been identified and thoroughly evaluated in a detailed process engineering study completed under the LPMEOH Part-2 contract (DE-AC22-85PC80007), which then became the basis for the current PDU modification/operating program. The focus of the Process Engineering Design was to optimize and simplifications focused on the slurry loop, which consists of the reactor, vapor/liquid separator, slurry heat exchanger, and slurry circulation pump. Two-Phase Gas Holdup tests began at LaPorte in June 1988 with nitrogen/oil and CO- rich gas/oil systems. The purpose of these tests was to study the hydrodynamics of the reactor, detect metal carbonyl catalyst poisons, and train operating personnel. Any effect of the new gas sparger and the internal heat exchanger would be revealed by comparing the hydrodynamic data with previous PDU hydrodynamic data. The Equipment Evaluation'' Run E-5 was conducted at the LaPorte LPMEOH PDU in July 1988. The objective of Run E-5 was to systematically evaluate each new piece of equipment (sparger, internal heat exchanger, V/L disengagement zone, demister, and cyclone) which had been added to the system, and attempt to run the reactor in an internal-only mode. In addition, a successful catalyst activation with a concentrated (45 wt % oxide) slurry was sought. 9 refs., 26 figs., 15 tabs.

  9. 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.

  10. Phase equilibria in subseafloor hydrothermal systems: A review of the role of redox, temperature, pH and dissolved Cl on the chemistry of hot spring fluids at mid-ocean ridges

    NASA Astrophysics Data System (ADS)

    Seyfried, W. E., Jr.; Ding, Kang

    Time series measurements of the chemistry of hot spring fluids at mid-ocean ridges (MOR) have revealed steady state concentrations of dissolved species that indicate solubility control by mineral phases in subseafloor reaction zones [Campbell et al., 1988a; Bowers et al., 1988; Butterfield et al. 1994]. That MOR hot spring fluids have relatively low measured pH values (3.1 to 3.9), and are variably depleted in Mg and SO4, while enriched in Ca, K, and Si [Von Damm, 1990] relative to seawater, is entirely consistent with heterogeneous equilibria involving feldspar, chlorite, epidote ± quartz and NaCl fluids at temperatures in the vicinity of 375-400°C [Seyfried et al., 1991]. The high concentrations of so-called "soluble" elements, such as Li, Rb, Cs, and B [Von Damm et al., 1985; Spivack and Edmond, 1987], however, require an abundance of fresh rock (basalt/diabase) relative to the mass of seawater (i.e., low fluid/rock ratio). That these elements also fall to reveal significant compositional changes in fluids from specific hot springs sampled several times over a six year period [Campbell et al., 1985a; Butterfield et al. 1994; Butterfield and Massoth 1994] indicates a non-static and expanding reaction zone caused by penetration of seawater into previously unaltered portions of a solidified magma chamber. Although most vent fluids reveal short term stability [Campbell et al. 1988a; Butterfield and Massoth 1994], this is not always the case, as evidenced by the temporal evolution of the composition of vent fluids at the North Cleft segment of the Juan de Fuca Ridge [Butterfield et al. 1991; Butterfield and Massoth, 1994], and at 9-10degN EPR [Von Damm et al. 1991].

  11. 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.

  12. 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}.

  13. Phase equilibria in the system Nd2O3- P2O5- H2O and growth of NdP5O14 single crystals under hydrothermal conditions

    NASA Astrophysics Data System (ADS)

    Yoshimura, Masahiro; Fujii, Kazutaka; Sōmiya, Shigeyuki

    1985-04-01

    Phase equilibria in the system Nd2O3- P2O5- H2O were determined under hydrothermal conditions at 500 and 350°C under 100 MPa by quenching techniques. There exist three types of neodymium phosphates: NdPO 4, NdP 3O 9 and NdP 5O 14, and a liquid phase of highly condensed phosphoric acid at both temperatures. The composition of the liquid phase with which NdP 5O 14 and NdP 3O 9 or NdP 3O 9 and NdPO 4 could coexist at 500°C was 3% Nd2O3-80% P2O5-17% H2O or 4% Nd2O3-74% P2O5 -22% H2O respectively, while that at 350°C changed to 2% Nd2O3-78% P2O5-20% H2O or 2% Nd2O3-75% P2O5-23% H2O respectively. These results indicate that the solubility curve of NdP 5O 14 had a positive slope against temperature, which allowed us to apply a temperature gradient method for the crystal growth of NdP 5O 14. Polyhedral crystals of 0.5 mm in maximum size were grown at the upper part of a gold capsule ( T⋍400°C) through the transportation due to Δ T=100°C after 10 days. These crystals had flat and smooth surfaces and contained less bubble-shaped inclusions than crystals synthesized under isothermal conditions. Crystals obtained at the lower part of the gold capsule ( T=500°C) were polyhedral 1 mm in maximum size. Growth experiments with Δ T=50°C yielded no crystals at the upper part in the capsule ( T⋍450°C), probably due to an insufficient transportation.

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

    DOE PAGES

    Wong-Ng, W.; Laws, W.; Lapidus, S. H.; ...

    2015-06-27

    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,more » (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). Lastly, ten solid solution tie-line regions and six three-phase regions were determined in the CaO–½Sm2O3–CoOz system in air.« less

  15. The hydrous phase equilibria (to 3 kbar) of an andesite and basaltic andesite from western Mexico: constraints on water content and conditions of phenocryst growth

    NASA Astrophysics Data System (ADS)

    Moore, Gordon; Carmichael, I. S. E.

    We have conducted high pressure (to 3 kbar), water saturated melting experiments on an andesite (62 wt% SiO2) and a basaltic andesite (55 wt% SiO2) from western Mexico. A close comparison between the experimental phase assemblages and their compositions, and the phenocryst assemblages of the lavas, is found in water saturated liquids, suggesting that the CO2 content was minimal in the fluid phase. Thus the historic lavas from Volcan Colima (with phenocrysts of orthopyroxene, augite, plagioclase, and hornblende) were stored at a temperature between 950-975°C, at a pressure between 700-1500 bars, and with a water content of 3.0-5.0 wt%. A hornblende andesite (spessartite) from Mascota, of nearly identical composition but with only amphibole phenocrysts, had a similar temperature but equilibrated at a minimum of 2000 bars pressure with a dissolved water content of at least 5.5 wt% in the liquid. Experiments on the basaltic andesite show that the most common natural phenocryst assemblages (olivine, +/-augite, +/-plagioclase) could have precipitated at temperatures from 1000-1150°C, in liquids with a wide range of dissolved water content ( 2.0-6.0 wt%) and a corresponding pressure range. A lava of the same bulk composition with phenocrysts of hornblende, olivine, plagioclase, and augite is restricted to temperatures below 1000°C and pressures below 2500bars, corresponding to <5.5 wt% water in the residual liquid. Although there is some evidence for mixing in the andesites (sporadic olivine phenocrysts), the broad theme of the history of both lava types is that the phenocryst assemblages for both the andesitic magmas and basaltic andesitic magmas are generated from degassing and reequilibration on ascent of initially hydrous parents containing greater than 6 wt% water. Indeed andesitic magmas could be related to a basaltic andesite parent by hornblende-plagioclase fractionation under the same hydrous conditions.

  16. 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.

  17. Subsolidus phase equilibria and properties in the system Bi 2O 3:Mn 2O 3±x:Nb 2O 5

    NASA Astrophysics Data System (ADS)

    Vanderah, T. A.; Lufaso, M. W.; Adler, A. U.; Levin, I.; Nino, J. C.; Provenzano, V.; Schenck, P. K.

    2006-11-01

    Subsolidus phase relations have been determined for the Bi-Mn-Nb-O system in air (750-900 °C). Phases containing Mn 2+, Mn 3+, and Mn 4+ were all observed. Ternary compound formation was limited to pyrochlore (A 2B 2O 6O'), which formed a substantial solid solution region at Bi-deficient stoichiometries (relative to Bi 2(Mn,Nb) 2O 7) suggesting that ≈14-30% of the A-sites are occupied by Mn (likely Mn 2+). X-ray powder diffraction data confirmed that all Bi-Mn-Nb-O pyrochlores form with structural displacements, as found for the analogous pyrochlores with Mn replaced by Zn, Fe, or Co. A structural refinement of the pyrochlore 0.4000:0.3000:0.3000 Bi 2O 3:Mn 2O 3±x:Nb 2O 5 using neutron powder diffraction data is reported with the A and O' atoms displaced (0.36 and 0.33 Å, respectively) from ideal positions to 96g sites, and with Mn 2+ on A-sites and Mn 3+ on B-sites (Bi 1.6Mn 2+0.4(Mn 3+0.8Nb 1.2)O 7, Fd3¯m (♯227), a=10.478(1) Å); evidence of A or O' vacancies was not found. The displacive disorder is crystallographically analogous to that reported for Bi 1.5Zn 0.92Nb 1.5O 6.92, which has a similar concentration of small B-type ions on the A-sites. EELS spectra for this pyrochlore were consistent with an Mn oxidation between 2+ and 3+. Bi-Mn-Nb-O pyrochlores exhibited overall paramagnetic behavior with negative Curie-Weiss temperature intercepts, slight superparamagnetic effects, and depressed observed moments compared to high-spin, spin-only values. At 300 K and 1 MHz the relative dielectric permittivity of Bi 1.600Mn 1.200Nb 1.200O 7 was ≈128 with tan δ=0.05; however, at lower frequencies the sample was conductive which is consistent with the presence of mixed-valent Mn. Low-temperature dielectric relaxation such as that observed for Bi 1.5Zn 0.92Nb 1.5O 6.92 and other bismuth-based pyrochlores was not observed. Bi-Mn-Nb-O pyrochlores were readily obtained as single crystals and also as textured thin films using pulsed laser deposition.

  18. 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}.

  19. Outlook on the phase equilibria of the innovative system of "protected glycerol": 1,4-dioxaspiro[4.5]decane-2-methanol and alternative solvents.

    PubMed

    Melo, Catarina I; Rodrigues, Ana I; Bogel-Łukasik, Rafał; Bogel-Łukasik, Ewa

    2012-02-23

    Fundamental data on 1,4-dioxaspiro[4.5]decane-2-methanol are scarce. This work presents the foremost systematic data on the solubility of 1,4-dioxaspiro[4.5]decane-2-methanol in sustainable solvents such as water and ionic liquids accompanied by the interpretation of interactions occurring in such binary systems. 1,4-Dioxaspiro[4.5]decane-2-methanol, here called protected glycerol, has been synthesized in order to protect the two hydroxyl groups of glycerol, thus avoiding the formation of side products in a specific process. A series of imidazolium salts accompanied by pyridinium, phosphonium, and ammonium ones with various types of counterions were used in this study. The liquid-liquid and solid-liquid equilibrium measurements in binary systems were carried out by using a dynamic method at atmospheric pressure over the temperature range from 273.00 to 378.30 K or below the boiling point of the solvent. Among all tested sustainable solvents, protected glycerol exhibited limited solubility, with only a few of them in the temperature range studied. The majority of the examined ionic liquids, either hydrophilic or hydrophobic, showed complete miscibility with this monohydroxyol. The Fourier-transform infrared (FTIR) spectroscopy studies of solute and solvents showing a miscibility gap and of their mixtures were performed to obtain insight into major inter- and intramolecular interactions in the investigated systems. Furthermore, the differential scanning calorimetry was used for the first time to determine the melting point, the enthalpy of melting, and the temperature and enthalpy of the solid-solid phase transition of 1-allyl-3-methylimidazolium chloride [Amim][Cl]. The results for the solubility of protected glycerol in sustainable solvents can be used to design future alternative reactions, such as telomerization with protected glycerol in ionic liquids for more specific building blocks and extraction/or separation that involves these mixtures.

  20. 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

  1. 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)

  2. 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%.

  3. Phase Equilibria of Stored Chemical Energy Reactants.

    DTIC Science & Technology

    1984-07-25

    lithia were LL202 and Li2CO3 , respectively. The reagent grade carbonate , dried at 160 OC under vacuum and weighed in a dry box, could be used to prepare...Testing of sintered lithium aluminate structures in molten carbonate fuel cells: J. Electrochem. Soc., V. 127, No. 8, p. 1766-8. Sinyh, R. N.; Dusek, J. T...and Sim, J. W., 1981, Fabrication and properties of a porous lithium aluminate electrolyte retainer for molten carbonate fuel cells: Am. Ceram. Soc

  4. Free-boundary magnetohydrodynamic equilibria with flow

    NASA Astrophysics Data System (ADS)

    Schmitt, R. F.; Guazzotto, L.; Strauss, H.; Park, G. Y.; Chang, C.-S.

    2011-02-01

    The finite-element M3D code [W. Park et al., Phys. Plasmas 6, 1796 (1999)] has been modified to include a free-boundary equilibrium solver with arbitrary toroidal and poloidal flows. With this modification, the M3D code now has the capability to self-consistently model two essential ingredients necessary for equilibrium calculations in the edge region, namely, free-boundary and arbitrary flow. As a free-boundary code, M3D includes the separatrix and scrape-off layer regions in the equilibrium calculation. Poloidal flows in the subsonic, supersonic, and transonic regimes can be calculated with the new version of the M3D code. Calculation results show that the presence of equilibrium flows, in particular those next to the plasma boundary, can considerably influence the position of the X-point and magnetic separatrix shape/location and hence the position of the strike point on the divertor plates. Moreover, it is shown that poloidal flow is not a rigid-body rotation, with the fastest flows occurring on the inboard side of the plasma. A numerical confirmation of the "de Laval nozzle" model of Betti and Freidberg [R. Betti and J. P. Freidberg, Phys. Plasmas 7, 2439 (2000)] for free-boundary equilibrium calculations is obtained, with the formation of the predicted discontinuities between regions of subsonic and supersonic flows (with respect to the poloidal sound speed). Finally, a detailed comparison between isentropic and isothermal equilibria is presented, showing qualitative analogies and quantitative differences.

  5. Inefficiency of Nash Equilibria. I

    DTIC Science & Technology

    1982-03-12

    continuously for U’ near csEA a’ This also shows that for il close to , D6?’)(X) fl (IW’, f ) - * for a a hence we may assume U0 open.all * 6 A A Furthermore...34 Journal of Economic Theory 22 (1980), 363-376. 14] P. Dubey, A. as-Colell and M. Shubik, "Efficiency Properties of Strategic Market Games: An...Axiomatic Approach," Journal of Economic Theory 22 (1980), 339-362. [5] P. Dubey and J. D. Rogsvski, "Inefficiency of Nash Equilibria: II," forthcoming

  6. 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.

  7. 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.

  8. 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

  9. 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…

  10. 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.

  11. Qualitative modifications and new dynamic phases in the phase diagram of one-dimensional superconducting wires driven with electric currents

    NASA Astrophysics Data System (ADS)

    Kallush, Shimshon; Berger, Jorge

    2014-06-01

    After an initial transient period, the conduction regime in a one-dimensional superconducting wire that carries a fixed current is either normal, periodic, or stationary. The phase diagram for these possibilities was studied in Phys. Rev. Lett. 99, 167003 (2007), 10.1103/PhysRevLett.99.167003 for particular values of the length and the material parameters. We have extended this study to arbitrary length and to a range of material parameters that includes realistic values. Variation of the length leads to scaling laws for the phase diagram. Variation of the material parameters leads to new qualitative features and new phases, including a parameter region in which all three regimes are possible.

  12. 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.

  13. Chemical modification of nucleotide bases and mRNA editing depend on hexamer or nucleoprotein phase in Sendai virus nucleocapsids.

    PubMed Central

    Iseni, Frédéric; Baudin, Florence; Garcin, Dominique; Marq, Jean-Baptiste; Ruigrok, Rob W H; Kolakofsky, Daniel

    2002-01-01

    The minus-strand genome of Sendai virus is an assembly of the nucleocapsid protein (N) and RNA, in which each N subunit is associated with precisely 6 nt. Only genomes that are a multiple of 6 nt long replicate efficiently or are found naturally, and their replication promoters contain sequence elements with hexamer repeats. Paramyxoviruses that are governed by this hexamer rule also edit their P gene mRNA during its synthesis, by G insertions, via a controlled form of viral RNA polymerase "stuttering" (pseudo-templated transcription). This stuttering is directed by a cis-acting sequence (3' UNN UUUUUU CCC), whose hexamer phase is conserved within each virus group. To determine whether the hexamer phase of a given nucleotide sequence within nucleocapsids affected its sensitivity to chemical modification, and whether hexamer phase of the mRNA editing site was important for the editing process, we prepared a matched set of viruses in which a model editing site was displaced 1 nt at a time relative to the genome ends. The relative abilities of these Sendai viruses to edit their mRNAs in cell culture infections were examined, and the ability of DMS to chemically modify the nucleotides of this cis-acting signal within resting viral nucleocapsids was also studied. Cytidines at hexamer phases 1 and 6 were the most accessible to chemical modification, whereas mRNA editing was most extensive when the stutter-site C was in positions 2 to 5. Apparently, the N subunit imprints the nucleotide sequence it is associated with, and affects both the initiation of viral RNA synthesis and mRNA editing. The N-subunit assembly thus appears to superimpose another code upon the genetic code. PMID:12212849

  14. Investigation of the phase equilibria and phase transformations associated with the Bi2Sr2CaCu2Oy superconductor

    SciTech Connect

    Holesinger, Terry

    1993-12-09

    The solid solution region and reaction kinetics of the Bi2Sr2CaCu2Oy (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 Bi2Sr2-xCaxCuOy (2201) and Cu2O followed by Bi2Sr3-xCaxOy, 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 Bi2Sr3-xCaxOy (23x) and Bi2Sr2-xCaxOy (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.

  15. 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.

  16. Applications of Surface Modification Techniques in Enhancement of Phase Change Heat Transfer

    NASA Astrophysics Data System (ADS)

    Leu, Tzong-Shyng; Lin, Hung-Wen; Wu, Tseng-Hsin

    When saturated vapor passes over a colder substrate, liquid drops nucleate and grow by coalescence with surrounding drops. Typically speaking, nucleation and growth rates of water droplets are faster on a hydrophilic surface than on a hydrophobic surface. However, heat transfer efficiency degrades once surface becomes filmwise condensation. In this paper, vapor condensing on a gradient surface to prevent filmwise condensation is studied. New gradient surfaces are fabricated. It is demonstrated that 10% increase of condensation heat flux can be achieved on a silicon wafer with C = 1 mm gradient surface. The main mechanism for heat transfer enhancement is found to be that drops condensing on C = 1 mm gradient surface begin to move at a much smaller size compared with those on silicon wafer without modification.

  17. Phasing of lysozyme using one-wavelength anomalous scattering of sulphur atoms through the combination of direct methods and density modification

    NASA Astrophysics Data System (ADS)

    Jiang, Fan; Gu, Yuan-Xin; Zheng, Chao-De; Fan, Hai-Fu

    2003-08-01

    A new method of combining one-wavelength anomalous scattering (OAS) phasing and density modification has been described, in which the improved phases from density modification are re-introduced into OAS phasing. In this way, the phases could be improved iteratively until convergence. The OAS phasing method is based on the previously established sign-probability formula, which breaks the phase ambiguity in the OAS phasing. The implementation of this method has been available in CCP4 as OASIS. This method, although based on direct-methods, could also incorporate known phases and figures of merit into its sign-probability formula. In the implementation of OASIS, the known phases are from the positions of the anomalous scatters. In the current method, the known phases are from the density modification. The current method was tested on phasing a lysozyme crystal using anomalous scattering of sulphur atoms with diffraction data collected on an in-house x-ray source. The resulting map was well connected for the backbone atoms and clearly traceable, with an average map correlation coefficient of 0.6622 for the backbone atoms.

  18. X-ray elastography: Modification of x-ray phase contrast images using ultrasonic radiation pressure

    SciTech Connect

    Hamilton, Theron J.; Bailat, Claude; Rose-Petruck, Christoph; Diebold, Gerald J.; Gehring, Stephan; Laperle, Christopher M.; Wands, Jack

    2009-05-15

    The high resolution characteristic of in-line x-ray phase contrast imaging can be used in conjunction with directed ultrasound to detect small displacements in soft tissue generated by differential acoustic radiation pressure. The imaging method is based on subtraction of two x-ray images, the first image taken with, and the second taken without the presence of ultrasound. The subtraction enhances phase contrast features and, to a large extent, removes absorption contrast so that differential movement of tissues with different acoustic impedances or relative ultrasonic absorption is highlighted in the image. Interfacial features of objects with differing densities are delineated in the image as a result of both the displacement introduced by the ultrasound and the inherent sensitivity of x-ray phase contrast imaging to density variations. Experiments with ex vivo murine tumors and human tumor phantoms point out a diagnostic capability of the method for identifying tumors.

  19. 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...

  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.

  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. Experimental investigation of zoisite-clinozoisite phase equilibria in the system CaO-Fe2O3-Al2O3-SiO2-H2O

    NASA Astrophysics Data System (ADS)

    Brunsmann, A.; Franz, G.; Heinrich, W.

    2002-01-01

    The system Ca2Al3Si3O11(O/OH)-Ca2Al2FeSi3O11(O/OH), with emphasis on the Al-rich portion, was investigated by synthesis experiments at 0.5 and 2.0 GPa, 500-800 °C, using the technique of producing overgrowths on natural seed crystals. Electron microprobe analyses of overgrowths up to >100 µm wide have located the phase transition from clinozoisite to zoisite as a function of P-T-Xps and a miscibility gap in the clinozoisite solid solution. The experiments confirm a narrow, steep zoisite-clinozoisite two-phase loop in T-Xps section. Maximum and minimum iron contents in coexisting zoisite and clinozoisite are given by $X{ ps}{ zo} (max) = 1.9*10{ - 4} T+ 3.1*10{ - 2} P - 5.36*10{ - 2} and X{ ps}{ czo} (min) = (4.6 * 10{ - 4} - 4 * 10{ - 5} P)T + 3.82 * 10{ - 2} P - 8.76 * 10{ - 2} $ (P in GPa, T in °C). The iron-free end member reaction clinozoisite = zoisite has equilibrium temperatures of 185+/-50 °C at 0.5 GPa and 0+/-50 °C at 2.0 GPa, with ΔHr0=2.8+/-1.3 kJ/mol and ΔSr0=4.5+/-1.4 J/mol×K. At 0.5 GPa, two clinozoisite modifications exist, which have compositions of clinozoisite I 0.15 to 0.25 Xps and clinozoisite II >0.55 Xps. The upper thermal stability of clinozoisite I at 0.5 GPa lies slightly above 600 °C, whereas Fe-rich clinozoisite II is stable at 650 °C. The schematic phase relations between epidote minerals, grossular-andradite solid solutions and other phases in the system CaO-Al2O3-Fe2O3-SiO2-H2O are shown.

  3. Liquid-liquid equilibria for ternary polymer mixtures

    NASA Astrophysics Data System (ADS)

    Oh, Suk Yung; Bae, Young Chan

    2011-01-01

    A molecular thermodynamic model for multicomponent systems based on a closed-packed lattice model is presented based on two contributions; entropy and energy contribution. The calculated liquid-liquid equilibria of ternary chainlike mixtures agreed with Monte Carlo simulation results. The proposed model can satisfactorily predict Types 0, 1, 2 and 3 phase separations of the Treybal classification. The model parameters obtained from the binary systems were used to directly predict real ternary systems and the calculated results correlated well with experimental data using few adjustable parameters. Specific interactions in associated binary systems were considered using a secondary lattice.

  4. 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.

  5. A three-dimensional, three-phase, simulator for permeability modification treatments using gelled polymers

    SciTech Connect

    Gao, H.W.; Chang, M.M.

    1990-03-01

    A three-dimensional, (oil, water, and gas) simulator was developed by incorporating an in situ gelation model into a black oil simulator (BOAST). This simulator can be used to design permeability modification treatments and to assess the applicability of the method in oil fields using crosslinked polymer gels. Features of the simulator include: transport of each chemical species of the polymer/crosslinker system in porous media, gelation reaction kinetics of the polymer with crosslinking agents, rheology of the polymer and gel, inaccessible pore volume to macromolecules, adsorption of chemical species on rock surfaces, retention of gel on the rock matrix, and permeability reduction caused by the adsorption of polymer and gel. The simulator was validated by comparing the results of simulation runs on an in situ gelation model and polymer flooding with data reported in the literature. Three-dimensional sensitivity runs were performed using a two-layer reservoir model with a horizontal permeability contrast of 10:1 to investigate the effect of vertical to horizontal permeability contrast on incremental oil recovery and to determine the optimal time for initiation of a polymer gel treatment in a waterflood. 35 refs., 35 figs., 11 tabs.

  6. Valorization of BOF Steel Slag by Reduction and Phase Modification: Metal Recovery and Slag Valorization

    NASA Astrophysics Data System (ADS)

    Liu, Chunwei; Huang, Shuigen; Wollants, Patrick; Blanpain, Bart; Guo, Muxing

    2017-03-01

    Basic oxygen furnace (BOF) steel slag is a main byproduct in steelmaking, and its valorization is therefore of considerable interest, from a metal-recovery perspective and from a residue-utilization perspective. In the present study, the carbothermic reduction of BOF slag was investigated systematically. The reductions of Fe- and P-containing phases (i.e., oxide and compounds) are discussed. Effects of Al2O3 and SiO2 additions on the solidification microstructure and mineralogy associated with the reduction processes were also investigated. The formation and growth of the extracted metallic phase are discussed, and the mineralogy of the residue slag is determined. We conclude that by controlling the additions under a rapid cooling condition, it is possible to extract metallic iron as high-grade metal and simultaneously to utilize the remaining slag for construction applications.

  7. Improvement of chiral stationary phases based on cinchona alkaloids bonded to crown ethers by chiral modification.

    PubMed

    Zhao, Jianchao; Wu, Haixia; Wang, Dongqiang; Wu, Haibo; Cheng, Lingping; Jin, Yu; Ke, Yanxiong; Liang, Xinmiao

    2015-09-17

    To improve the chiral recognition capability of a cinchona alkaloid crown ether chiral stationary phase, the crown ether moiety was modified by the chiral group of (1S, 2S)-2-aminocyclohexyl phenylcarbamate. Both quinine and quinidine-based stationary phases were evaluated by chiral acids, chiral primary amines and amino acids. The quinine/quinidine and crown ether provided ion-exchange sites and complex interaction site for carboxyl group and primary amine group in amino acids, respectively, which were necessary for the chiral discrimination of amino acid enantiomers. The introduction of the chiral group greatly improved the chiral recognition for chiral primary amines. The structure of crown ether moiety was proved to play a dominant role in the chiral recognitions for chiral primary amines and amino acids.

  8. 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

  9. 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).

  10. On the Equilibria of the Extended Nematic Polymers under Elongational Flow

    DTIC Science & Technology

    2007-01-01

    nondipo- lar ) nematic rod ensembles where 〈m〉 = 0 [8, 11], the stable equilibria satisfy either s1 = s2 = s3 (isotropic phase) or s3 > s1 = s2...Doi- Onsager equation on the sphere with Maier-Saupe potential,” Communications in Mathe- matical Sciences, vol. 3, no. 2, pp. 201–218, 2005. [10] C

  11. 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.

  12. Computation of two-fluid, flowing equilibria

    NASA Astrophysics Data System (ADS)

    Steinhauer, Loren; Kanki, Takashi; Ishida, Akio

    2006-10-01

    Equilibria of flowing two-fluid plasmas are computed for realistic compact-toroid and spherical-tokamak parameters. In these examples the two-fluid parameter ɛ (ratio of ion inertial length to overall plasma size) is small, ɛ ˜ 0.03 -- 0.2, but hardly negligible. The algorithm is based on the nearby-fluids model [1] which avoids a singularity that otherwise occurs for small ɛ. These representative equilibria exhibit significant flows, both toroidal and poloidal. Further, the flow patterns display notable flow shear. The importance of two-fluid effects is demonstrated by comparing with analogous equilibria (e.g. fixed toroidal and poloidal current) for a static plasma (Grad-Shafranov solution) and a flowing single-fluid plasma. Differences between the two-fluid, single-fluid, and static equilibria are highlighted: in particular with respect to safety factor profile, flow patterns, and electrical potential. These equilibria are computed using an iterative algorithm: it employs a successive-over-relaxation procedure for updating the magnetic flux function and a Newton-Raphson procedure for updating the density. The algorithm is coded in Visual Basic in an Excel platform on a personal computer. The computational time is essentially instantaneous (seconds). [1] L.C. Steinhauer and A. Ishida, Phys. Plasmas 13, 052513 (2006).

  13. 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.

  14. The effect of gas plasma modification on platelet and contact phase activation processes.

    PubMed

    Rhodes, Nicholas P; Wilson, Darren J; Williams, Rachel L

    2007-11-01

    Medical-grade polytetrafluoroethylene (PTFE), polydimethylsiloxane (PDMS), polyetherurethane (PEU) and ultrahigh molecular weight polyethylene (UHMWPE) were plasma treated with O2, Ar, N2 and NH3. Their surface properties were characterised using X-ray photoelectron spectroscopy (XPS), static secondary ion mass spectroscopy (SSIMS), atomic force microscopy (AFM) and dynamic contact angle (DCA) analysis. Platelet adhesion, aggregation, activation and release of microparticles were determined after contact with whole blood in a cone and plate viscometer. Activation of the coagulation system was quantified in a static environment using a partial thromboplastin time (PTT) assay. The chemical compositions of the untreated surfaces were found to be very similar to those of the bulk material except for PEU, whose surface was comprised almost entirely of soft ether segments. For all materials, the different plasma treatments resulted in moderate etching with the incorporation of functional groups and removal of side groups: defluorination, dehydrogenation, cleavage of methyl side groups and soft segments for PTFE, UHMWPE, PDMS and PEU, respectively. Consequently, plasma treatment resulted in increased wettability in all cases. Blood contact with the virgin materials resulted in activation of platelets and the clotting cascade. Plasma treatment resulted in a significant reduction in platelet adhesion for all materials and all treatments. In the case of PTFE and PEU, the activation status of these cells was also reduced. Plasma treatment of all materials reduced fluid-phase CD62P expression. Platelet aggregate size correlated well with degree of aggregate formation, but many treatments increased the degree of aggregation, as was the case for microparticle shedding. There was no correlation between CD62P expression, aggregate formation and platelet microparticle (PMP) shedding. It is concluded that despite incorporation of the same chemical groups, the pattern of response to

  15. Tokamak equilibria with reversed current density.

    PubMed

    Martynov, A A; Medvedev, S Yu; Villard, L

    2003-08-22

    Observations of nearly zero toroidal current in the central region of tokamaks (the "current hole") raises the question of the existence of toroidal equilibria with very low or reversed current in the core. The solutions of the Grad-Shafranov equilibrium equation with hollow toroidal current density profile including negative current density in the plasma center are investigated. Solutions of the corresponding eigenvalue problem provide simple examples of such equilibrium configurations. More realistic equilibria with toroidal current density reversal are computed using a new equilibrium problem formulation and computational algorithm which do not assume nested magnetic surfaces.

  16. 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

  17. 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

  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. 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.

  20. 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…

  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. A Semantical Approach to Equilibria and Rationality

    NASA Astrophysics Data System (ADS)

    Pavlovic, Dusko

    Game theoretic equilibria are mathematical expressions of rationality. Rational agents are used to model not only humans and their software representatives, but also organisms, populations, species and genes, interacting with each other and with the environment. Rational behaviors are achieved not only through conscious reasoning, but also through spontaneous stabilization at equilibrium points.

  3. X- and Y-line equilibria

    SciTech Connect

    Yoon, P. H.; Lui, A. T. Y.

    2007-10-15

    In this Brief Communication, it is shown that an analytical solution for an exact two-dimensional X- or Y-line equilibrium may be constructed quite easily on the basis of the fundamental theoretical equation. The equilibria discussed in the present report show the potential for a rich variety of current sheet structures that satellites may encounter in space.

  4. Correlation between conformational equilibria of free host and guest binding affinity in non-preorganized receptors.

    PubMed

    Carrillo, Romen; Morales, Ezequiel Q; Martín, Víctor S; Martín, Tomás

    2013-08-16

    Positive cooperativity between host conformational equilibria and guest binding has been widely reported in protein receptors. However, reported examples of this kind of cooperativity in synthetic hosts are scarce and largely serendipitous, among other things because it is hard to envision systems which display this kind of cooperativity. In order to shed some light on the correlation between conformational equilibria of free host and guest binding, selected structural modifications have been performed over a family of nonpreorganized hosts in order to induce conformational changes and to analyze their effect on the binding affinity. The conformational effect was evaluated by a theoretical conformational search and correlated with the ability of the receptors. All data suggest that those receptors that display the best association constants are able to sample folded conformations analogous to the conformational requirements for the binding of the guests. On the contrary, for those receptors where folded conformers are scarce, then the association constant and enantioselectivity clearly drop.

  5. Sedimentation and multiphase equilibria in suspensions of colloidal hard rods.

    PubMed

    Savenko, S V; Dijkstra, Marjolein

    2004-11-01

    Sedimentation and multiphase equilibria in a suspension of hard colloidal rods are explored by analyzing the (macroscopic) osmotic equilibrium conditions. We observe that gravity enables the system to explore a whole range of phases varying from the most dilute phase to the densest phase, i.e., from the isotropic (I), to the nematic (N), to the smectic (Sm), to the crystal (K) phase. We determine the phase diagrams for hard spherocylinders with a length-to-diameter ratio of 5 for a semi-infinite system and a system with fixed container height using a bulk equation of state obtained from simulations. Our results show that gravity leads to multiphase coexistence for the semi-infinite system, as we observe I, I+N, I+N+Sm , or I+N+Sm+K coexistence, while the finite system shows I, N, Sm, K, I+N, N+Sm, Sm+K, I+N+Sm, N+Sm+K , and I+N+Sm+K phase coexistence. In addition, we compare our theoretical predictions for the phase behavior and the density profiles with Monte Carlo simulations for the semi-infinite system and we find good agreement with our theoretical predictions.

  6. Nanophase transition metal oxides show large thermodynamically driven shifts in oxidation-reduction equilibria.

    PubMed

    Navrotsky, Alexandra; Ma, Chengcheng; Lilova, Kristina; Birkner, Nancy

    2010-10-08

    Knowing the thermodynamic stability of transition metal oxide nanoparticles is important for understanding and controlling their role in a variety of industrial and environmental systems. Using calorimetric data on surface energies for cobalt, iron, manganese, and nickel oxide systems, we show that surface energy strongly influences their redox equilibria and phase stability. Spinels (M(3)O(4)) commonly have lower surface energies than metals (M), rocksalt oxides (MO), and trivalent oxides (M(2)O(3)) of the same metal; thus, the contraction of the stability field of the divalent oxide and expansion of the spinel field appear to be general phenomena. Using tabulated thermodynamic data for bulk phases to calculate redox phase equilibria at the nanoscale can lead to errors of several orders of magnitude in oxygen fugacity and of 100 to 200 kelvin in temperature.

  7. 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.

  8. Effect of Nd modification on electrical properties of mixed-layer Aurivillius phase Bi4Ti3O12-SrBi4Ti4O15

    NASA Astrophysics Data System (ADS)

    Wang, Wei; Gu, Shi-Pu; Mao, Xiang-Yu; Chen, Xiao-Bing

    2007-07-01

    The effect of Nd modification on ferro-, piezo-, and dielectric properties of intergrowth Bi4Ti3O12-SrBi4Ti4O15 ceramics was investigated. X-ray diffraction and Raman scattering were used to identify the crystal phase and to distinguish the doping sites. With increasing Nd content up to 0.50, both remanent polarization (2Pr) and piezoelectric coefficient (d33) were found to increase and reach the maximum value of 33.2 μC/cm2 and 14 pC/N, respectively, which gained an enlargement over 1.7 times in 2Pr and a desirable 75% increment in d33 value. However, further Nd modification starts to deteriorate the ferro- and piezoelectric behavior. Impedance spectroscopy shows the activation energy of conductivity increased with increasing Nd content, which can be regarded as direct proof of the restraint of oxygen vacancies. The thermal variations of dielectric permittivity and loss tan δ with Nd content show the characteristic of diffuse phase transformation while the convincible defect-related relaxation phenomenon was not found. Interestingly, in contrast to La modification, Nd modification does not induce the relaxor behavior even at very high doping content.

  9. 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.

  10. 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.

  11. 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.

  12. 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.

  13. Algebraic geometrization of the Kuramoto model: Equilibria and stability analysis

    NASA Astrophysics Data System (ADS)

    Mehta, Dhagash; Daleo, Noah S.; Dörfler, Florian; Hauenstein, Jonathan D.

    2015-05-01

    Finding equilibria of the finite size Kuramoto model amounts to solving a nonlinear system of equations, which is an important yet challenging problem. We translate this into an algebraic geometry problem and use numerical methods to find all of the equilibria for various choices of coupling constants K, natural frequencies, and on different graphs. We note that for even modest sizes (N ˜ 10-20), the number of equilibria is already more than 100 000. We analyze the stability of each computed equilibrium as well as the configuration of angles. Our exploration of the equilibrium landscape leads to unexpected and possibly surprising results including non-monotonicity in the number of equilibria, a predictable pattern in the indices of equilibria, counter-examples to conjectures, multi-stable equilibrium landscapes, scenarios with only unstable equilibria, and multiple distinct extrema in the stable equilibrium distribution as a function of the number of cycles in the graph.

  14. Quantum Nash Equilibria and Quantum Computing

    NASA Astrophysics Data System (ADS)

    Fellman, Philip Vos; Post, Jonathan Vos

    In 2004, At the Fifth International Conference on Complex Systems, we drew attention to some remarkable findings by researchers at the Santa Fe Institute (Sato, Farmer and Akiyama, 2001) about hitherto unsuspected complexity in the Nash Equilibrium. As we progressed from these findings about heteroclinic Hamiltonians and chaotic transients hidden within the learning patterns of the simple rock-paper-scissors game to some related findings on the theory of quantum computing, one of the arguments we put forward was just as in the late 1990's a number of new Nash equilibria were discovered in simple bi-matrix games (Shubik and Quint, 1996; Von Stengel, 1997, 2000; and McLennan and Park, 1999) we would begin to see new Nash equilibria discovered as the result of quantum computation. While actual quantum computers remain rather primitive (Toibman, 2004), and the theory of quantum computation seems to be advancing perhaps a bit more slowly than originally expected, there have, nonetheless, been a number of advances in computation and some more radical advances in an allied field, quantum game theory (Huberman and Hogg, 2004) which are quite significant. In the course of this paper we will review a few of these discoveries and illustrate some of the characteristics of these new "Quantum Nash Equilibria". The full text of this research can be found at http://necsi.org/events/iccs6/viewpaper.php?id-234

  15. 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.

  16. Phase Diagram Studies of ZnS Systems

    DTIC Science & Technology

    1988-09-01

    mechanical, processing of ZnS-base ’alloys’. Knowledge of the phase equilibria of various ZnS-rich systems is essential to achieve our objectives...initial studies of the solid-state phase equilibria in the ZnS-CdS and ZnS-Ga2s3 phase diagrams.

  17. 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)

  18. 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.

  19. 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…

  20. Nanophase Manganese Oxides: Chemisorbed Water and Small Particle Size Promote Large Thermodynamically Driven Shifts in Oxidation-Reduction Equilibria

    NASA Astrophysics Data System (ADS)

    Birkner, N.; Navrotsky, A.

    2011-12-01

    Manganese oxides are important in terrestrial and Martian settings, and changes in oxidation state (Mn 2+, 3+, 4+) produce different phases. This study focuses on changes in redox energetics at the nanoscale in the Mn-O system with water present. Nanophase hausmannite (Mn3O4), bixbyite (Mn2O3), and pyrolusite (MnO2) were synthesized using minor modifications of previously published methods, stored at room temperature, and then analyzed by powder-XRD, BET surface area measurement, and TGA for total water content. High-temperature oxide-melt drop solution calorimetry was performed on a series of characterized samples with known surface area and water content. The differential heat of water adsorption as a function of coverage was also measured. The surface enthalpies of manganese oxide phases, hausmannite (Mn3O4), bixbyite (Mn2O3), and pyrolusite (MnO2), were determined using the data from high-temperature oxide melt calorimetry and water adsorption calorimetry. Surface energy for the hydrous Mn3O4 tetragonal spinel phase is 0.96±0.08 J/m2, for Mn2O3 cubic phase is 1.29±0.10 J/m2, and for MnO2 cubic rutile phase is 1.64±0.10 J/m2. Surface energy for the anhydrous Mn3O4 is 1.31±0.08 J/m2, for Mn2O3 is 1.57±0.10 J/m2, and for MnO2 is 1.99±0.10 J/m2. Supporting preliminary findings, the spinel phase (hausmannite) has a lower surface energy than bixbyite, while the latter has a smaller surface energy than pyrolusite. We also observed phase changes, some of them rapidly reversible, associated with water adsorption/desorption for the nanophase manganese oxide assemblages. There are geochemical consequences. (1) At the nanoscale, both the pyrolusite/bixbyite and bixbyite/hausmannite equilibria are shifted to higher oxygen fugacity because the reduced phase has the lower surface energy. (2) The ready inter-conversion of phases with different oxidation states under aqueous conditions implies that, after a manganese oxide nanophase forms, it can easily transform to other

  1. Post-Synthesis Modification of the Aurivillius Phase Bi2SrTa2O9 via In Situ Microwave-Assisted "Click Reaction".

    PubMed

    Wang, Yanhui; Delahaye, Emilie; Leuvrey, Cédric; Leroux, Fabrice; Rabu, Pierre; Rogez, Guillaume

    2016-10-03

    A new strategy for the functionalization of layered perovskites is presented, based on the in situ post-synthesis modification of a prefunctionalized phase by copper(I)-catalyzed alkyne-azide cycloaddition (CuAAC). The microwave-assisted protonation and grafting of an alkyne alcohol provides the alkyne-functionalized precursor within a few hours, starting from Bi2SrTa2O9. The subsequent microwave-assisted in situ "click reaction" allows the post-synthesis modification of the precursor within ∼2 h, providing a layered perovskite functionalized by an alcohol-grafted 1,4-disubstituted-1H-1,2,3-triazole. Two compounds are described here, bearing an aliphatic and an aromatic substituent, which illustrates the general application of the method. This work opens new perspectives for the functionalization of layered perovskites, going beyond mere insertion/grafting reactions, and thus broadens the design possibilities and the range of applications of these hybrid systems.

  2. Phase equilibria in the Mo-Fe-P system at 800 °C and structure of ternary phosphide (Mo(1-x)Fe(x))3P (0.10 ≤ x ≤ 0.15).

    PubMed

    Oliynyk, Anton O; Lomnytska, Yaroslava F; Dzevenko, Mariya V; Stoyko, Stanislav S; Mar, Arthur

    2013-01-18

    Construction of the isothermal section in the metal-rich portion (<67 atom % P) of the Mo-Fe-P phase diagram at 800 °C has led to the identification of two new ternary phases: (Mo(1-x)Fe(x))(2)P (x = 0.30-0.82) and (Mo(1-x)Fe(x))(3)P (x = 0.10-0.15). The occurrence of a Co(2)Si-type ternary phase (Mo(1-x)Fe(x))(2)P, which straddles the equiatomic composition MoFeP, is common to other ternary transition-metal phosphide systems. However, the ternary phase (Mo(1-x)Fe(x))(3)P is unusual because it is distinct from the binary phase Mo(3)P, notwithstanding their similar compositions and structures. The relationship has been clarified through single-crystal X-ray diffraction studies on Mo(3)P (α-V(3)S-type, space group I42m, a = 9.7925(11) Å, c = 4.8246(6) Å) and (Mo(0.85)Fe(0.15))(3)P (Ni(3)P-type, space group I4, a = 9.6982(8) Å, c = 4.7590(4) Å) at -100 °C. Representation in terms of nets containing fused triangles provides a pathway to transform these closely related structures through twisting. Band structure calculations support the adoption of these structure types and the site preference of Fe atoms. Electrical resistivity measurements on (Mo(0.85)Fe(0.15))(3)P reveal metallic behavior but no superconducting transition.

  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. 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.

  5. Relativistic thermal plasmas - Pair processes and equilibria

    NASA Technical Reports Server (NTRS)

    Lightman, A. P.

    1982-01-01

    The work of Bisnovatyi-Kogan, Zel'dovich and Sunyaev (1971) is extended and generalized, through the inclusion of pair-producing photon processes and effects due to the finite size of the plasma, in an investigation of the equilibria of relativistic thermal plasmas which takes into account electron-positron creation and annihilation and photons produced within the plasma. It is shown that the bridge between an effectively thin plasma and an effectively thick plasma occurs in the transrelativistic region, where the dimensionless temperature value is between 0.1 and 1.0 and the temperature remains in this region over a great luminosity range.

  6. 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.

  7. 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.

  8. Phase equilibria in the YBCuO system and melt processing of Ag clad Y 1Ba 2Cu 3O 7- x tapes at reduced oxygen partial pressures

    NASA Astrophysics Data System (ADS)

    MacManus-Driscoll, J. L.; Bravman, J. C.; Beyers, R. B.

    1995-02-01

    We have undertaken phase-stability studies of Y 1Ba 2Cu 3O 7- x(+Ag) and BaCu 2O 2 (+Ag) over the temperature range 780°C-950°C and oxygen partial pressure range 1.0 × 10 -6-2.0 × 10 -1 atm. Ag was found to have no effect on the thermodynamic stability of either phase. Partial melting of YBCO was found at temperatures as low as 800°C ± 10°C, with significant peritectic melting at temperatures as low as 900°C ± 10°C. These thermochemical studies have enabled us to determine the optimum conditions for reduced temperature and pressure (RTP) processing of Ag clad Y 1Ba 2Cu 3O 7- x pellets and tapes. The classic domain structure with strong texturing over short lengths was produced in samples melt processed by controlling oxygen partial pressure at a fixed temperature. The RTP method has the advantage that the second phase Y 2BaCuO 5 particle size can be controlled. Moreover, the technique offers the promise of long lengths of flexible Y 1Ba 2Cu 3O 7- x tapes with high current carrying capability.

  9. Modification of Rayleigh-Plesset Theory for Reproducing Dynamics of Cavitation Bubbles in Liquid-Phase Laser Ablation

    NASA Astrophysics Data System (ADS)

    Soliman, Wafaa; Nakano, Tetsutaro; Takada, Noriharu; Sasaki, Koichi

    2010-11-01

    The solution of the conventional Rayleigh-Plesset equation did not agree with the experimental results on the temporal variations of the sizes of cavitation bubbles produced by laser ablation in water. In this work, we modified the conventional Rayleigh-Plesset theory in the following two points to reproduce the experimental observation theoretically. One was to introduce the effect of the contact angle among the water, the cavitation bubble, and the ablation target. The other was to treat the surface tension and the kinematic viscosity coefficient of water as additional adjusting parameters to fit the theoretical result with the experimental observation. The latter modification was effective especially for laser ablation in the pressurized water. Better agreement between the theoretical and the experimental results was realized with the help of these modifications, but anomalous thermodynamic parameters were necessary to obtain the best fitting. We evaluated the pressures and the temperatures inside the cavitation bubbles.

  10. 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.

  11. 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.

  12. 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.

  13. 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.

  14. Phase Transition in Cs 2KMnF 6: Crystal Structures of Low- and High-Temperature Modifications

    NASA Astrophysics Data System (ADS)

    Xu, Y.; Carlson, S.; Sjödin, A.; Norrestam, R.

    2000-03-01

    Crystalline Cs2KMnF6, when prepared below 500°C, adopts a tetragonal elpasolite structure type. Differential scanning calorimetric investigations indicated that Cs2KMnF6 undergoes a phase transition from the low-temperature tetragonal phase (LT) to a high-temperature phase (HT) at about 530°C. Single crystals of the new HT phase could be obtained by annealing a crystalline LT specimen at 600°C followed by rapid quenching to room temperature. In the present study the structures of both phases have been studied by single-crystal X-ray diffraction techniques. The LT phase has the tetragonal space group symmetry I4/mmm, with unit-cell parameters a=6.319(1) (a·2=8.936) and c=9.257(2) Å, and Z=2. The HT phase has the cubic symmetry Fm3m, with the cell parameter a=9.067 Å and Z=4. Structural models of the LT and HT phases have been refined vs collected single-crystal X-ray reflection data to R values of 0.034 and 0.022, respectively. The uneven Mn-F bond distance distribution in the LT form, four bonds of 1.860(6) two of 2.034(9) Å, are typical for an octahedrally coordinated high-spin Mn3+ ion affected by Jahn-Teller effects. Due to symmetry constraints, all six octahedral Mn-F bonds in the HT form are equal to 1.931(5) Å. However, the mean square atomic displacement parameters of the fluorine atoms increases significantly from about 0.022 Å2 for the LT phase to 0.042 Å2 for the HT phase. The increased displacement parameters indicate that the phase transition from the LT to the HT form is associated with a directional disorder of the Jahn-Teller distortions around the Mn3+ ions.

  15. Modification of linear prepolymers to tailor heterogeneous network formation through photo-initiated Polymerization-Induced Phase Separation.

    PubMed

    Szczepanski, Caroline R; Stansbury, Jeffrey W

    2015-07-23

    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/cm(2)), the rate of network formation prohibited significant phase separation, even when thermodynamically preferred. A staged curing approach, which utilizes low intensity irradiation (Io=300µW/cm(2)) 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.

  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. New apparatus for simultaneous determination of phase equilibria and rheological properties of fluids at high pressures: Its application to coal pastes studies up to 773 K and 30 MPa

    SciTech Connect

    Cohen, A.; Richon, D.

    1986-06-01

    In this article, we present a new apparatus based on a static method to simultaneously measure rheological properties of a dense (liquid or liquid+solid) medium and sample phases (dense and gaseous) for analysis purposes. It was especially designed to study coal pastes in the working conditions of hydroliquefaction processes. It can also be used to study other mediums such as asphalts and polymers. The rheometer part of the apparatus was already tested and results published in a previous paper. The ability of the new apparatus to get reliable vapor--liquid equilibrium data in the range of thermal stability of chemical materials is shown as a result of measurements on the nitrogen-n-heptane system at 497.1 K and the methane-n-hexadecane system at 623.1 K and comparison to literature's data. Reproducibility tests have displayed very small data dispersion.

  18. Phase equilibria in the NaF-CdO-NaPO3 system at 873 K and crystal structure and physico-chemical characterizations of the new Na2CdPO4F fluorophosphate

    NASA Astrophysics Data System (ADS)

    Aboussatar, Mohamed; Mbarek, Aïcha; Naili, Houcine; El-Ghozzi, Malika; Chadeyron, Geneviève; Avignant, Daniel; Zambon, Daniel

    2017-04-01

    Isothermal sections of the diagram representing phase relationships in the NaF-CdO-NaPO3 system have been investigated by solid state reactions and powder X-ray diffraction. This phase diagram investigation confirms the polymorphism of the NaCdPO4 side component and the structure of the ß high temperature polymorph (orthorhombic, space group Pnma and unit cell parameters a=9.3118(2), b=7.0459(1), c=5.1849(1) Å has been refined. A new fluorophosphate, Na2CdPO4F, has been discovered and its crystal structure determined and refined from powder X-ray diffraction data. It exhibits a new 3D structure with orthorhombic symmetry, space group Pnma and unit cell parameters a=5.3731(1), b=6.8530(1), c=12.2691(2) Å. The structure is closely related to those of the high temperature polymorph of the nacaphite Na2CaPO4F and the fluorosilicate Ca2NaSiO4F but differs essentially in the cationic repartition since the structure is fully ordered with one Na site (8d) and one Cd site (4c). Relationships with other Na2MIIPO4F (MII=Mg, Ca, Mn, Fe, Co, Ni) have been examined and the crystal-chemical and topographical analysis of these fluorophosphates is briefly reviewed. IR, Raman, optical and 19F, 23Na, 31P MAS NMR characterizations of Na2CdPO4F have been investigated.

  19. Persistent photoinduced modifications in the phase-separated states of L a2 -2 xS r1 +2 xM n2O7

    NASA Astrophysics Data System (ADS)

    Sun, Kai; Sun, Shuaishuai; Li, Xingyuan; Li, Zhongwen; Zhang, Ruixin; Wei, Linlin; Guo, Cong; Zheng, Dingguo; Tian, Huanfang; Yang, Huaixin; Li, Jianqi

    2016-11-01

    Reentrant charge-ordering transition (RCOT) in the bilayered perovskite manganite L a2 -2 xS r1 +2 xM n2O7 can yield observable changes in both the structural and physical properties associated with phase separation. Our recent measurements show that laser illumination can result in persistent modifications of both the resistance and microstructure in the phase-separated (PS) states. Measurements of photoinduced effects on an x =0.6 sample reveal a persistent increase of the resistance by as much as 40%. Low-temperature laser in situ transmission electron microscope observations clearly show that in situ laser irradiation can modify the PS nature and strengthen the charge-ordered state. We attribute these photoinduced phenomena to the optical modulation of the hole concentration in the Mn O2 layers and the alteration of the local Mn orbital configurations in the PS states.

  20. A molecular-thermodynamic framework for asphaltene-oil equilibria

    SciTech Connect

    Wu, J.; Prausnitz, J.M. |; Firoozabadi, A.

    1997-02-01

    Asphaltene precipitation is a perennial problem in production and refinery of crude oils. To avoid precipitation, it is useful to predict the solubility of asphaltenes in petroleum liquids as a function of temperature, pressure and liquid-phase composition. In the molecular-thermodynamic model presented here, both asphaltenes and resins are represented by pseudo-pure components, and all other components in the solution are represented by a continuous medium which affects interactions among asphaltene and resin particles. The effect of the medium on asphaltene-asphaltene, resin-asphaltene, resin-resin pair interactions is taken into account through its density and molecular-dispersion properties. To obtain expressions for the chemical potential of asphaltene and for the osmotic pressure of an asphaltene-containing solution, the authors use the integral theory of fluids coupled with the SAFT model to allow for asphaltene aggregation and for adsorption of resin on asphaltene particles. With these expressions, a variety of experimental observations can be explained including the effects of temperature, pressure and composition on the phase behavior of asphaltene-containing fluids. For engineering application, the molecular parameters in this model must be correlated to some macroproperties of oil such as density and molecular weight. When such correlations are established, it will be possible to calculate asphaltene-precipitation equilibria at a variety of conditions for realistic systems.

  1. 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.

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

    SciTech Connect

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

    2015-06-27

    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). Lastly, ten solid solution tie-line regions and six three-phase regions were determined in the CaO–½Sm2O3–CoOz system in air.

  3. Integrated Modeling of Time Evolving 3D Kinetic MHD Equilibria and NTV Torque

    NASA Astrophysics Data System (ADS)

    Logan, N. C.; Park, J.-K.; Grierson, B. A.; Haskey, S. R.; Nazikian, R.; Cui, L.; Smith, S. P.; Meneghini, O.

    2016-10-01

    New analysis tools and integrated modeling of plasma dynamics developed in the OMFIT framework are used to study kinetic MHD equilibria evolution on the transport time scale. The experimentally observed profile dynamics following the application of 3D error fields are described using a new OMFITprofiles workflow that directly addresses the need for rapid and comprehensive analysis of dynamic equilibria for next-step theory validation. The workflow treats all diagnostic data as fundamentally time dependent, provides physics-based manipulations such as ELM phase data selection, and is consistent across multiple machines - including DIII-D and NSTX-U. The seamless integration of tokamak data and simulation is demonstrated by using the self-consistent kinetic EFIT equilibria and profiles as input into 2D particle, momentum and energy transport calculations using TRANSP as well as 3D kinetic MHD equilibrium stability and neoclassical transport modeling using General Perturbed Equilibrium Code (GPEC). The result is a smooth kinetic stability and NTV torque evolution over transport time scales. Work supported by DE-AC02-09CH11466.

  4. Stability of certain families of ideal magnetohydrodynamic equilibria.

    PubMed

    Núñez, Manuel

    2003-01-01

    The equations of ideal magnetohydrodynamic equilibria posses a number of symmetries that may be used to generate a family of hitherto unknown equilibria if there exists a foliation of the original one by magnetic surfaces. In addition to the possibility of producing analytic equilibria from old ones, this family is studied to find among its members those with minimal energy, those lasting longer under slightly resistive conditions, and those linearly stable. It is shown that in general none of these properties implies any other, thus clarifying the difference among these concepts.

  5. 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

    2016-12-01

    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 P1 c1, 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

  6. Phase equilibria in the system K2O-FeO-MgO-Al2O3-SiO2-H2O-CO2 and the stability limit of stilpnomelane in metamorphosed Precambrian iron-formations

    NASA Astrophysics Data System (ADS)

    Miyano, Takashi; Klein, Cornelis

    1989-08-01

    The phase relations of Al- and Fe-bearing silicates in the system K2O-FeO-MgO-Al2O3-SiO2-H2O-CO2, in the presence of quartz and magnetite, are discussed on the basis of mineralogic and petrologic data from Precambrian iron-formations and blueschist facies meta-ironstone from the Franciscan Formation, California. These relations allow an estimation of the physiochemical conditions during low-grade metamorphism of iron-formations. Petrologic data together with available experimental and predicted thermodynamic data on the associated minerals place the upper stability limit of stilpnomelane in iron-formations at about 430 470° C and 5 6 kilobars. Fe-end member stilpnomelane can persist to a maximum temperature of 500° C and pressures up to 6 7 kilobars, although it is unlikely to occur in metamorphosed iron-formations. In iron-formation occurrences the stilpnomelane stability field is bordered by four equilibrium reactions with the assemblages stilpnomelane-zussmanite-chlorite-minnesotaite, stilpnomelane-zussmanite-chlorite-grunerite, stilpnomelane-biotite-chlorite-grunerite, and stilpnomelane-biotite-almandine-grunerite. The stability field is reduced by increasing X(CO2) and X {Mg/Stil}, and is also a function of a( K +)/ a( H +) in the metamorphic fluid. If the value of a( K +)/ a( H +) is smaller than that defined by the above assemblages, stilpnomelane decomposes to chlorite, but if larger, it is replaced by biotite. At pressures less than 4 kilobars, the zussmanite field is restricted to a very high value of a( K +)/a( H +) (> 5.0 in log units at 1.0 kilobar) where iron-formation assemblages are not stable.

  7. Thermodynamic data of lawsonite and zoisite in the system CaO-Al2O3-SiO2-H2O based on experimental phase equilibria and calorimetric work

    NASA Astrophysics Data System (ADS)

    Grevel, Klaus-Dieter; Schoenitz, Mirko; Skrok, Volker; Navrotsky, Alexandra; Schreyer, Werner

    2001-08-01

    The enthalpy of drop-solution in molten 2PbO.B2O3 of synthetic and natural lawsonite, CaAl2(Si2O7)(OH)2.H2O, was measured by high-temperature oxide melt calorimetry. The enthalpy of formation determined for the synthetic material is ΔfHOxides=-168.7+/-3.4 kJ mol-1, or ΔfH0298=-4,872.5+/-4.0 kJ mol-1. These values are in reasonable agreement with previously published data, although previous calorimetric work yielded slightly more exothermic data and optimisation methods resulted in slightly less exothermic values. The equilibrium conditions for the dehydration of lawsonite to zoisite, kyanite and quartz/coesite at pressures and temperatures up to 5 GPa and 850 °C were determined by piston cylinder experiments. These results, other recent phase equilibrium data, and new calorimetric and thermophysical data for lawsonite and zoisite, Ca2Al3(SiO4)(Si2O7)O(OH), were used to constrain a mathematical programming analysis of the thermodynamic data for these two minerals in the chemical system CaO-Al2O3-SiO2-H2O (CASH). The following data for lawsonite and zoisite were obtained: ΔfH0298 (lawsonite)=-4,865.68 kJ mol-1 , S0298 (lawsonite)=229.27 J K-1 mol-1 , ΔfH0298 (zoisite)=-6,888.99 kJ mol-1 , S0298 (zoisite)=297.71 J K-1 mol-1 . Additionally, a recalculation of the bulk modulus of lawsonite yielded K=120.7 GPa, which is in good agreement with recent experimental work.

  8. 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.

  9. 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.

  10. 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.

  11. Vapor-Phase Deposition and Modification of Metal-Organic Frameworks: State-of-the-Art and Future Directions.

    PubMed

    Stassen, Ivo; De Vos, Dirk; Ameloot, Rob

    2016-10-04

    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.

  12. Diazonium modification of porous graphitic carbon with catechol and amide groups for hydrophilic interaction and attenuated reversed phase liquid chromatography.

    PubMed

    Iverson, Chad D; Zhang, Ya; Lucy, Charles A

    2015-11-27

    Porous graphitic carbon (PGC) is an increasingly popular and attractive phase for HPLC on account of its chemical and thermal stability, and its unique separation mechanism. However, native PGC is strongly hydrophobic and in some instances excessively retentive. As part of our effort to build a library of hydrophilic covalently modified PGC phases, we functionalized PGC with catechol and amide groups by means of aryl diazonium chemistry to produce two new phases. Successful grafting was confirmed by X-ray photoelectron spectroscopy (XPS). Under HILIC conditions, the Catechol-PGC showed up to 5-fold increased retention relative to unmodified PGC and selectivity that differed from four other HILIC phases. Under reversed phase conditions, the Amide-PGC reduced the retentivity of PGC by almost 90%. The chromatographic performance of Catechol-PGC and Amide-PGC is demonstrated by separations of nucleobases, nucleosides, phenols, alkaline pharmaceuticals, and performance enhancing stimulants. These compounds had retention factors (k) ranging from 0.5 to 13.

  13. 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.

  14. Current profile modification during lower hybrid current drive in the Princeton Beta Experiment-Modification

    SciTech Connect

    Kaita, R.; Bell, R.; Batha, S.H.

    1996-02-01

    Current profile modification with lower hybrid waves has been demonstrated in the Princeton Beta Experiment-Modification tokamak. When the n{parallel} spectrum of the launched waves was varied, local changes in the current profile were observed according to equilibria reconstructed from motional Stark effect polarimetry measurements. Changes in the central safety factor (q) were also determined to be a function of the applied radio frequency (rf) power. These results have been modeled with the Tokamak Simulation Code/Lower Hybrid Simulation Code, which is able to duplicate the general trends seen in the data.

  15. The phase speed of artificial field-aligned irregularities observed by CUTLASS during HF modification of the auroral ionosphere

    NASA Astrophysics Data System (ADS)

    Eglitis, P.; Robinson, T. R.; Rietveld, M. T.; Wright, D. M.; Bond, G. E.

    1998-02-01

    The RF heater facility at Ramfjordmoen, Tromsø can generate field-aligned plasma irregularities in the field of view of the Cooperative UK Twin-Located Auroral Sounding System (CUTLASS) coherent backscatter radar at Hankasalmi, Finland. In a recent set of experiments conducted in April 1996, the phase speed of the generated plasma irregularities has been compared with independent measurements of the plasma drift velocity observed by the European Incoherent Scatter radar facility. The phase speed of the plasma irregularities is found to be equal to the component of the plasma drift velocity in the direction of propagation of the plasma wave. This result is a further verification of the high performance of the CUTLASS radar and also demonstrates how artificially generated plasma irregularities can be employed to detect small plasma drift velocities and contribute to geophysical research. The characteristics of the Doppler spectrum of the artificial plasma waves are also described and discussed.

  16. Modification of the murakami retention model in reversed-phase high-performance liquid chromatography for micellar chromatographic separations

    NASA Astrophysics Data System (ADS)

    Loginova, L. P.; Boichenko, A. P.; Kulikov, A. Yu.

    2008-09-01

    A retention model for micellar liquid chromatography was tested based on the data of separation of three benzodiazepins and six β-blockers. The model was obtained by analyzing changes in the microenvironment of a sorbate in transferring from the mobile to stationary phase. It can be used to describe the retention of benzodiazepins, which are neutral under the separation conditions, and the positively charged β-blockers. The calculated model coefficients are indicative of an increase in the number of 1-pentanol molecules and sodium dodecyl sulfate monomers in the microenvironment of the sorbates in transferring from the mobile to stationary phase. The solvation of the positive β-blockers by anionic surfactant monomers was higher than that of neutral benzodiazepins.

  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. Vaporization Behavior, Phase Equilibria, and Thermodynamic Stabilities of Nickel Phosphides.

    DTIC Science & Technology

    1984-10-04

    ABSTRACT (Continue an revwee side if neceeear and Identlly by block number) The equilibrium vaporization reactions, 12 Ni2P(s) = 2 Ni12P5 (s) + P2(g...and 6.8 Ni12P5 (s) = 32 Ni2.55P(s) + P2(g), have been studied by mass-loss effusion in the temperature range 1237-1401 K. The results were combined with...of atomization, 0 ~/R, respectively, in kilokelvins at 298.15 K: 1/4 Ni P(s), -5.94±0.5, 54.8; 1/3.55 Ni2 5 P(s), -6.65±0.5, 55.2; 1/17 Ni12P5 ( -6.73

  19. 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.

  20. Tokamak equilibria and edge stability when non-axisymmetric fields are applied

    NASA Astrophysics Data System (ADS)

    Ham, C. J.; Chapman, I. T.; Simpson, J.; Suzuki, Y.

    2015-05-01

    Tokamaks are traditionally viewed as axisymmetric devices. However this is not always true, for example in the presence of saturated instabilities, error fields, or resonant magnetic perturbations (RMPs) applied for edge localized mode (ELM) control. We use the VMEC code (Hirshman and Whitson 1983 Phys. Fluids 26 3553) to calculate three dimensional equilibria by energy minimization for tokamak plasmas. MAST free boundary equilibria have been calculated with profiles for plasma pressure and current derived from two dimensional reconstruction. It is well known that ELMs will need to be controlled in ITER to prevent damage that may limit the lifetime of the machine (Loarte et al 2003 Plasma Phys. Control. Fusion 45 1549). ELM control has been demonstrated on several tokamaks including MAST (Kirk et al 2013 Nucl. Fusion 53 043007). However the application of RMPs causes the plasma to gain a displacement or corrugation (Liu et al 2011 Nucl. Fusion 51 083002). Previous work has shown that the phase and size of these corrugations is in agreement with experiment (Chapman et al 2012 Plasma Phys. Control. Fusion 54 105013). The interaction of these corrugations with the plasma control system (PCS) may cause high heat loads at certain toroidal locations if care is not taken (Chapman et al 2014 Plasma Phys. Control. Fusion 56 075004). VMEC assumes nested flux surfaces but this assumption has been relaxed in other stellarator codes. These codes allow equilibria where magnetic islands and stochastic regions can form. We show some initial results using the HINT2 code (Suzuki et al 2006 Nucl. Fusion 46 L19). The Mercier stability of VMEC equilibria with RMPs applied is calculated. The geodesic curvature contribution can be strongly influenced by helical Pfirsch-Schlüter currents driven by the applied RMPs. ELM mitigation is not fully understood but one of the factors that influences peeling-ballooning stability, which is linked to ELMs, is a three dimensional corrugation of the

  1. Phase formation and mechanical/tribological modification induced by nitrogen high temperature plasma based ion implantation into molybdenum

    NASA Astrophysics Data System (ADS)

    Carreri, F. C.; Oliveira, R. M.; Oliveira, A. C.; Silva, M. M. N. F.; Ueda, M.; Silva, M. M.; Pichon, L.

    2014-08-01

    Transition metal nitrides present high hardness, good wear resistance and chemical stability. The formation of a surface layer of these materials on different types of substrates can improve surface properties without changing bulk characteristics. Molybdenum is used in many technological applications and the search for ways to effectively improve its properties is justified. In this work nitrogen ions were implanted into molybdenum by means of high temperature plasma based ion implantation (HTPBII), in order to produce a layer of molybdenum nitride on the surface of the material. The treatment was performed in the temperature range of 800-1200 °C, for 1 h. X-ray diffraction spectra showed the presence of the cubic-Mo2N phase in most of the samples. The tetragonal-Mo2N phase was also observed, depending on treatment conditions. Glow discharge optical emission spectroscopy was used to study the composition and thickness of the nitride layer. A 12 μm thick Mo2N layer was observed for samples treated at 1100 °C, although beyond this temperature threshold, a significant amount of nitride can no longer be produced. In relation to the surface mechanical properties, a ninefold increase in surface hardness was obtained, as well as a decrease in the friction coefficient. Wear against an alumina ball was not observed.

  2. 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.

  3. 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.

  4. Theories of multiple equilibria and weather regimes : A critical reexamination. II - Baroclinic two-layer models

    NASA Technical Reports Server (NTRS)

    Cehelsky, Priscilla; Tung, Ka Kit

    1987-01-01

    Previous results based on low- and intermediate-order truncations of the two-layer model suggest the existence of multiple equilibria and/or multiple weather regimes for the extratropical large-scale flow. The importance of the transient waves in the synoptic scales in organizing the large-scale flow and in the maintenance of weather regimes was emphasized. The result shows that multiple equilibria/weather regimes that are present in lower-order models examined disappear when a sufficient number of modes are kept in the spectral expansion of the solution to the governing partial differential equations. Much of the chaotic behavior of the large-scale flow that is present in intermediate-order models is now found to be spurious. Physical reasons for the drastic modification are offered. A peculiarity in the formulation of most existing two-layer models is noted that also tends to exaggerate the importance of baroclinic processes and increase the degree of unpredictability of the large-scale flow.

  5. Francisella Tularensis Blue–Gray Phase Variation Involves Structural Modifications of Lipopolysaccharide O-Antigen, Core and Lipid A and Affects Intramacrophage Survival and Vaccine Efficacy

    PubMed Central

    Soni, Shilpa; Ernst, Robert K.; Muszyński, Artur; Mohapatra, Nrusingh P.; Perry, Malcolm B.; Vinogradov, Evgeny; Carlson, Russell W.; Gunn, John S.

    2010-01-01

    Francisella tularensis is a CDC Category A biological agent and a potential bioterrorist threat. There is no licensed vaccine against tularemia in the United States. A long-standing issue with potential Francisella vaccines is strain phase variation to a gray form that lacks protective capability in animal models. Comparisons of the parental strain (LVS) and a gray variant (LVSG) have identified lipopolysaccharide (LPS) alterations as a primary change. The LPS of the F. tularensis variant strain gains reactivity to F. novicida anti-LPS antibodies, suggesting structural alterations to the O-antigen. However, biochemical and structural analysis of the F. tularensis LVSG and LVS LPS demonstrated that LVSG has less O-antigen but no major O-antigen structural alterations. Additionally, LVSG possesses structural differences in both the core and lipid A regions, the latter being decreased galactosamine modification. Recent work has identified two genes important in adding galactosamine (flmF2 and flmK) to the lipid A. Quantitative real-time PCR showed reduced transcripts of both of these genes in the gray variant when compared to LVS. Loss of flmF2 or flmK caused less frequent phase conversion but did not alter intramacrophage survival or colony morphology. The LVSG strain demonstrated an intramacrophage survival defect in human and rat but not mouse macrophages. Consistent with this result, the LVSG variant demonstrated little change in LD50 in the mouse model of infection. Furthermore, the LVSG strain lacks the protective capacity of F. tularensis LVS against virulent Type A challenge. These data suggest that the LPS of the F. tularensis LVSG phase variant is dramatically altered. Understanding the mechanism of blue to gray phase variation may lead to a way to inhibit this variation, thus making future F. tularensis vaccines more stable and efficacious. PMID:21687776

  6. 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.

  7. 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.

  8. Kinetic equilibria of very high- β plasmas

    NASA Astrophysics Data System (ADS)

    Steinhauer, Loren; TAE Team

    2015-11-01

    Plasma equilibria with many large ion orbits, such as an advanced beam-driven field-reversed configuration, are neither static (Grad-Shafranov) nor describable as a flowing, multi-fluid. A fully-kinetic treatment of the ions is essential for such high- β plasmas. A kinetic equilibrium is needed to properly support realistic stability and transport analyses, both of which are strongly affected by large-orbit ions. A hybrid equilibrium model has been developed with a fully-kinetic treatment of both thermal ions and a rapidly-rotating ``beam-ion'' component, such as produced by neutral beam injection, relevant to the C-2U experiments at TAE. It employs analytic Vlasov solutions in that the distribution depends only on the two constants of motion, the Hamiltonian (H) and the canonical angular momentum (Pθ) . Electrons are treated as a pressure-bearing fluid. Since realistic forms of f (H ,Pθ) are affected by collisions, f is limited to solutions of a simplified Fokker-Planck equation. Importantly, a kinetic end-loss condition applies to unconfined ions, using a particle sink at a rate consistent with Monte-Carlo-like simulations of end loss accounting for a strong end mirror.

  9. 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.

  10. 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

    2015-05-08

    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.

  11. Use of reconstructed 3D VMEC equilibria to match effects of toroidally rotating discharges in DIII-D

    SciTech Connect

    Wingen, Andreas; Wilcox, Robert S.; Cianciosa, Mark R.; Seal, Sudip K.; Unterberg, Ezekial A.; Hanson, Jeremy M.; Hirshman, Steven Paul; Lao, L. L.; Logan, N. C.; Paz-Soldan, Carlos; Shafer, Morgan W.

    2016-10-13

    Here, a technique for tokamak equilibrium reconstructions is used for multiple DIII-D discharges, including L-mode and H-mode cases when weakly 3D fields $\\left(\\delta B/B\\sim {{10}^{-3}}\\right)$ are applied. The technique couples diagnostics to the non-linear, ideal MHD equilibrium solver VMEC, using the V3FIT code, to find the most likely 3D equilibrium based on a suite of measurements. It is demonstrated that V3FIT can be used to find non-linear 3D equilibria that are consistent with experimental measurements of the plasma response to very weak 3D perturbations, as well as with 2D profile measurements. Observations at DIII-D show that plasma rotation larger than 20 krad s–1 changes the relative phase between the applied 3D fields and the measured plasma response. Discharges with low averaged rotation (10 krad s–1) and peaked rotation profiles (40 krad s–1) are reconstructed. Similarities and differences to forward modeled VMEC equilibria, which do not include rotational effects, are shown. Toroidal phase shifts of up to ${{30}^{\\circ}}$ are found between the measured and forward modeled plasma responses at the highest values of rotation. The plasma response phases of reconstructed equilibra on the other hand match the measured ones. This is the first time V3FIT has been used to reconstruct weakly 3D tokamak equilibria.

  12. Use of reconstructed 3D VMEC equilibria to match effects of toroidally rotating discharges in DIII-D

    NASA Astrophysics Data System (ADS)

    Wingen, A.; Wilcox, R. S.; Cianciosa, M. R.; Seal, S. K.; Unterberg, E. A.; Hanson, J. M.; Hirshman, S. P.; Lao, L. L.; Logan, N. C.; Paz-Soldan, C.; Shafer, M. W.

    2017-01-01

    A technique for tokamak equilibrium reconstructions is used for multiple DIII-D discharges, including L-mode and H-mode cases when weakly 3D fields ≤ft(δ B/B˜ {{10}-3}\\right) are applied. The technique couples diagnostics to the non-linear, ideal MHD equilibrium solver VMEC, using the V3FIT code, to find the most likely 3D equilibrium based on a suite of measurements. It is demonstrated that V3FIT can be used to find non-linear 3D equilibria that are consistent with experimental measurements of the plasma response to very weak 3D perturbations, as well as with 2D profile measurements. Observations at DIII-D show that plasma rotation larger than 20 krad s-1 changes the relative phase between the applied 3D fields and the measured plasma response. Discharges with low averaged rotation (10 krad s-1) and peaked rotation profiles (40 krad s-1) are reconstructed. Similarities and differences to forward modeled VMEC equilibria, which do not include rotational effects, are shown. Toroidal phase shifts of up to {{30}\\circ} are found between the measured and forward modeled plasma responses at the highest values of rotation. The plasma response phases of reconstructed equilibra on the other hand match the measured ones. This is the first time V3FIT has been used to reconstruct weakly 3D tokamak equilibria.

  13. Use of reconstructed 3D VMEC equilibria to match effects of toroidally rotating discharges in DIII-D

    DOE PAGES

    Wingen, Andreas; Wilcox, Robert S.; Cianciosa, Mark R.; ...

    2016-10-13

    Here, a technique for tokamak equilibrium reconstructions is used for multiple DIII-D discharges, including L-mode and H-mode cases when weakly 3D fieldsmore » $$\\left(\\delta B/B\\sim {{10}^{-3}}\\right)$$ are applied. The technique couples diagnostics to the non-linear, ideal MHD equilibrium solver VMEC, using the V3FIT code, to find the most likely 3D equilibrium based on a suite of measurements. It is demonstrated that V3FIT can be used to find non-linear 3D equilibria that are consistent with experimental measurements of the plasma response to very weak 3D perturbations, as well as with 2D profile measurements. Observations at DIII-D show that plasma rotation larger than 20 krad s–1 changes the relative phase between the applied 3D fields and the measured plasma response. Discharges with low averaged rotation (10 krad s–1) and peaked rotation profiles (40 krad s–1) are reconstructed. Similarities and differences to forward modeled VMEC equilibria, which do not include rotational effects, are shown. Toroidal phase shifts of up to $${{30}^{\\circ}}$$ are found between the measured and forward modeled plasma responses at the highest values of rotation. The plasma response phases of reconstructed equilibra on the other hand match the measured ones. This is the first time V3FIT has been used to reconstruct weakly 3D tokamak equilibria.« less

  14. 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.

  15. Behavior modification.

    PubMed

    Pelham, W E; Fabiano, G A

    2000-07-01

    Attention deficit/hyperactivity disorder (ADHD) is a chronic and substantially impairing disorder. This means that treatment must also be chronic and substantial. Behavior Modification, and in many cases, the combination of behavior modification and stimulant medication, is a valid, useful treatment for reducing the pervasive impairment experienced by children with ADHD. Based on the research evidence reviewed, behavior modification should be the first line of treatment for children with ADHD.

  16. 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.

  17. From Nash to Cournot-Nash equilibria via the Monge-Kantorovich problem.

    PubMed

    Blanchet, Adrien; Carlier, Guillaume

    2014-11-13

    The notion of Nash equilibria plays a key role in the analysis of strategic interactions in the framework of N player games. Analysis of Nash equilibria is however a complex issue when the number of players is large. In this article, we emphasize the role of optimal transport theory in (i) the passage from Nash to Cournot-Nash equilibria as the number of players tends to infinity and (ii) the analysis of Cournot-Nash equilibria.

  18. 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.

  19. 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.

  20. 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.

  1. 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

  2. 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

  3. 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.

  4. Water equilibria and management using a two-volume model of a polymer electrolyte fuel cell

    NASA Astrophysics Data System (ADS)

    Karnik, Amey Y.; Stefanopoulou, Anna G.; Sun, Jing

    In this paper, we introduce a modified interpretation of the water activity presented in Springer et al. [T.E. Springer, T.A. Zawodzinski, S. Gottesfeld, Polymer electrolyte fuel cell model, J. Electrochem. Soc. 138 (8) (1991) 2334-2342]. The modification directly affects the membrane water transport between the anode and the cathode (two electrodes) of the polymer electrolyte membrane (PEM) fuel cell in the presence of liquid water inside the stack. The modification permits calibration of a zero-dimensional isothermal model to predict the flooding and drying conditions in the two electrodes observed at various current levels [D. Spernjak, S. Advani, A.K. Prasad, Experimental investigation of liquid water formation and transport in a transparent single-serpentine PEM fuel cell, in: Proceedings of the Fourth International Conference on Fuel Cell Science, Engineering and Technology (FUELCELL2006-97271), June 2006]. Using this model the equilibria of the lumped water mass in the two electrodes are analyzed at various flow conditions of the stack to determine stable and unstable (liquid water growth) operating conditions. Two case studies of water management through modification of cathode inlet humidification and anode water removal are then evaluated using this model. The desired anode water removal and the desired cathode inlet humidification are specified based upon (i) the water balance requirements, (ii) the desired conditions in the electrodes, and (iii) the maximum membrane transport at those conditions.

  5. a Molecular Approach to Electrolyte Solutions: Predicting Phase Behavior and Thermodynamic Properties of Single and Binary-Solvent Systems

    NASA Astrophysics Data System (ADS)

    Gering, Kevin Leslie

    A molecular formulation based on modern liquid state theory is applied to the properties and phase behavior of electrolyte systems containing volatile species. An electrolyte model based on the exponential modification of the Mean Spherical Approximation (EXP-MSA) is used to describe the cation-cation, cation-anion, and anion-anion distributions of the ionic species. This theory represents an improvement over the nonmodified MSA approach, and goes beyond the usual Debye-Huckel theory and Pitzer correlation for treating concentrated solutions. Electrolyte solutions such as water-salt, ammonia-salt, mixed salts, and mixed -solvent systems are investigated over a wide range of temperatures, pressures, and compositions. The usual salt properties, such as osmotic and mean activity coefficients and other thermodynamic properties (enthalpies), are calculated. The predictions are accurate to saturation limits. In addition, an iterative method is presented that is used to predict vapor-liquid equilibria (VLE) and thermodynamic properties of single-salt multisolvent electrolytes of the form solvent-cosolvent-salt. In this method, a local composition model (LCM) and EXP-MSA theory are combined with traditional phase equilibria relations to estimate the pressures and compositions of a vapor phase in equilibrium with a binary-solvent electrolyte. Also, a pseudo-solvent model is proposed as a means of obtaining a variety of averaged liquid phase electrolyte properties. To predict preferential solvation in mixed solvents, a general framework is developed that is based on predicted solvation numbers of each solvent. Preferential solvation will be shown to influence VLE. Results show that phase equilibria is accurately predicted by the above iterative method. Three mixed-solvent electrolyte systems are investigated: water -ethylene glycol-LiBr, ammonia-water-LiBr, and methanol -water-LiCl. Finally, the above electrolyte model is utilized in predicting design criteria for a single

  6. 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.

  7. 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) ...

  8. 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…

  9. 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)

  10. 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.

  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. 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.

  13. Global isochrons of a planar system near a phaseless set with saddle equilibria

    NASA Astrophysics Data System (ADS)

    Hannam, James; Krauskopf, Bernd; Osinga, Hinke M.

    2016-11-01

    Given an attracting periodic orbit of a system of ordinary differential equations, one can assign an asymptotic phase to any initial condition that approaches such a periodic orbit. All initial conditions with the same asymptotic phase lie on what is known as an isochron. Isochrons foliate the basin of attraction, and may have intriguing geometric properties. We present here two cases of a planar vector field for which the basin boundary — also referred to as the phaseless set — contains saddle equilibria and their stable manifolds. A continuation-based approach, in combination with Poincaré compactification when the basin is unbounded, allows us to compute isochrons accurately and visualise them as smooth curves to clarify their overall geometry.

  14. 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

  15. Implicit PIC Simulations of Magnetospheric Reconnection Initialized with Fully Kinetic Asymmetric Current-Sheet Equilibria

    NASA Astrophysics Data System (ADS)

    Newman, David L.; Goldman, Martin V.; Lapenta, Giovanni; Markidis, Stefano

    2013-10-01

    A family of one-dimensional kinetic current sheet equilibria has been developed in which the density difference across the sheet is maintained by ambipolar electric fields (with E perpendicular to J and B). These electric fields can form an effective potential barrier that allows particles of one species (e.g., electrons) with the same energy to have different phase-space densities on the two sides of the current sheet, thereby breaking the symmetry. Such solutions necessarily require the inclusion of non-Maxwellian features, and share characteristics with double layers and other nonlinear electrostatic structures. Implicit PIC simulations were initialized with the electron and ion distribution functions corresponding to specific solutions of this type and were found to behave as equilibria that are subject to an asymmetric tearing-mode-like instability. As expected, the instability growth rate increases as the width of the current sheet decreases. Imposing a weak perturbation on the equilibrium allows for a controlled study of the evolution of the asymmetric reconnecting plasma. Examples will be presented of the evolution for different initial states relevant to magnetospheric reconnection, including varying values of the guide magnetic field. Research supported by NSF and NASA.

  16. 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

    2016-09-02

    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

  17. 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.

  18. Calculation of Ceramic Phase Diagrams

    DTIC Science & Technology

    1979-11-30

    Parameters were derived covering the liquid, spinel , periclase, corundum alpha and beta. DD IJAN73 1413 EDITIOW OF I NOV4SS IS OSSOLETE (/Ai/Ec-;/ 5 - -rZ7 77...Lattice Stability, Solution and Compound Phase Parameters were derived covering the liquid, spinel , periclase, corundum alpha and beta quartz, crystobalite...and compound phase parameters for the liquid, spinel , corundum and periclase phases can be employed to calculate phase equilibria activity, vapor

  19. 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.

  20. 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.