Sample records for equilibrium phase experimental

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

    PubMed Central

    Solozhenko, Vladimir L.; Kurakevych, Oleksandr O.

    2013-01-01

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

  2. Phase Equilibrium, Chemical Equilibrium, and a Test of the Third Law: Experiments for Physical Chemistry.

    ERIC Educational Resources Information Center

    Dannhauser, Walter

    1980-01-01

    Described is an experiment designed to provide an experimental basis for a unifying point of view (utilizing theoretical framework and chemistry laboratory experiments) for physical chemistry students. Three experiments are described: phase equilibrium, chemical equilibrium, and a test of the third law of thermodynamics. (Author/DS)

  3. Phase Equilibrium Investigations of Planetary Materials

    NASA Technical Reports Server (NTRS)

    Grove, T. L.

    2005-01-01

    This grant provided funds to carry out phase equilibrium studies on the processes of chemical differentiation of the moon and the meteorite parent bodies, during their early evolutionary history. Several experimental studies examined processes that led to the formation of lunar ultramafic glasses. Phase equilibrium studies were carried out on selected low-Ti and high-Ti lunar ultramafic glass compositions to provide constraints on the depth range, temperature and processes of melt generation and/or assimilation. A second set of experiments examined the role of sulfide melts in core formation processes in the earth and terrestrial planets. The major results of each paper are discussed, and copies of the papers are attached as Appendix I.

  4. Group Contribution Methods for Phase Equilibrium Calculations.

    PubMed

    Gmehling, Jürgen; Constantinescu, Dana; Schmid, Bastian

    2015-01-01

    The development and design of chemical processes are carried out by solving the balance equations of a mathematical model for sections of or the whole chemical plant with the help of process simulators. For process simulation, besides kinetic data for the chemical reaction, various pure component and mixture properties are required. Because of the great importance of separation processes for a chemical plant in particular, a reliable knowledge of the phase equilibrium behavior is required. The phase equilibrium behavior can be calculated with the help of modern equations of state or g(E)-models using only binary parameters. But unfortunately, only a very small part of the experimental data for fitting the required binary model parameters is available, so very often these models cannot be applied directly. To solve this problem, powerful predictive thermodynamic models have been developed. Group contribution methods allow the prediction of the required phase equilibrium data using only a limited number of group interaction parameters. A prerequisite for fitting the required group interaction parameters is a comprehensive database. That is why for the development of powerful group contribution methods almost all published pure component properties, phase equilibrium data, excess properties, etc., were stored in computerized form in the Dortmund Data Bank. In this review, the present status, weaknesses, advantages and disadvantages, possible applications, and typical results of the different group contribution methods for the calculation of phase equilibria are presented.

  5. Phase equilibrium measurements on nine binary mixtures

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

    Wilding, W.V.; Giles, N.F.; Wilson, L.C.

    1996-11-01

    Phase equilibrium measurements have been performed on nine binary mixtures. The PTx method was used to obtain vapor-liquid equilibrium data for the following systems at two temperatures each: (aminoethyl)piperazine + diethylenetriamine; 2-butoxyethyl acetate + 2-butoxyethanol; 2-methyl-2-propanol + 2-methylbutane; 2-methyl-2-propanol + 2-methyl-2-butene; methacrylonitrile + methanol; 1-chloro-1,1-difluoroethane + hydrogen chloride; 2-(hexyloxy)ethanol + ethylene glycol; butane + ammonia; propionaldehyde + butane. Equilibrium vapor and liquid phase compositions were derived form the PTx data using the Soave equation of state to represent the vapor phase and the Wilson or the NRTL activity coefficient model to represent the liquid phase. A large immiscibility region existsmore » in the butane + ammonia system at 0 C. Therefore, separate vapor-liquid-liquid equilibrium measurements were performed on this system to more precisely determine the miscibility limits and the composition of the vapor phase in equilibrium with the two liquid phases.« less

  6. The deconfining phase transition in and out of equilibrium

    NASA Astrophysics Data System (ADS)

    Bazavov, Oleksiy

    Recent experiments carried out at the Relativistic Heavy Ion Collider at the Brookhaven National Laboratory provide strong evidence that a matter can be driven from a confined, low-temperature phase, observed in our every day world into a deconfined high-temperature phase of liberated quarks and gluons. The equilibrium and dynamical properties of the deconfining phase transition are thus of great theoretical interest, since they also provide an information about the first femtoseconds of the evolution of our Universe, when the hot primordial soup while cooling has undergone a chain of phase transitions. The aspects of the deconfining phase transition studied in this work include: the dynamics of the SU(3) gauge theory after the heating quench (which models rapid heating in the heavy-ion collisions), equilibrium properties of the phase transition in the SU(3) gauge theory with boundaries at low temperature (small volumes at RHIC suggest that boundary effects cannot be neglected and periodic boundary conditions normally used in lattice simulations do not correspond to the experimental situation), and a study of the order of the transition in U(1) gauge theory.

  7. Semi-experimental equilibrium structure of pyrazinamide from gas-phase electron diffraction. How much experimental is it?

    NASA Astrophysics Data System (ADS)

    Tikhonov, Denis S.; Vishnevskiy, Yury V.; Rykov, Anatolii N.; Grikina, Olga E.; Khaikin, Leonid S.

    2017-03-01

    A semi-experimental equilibrium structure of free molecules of pyrazinamide has been determined for the first time using gas electron diffraction method. The refinement was carried using regularization of geometry by calculated quantum chemical parameters. It is discussed to which extent is the final structure experimental. A numerical approach for estimation of the amount of experimental information in the refined parameters is suggested. The following values of selected internuclear distances were determined (values are in Å with 1σ in the parentheses): re(Cpyrazine-Cpyrazine)av = 1.397(2), re(Npyrazine-Cpyrazine)av = 1.332(3), re(Cpyrazine-Camide) = 1.493(1), re(Namide-Camide) = 1.335(2), re(Oamide-Camide) = 1.219(1). The given standard deviations represent pure experimental uncertainties without the influence of regularization.

  8. Phase equilibrium measurements on twelve binary mixtures

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

    Giles, N.F.; Wilson, H.L.; Wilding, W.V.

    1996-11-01

    Phase equilibrium measurements have been performed on twelve binary mixtures. The PTx method was used to obtain vapor-liquid equilibrium data for the following binary systems at two temperatures each: ethanethiol + propylene; nitrobenzene + methanol; pyridine + ethyl acetate; octane + tert-amyl methyl ether; diisopropyl ether + butane; 1,3-dichloro-2-propanol + epichlorohydrin; 2,3-dichloro-1-propanol + epichlorohydrin; 2,3-epoxy-1-propanol + epichlorohydrin; 3-chloro-1,2-propanediol + epichlorohydrin; methanol + hydrogen cyanide. For these systems, equilibrium vapor and liquid phase compositions were derived from the PTx data using the Soave equation of state to represent the vapor phase and the Wilson, NRTL, or Redlich-Kister activity coefficient model tomore » represent the liquid phase. The infinite dilution activity coefficient of methylamine in N-methyl-2-pyrrolidone was determined at three temperatures by performing PTx measurements on the N-methyl-2-pyrrolidone was determined at three temperatures by performing PTx measurements on the N-methyl-2-pyrrolidone-rich half of the binary. Liquid-liquid equilibrium studies were made on the triethylene glycol + 1-pentene system at two temperatures by directly analyzing samples taken from each liquid phase.« less

  9. Mapping Isobaric Aging onto the Equilibrium Phase Diagram.

    PubMed

    Niss, Kristine

    2017-09-15

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

  10. Effect of organic matters on CO2 hydrate phase equilibrium conditions in Na-montmorillonite clay

    NASA Astrophysics Data System (ADS)

    Park, T.; Kyung, D.; Lee, W.

    2013-12-01

    Formation of gas hydrates provides an attractive idea for storing greenhouse gases in a long-term stable geological formation. Since the phase equilibrium conditions of gas hydrates indicate the stability of hydrates, estimation of the phase equilibrium conditions of gas hydrates in marine geological conditions is necessary. In this study, we have identified the effects of organic matters (glycine, glucose, and urea) and solid surface (montmorillonite (MMT)) on the three-phase (liquid-hydrate-vapor) equilibrium conditions of CO2 hydrate. CO2 phase equilibrium experiments were conducted using 0.5mol% organic matter solutions with and without 10g soil mineral were experimentally conducted. Addition of organic matters shifted the phase equilibrium conditions of CO2 hydrate to the higher pressure or lower pressure region because of higher competition of water molecules due to the dissolved organic matters. Presence of MMT also leaded to the higher equilibrium pressure due to the interaction of cations with water molecules. By addition of organic matters to the clay suspension, the hydrate phase equilibrium conditions were less inhibited compared to those of MMT and organic matters independently. The diminished magnitudes by addition of organic matters to the clay suspension (MMT > MMT+urea > MMT+glycine > MMT+glucose > DIW) were different to the order of inhibition degree without MMT (Glucose > glycine > urea > DIW). X-ray diffraction (XRD), scanning electron microscope (SEM), and ion chromatography (IC) analysis were conducted to support the hypothesis that the organic matters interact with cations in MMT interlayer space, and leads to the less inhibition of phase equilibrium conditions. The present study provides basic information for the formation and dissociation of CO2 hydrates in the geological formation when sequestering CO2 as a form of CO2 hydrate.

  11. The Kibble-Zurek mechanism in phase transitions of non-equilibrium systems

    NASA Astrophysics Data System (ADS)

    Cheung, Hil F. H.; Patil, Yogesh S.; Date, Aditya G.; Vengalattore, Mukund

    2017-04-01

    We experimentally realize a driven-dissipative phase transition using a mechanical parametric amplifier to demonstrate key signatures of a second order phase transition, including a point where the susceptibilities and relaxation time scales diverge, and where the system exhibits a spontaneous breaking of symmetry. Though reminiscent of conventional equilibrium phase transitions, it is unclear if such driven-dissipative phase transitions are amenable to the conventional Landau-Ginsburg-Wilson paradigm, which relies on concepts of scale invariance and universality, and recent work has shown that such phase transitions can indeed lie beyond such conventional universality classes. By quenching the system past the critical point, we investigate the dynamics of the emergent ordered phase and find that our measurements are in excellent agreement with the Kibble-Zurek mechanism. In addition to verifying the Kibble-Zurek hypothesis in driven-dissipative phase transitions for the first time, we also demonstrate that the measured critical exponents accurately reflect the interplay between intrinsic coherent dynamics and environmental correlations, showing a clear departure from mean field exponents in the case of non-Markovian system-bath interactions. We further discuss how reservoir engineering and the imposition of artificial environmental correlations can result in the stabilization of novel many-body quantum phases and aid in the creation of exotic non-equilibrium states of matter.

  12. CFD analysis of laboratory scale phase equilibrium cell operation

    NASA Astrophysics Data System (ADS)

    Jama, Mohamed Ali; Nikiforow, Kaj; Qureshi, Muhammad Saad; Alopaeus, Ville

    2017-10-01

    For the modeling of multiphase chemical reactors or separation processes, it is essential to predict accurately chemical equilibrium data, such as vapor-liquid or liquid-liquid equilibria [M. Šoóš et al., Chem. Eng. Process.: Process Intensif. 42(4), 273-284 (2003)]. The instruments used in these experiments are typically designed based on previous experiences, and their operation verified based on known equilibria of standard components. However, mass transfer limitations with different chemical systems may be very different, potentially falsifying the measured equilibrium compositions. In this work, computational fluid dynamics is utilized to design and analyze laboratory scale experimental gas-liquid equilibrium cell for the first time to augment the traditional analysis based on plug flow assumption. Two-phase dilutor cell, used for measuring limiting activity coefficients at infinite dilution, is used as a test case for the analysis. The Lagrangian discrete model is used to track each bubble and to study the residence time distribution of the carrier gas bubbles in the dilutor cell. This analysis is necessary to assess whether the gas leaving the cell is in equilibrium with the liquid, as required in traditional analysis of such apparatus. Mass transfer for six different bio-oil compounds is calculated to determine the approach equilibrium concentration. Also, residence times assuming plug flow and ideal mixing are used as reference cases to evaluate the influence of mixing on the approach to equilibrium in the dilutor. Results show that the model can be used to predict the dilutor operating conditions for which each of the studied gas-liquid systems reaches equilibrium.

  13. CFD analysis of laboratory scale phase equilibrium cell operation.

    PubMed

    Jama, Mohamed Ali; Nikiforow, Kaj; Qureshi, Muhammad Saad; Alopaeus, Ville

    2017-10-01

    For the modeling of multiphase chemical reactors or separation processes, it is essential to predict accurately chemical equilibrium data, such as vapor-liquid or liquid-liquid equilibria [M. Šoóš et al., Chem. Eng. Process Intensif. 42(4), 273-284 (2003)]. The instruments used in these experiments are typically designed based on previous experiences, and their operation verified based on known equilibria of standard components. However, mass transfer limitations with different chemical systems may be very different, potentially falsifying the measured equilibrium compositions. In this work, computational fluid dynamics is utilized to design and analyze laboratory scale experimental gas-liquid equilibrium cell for the first time to augment the traditional analysis based on plug flow assumption. Two-phase dilutor cell, used for measuring limiting activity coefficients at infinite dilution, is used as a test case for the analysis. The Lagrangian discrete model is used to track each bubble and to study the residence time distribution of the carrier gas bubbles in the dilutor cell. This analysis is necessary to assess whether the gas leaving the cell is in equilibrium with the liquid, as required in traditional analysis of such apparatus. Mass transfer for six different bio-oil compounds is calculated to determine the approach equilibrium concentration. Also, residence times assuming plug flow and ideal mixing are used as reference cases to evaluate the influence of mixing on the approach to equilibrium in the dilutor. Results show that the model can be used to predict the dilutor operating conditions for which each of the studied gas-liquid systems reaches equilibrium.

  14. Experimental determination of thermodynamic equilibrium in biocatalytic transamination.

    PubMed

    Tufvesson, Pär; Jensen, Jacob S; Kroutil, Wolfgang; Woodley, John M

    2012-08-01

    The equilibrium constant is a critical parameter for making rational design choices in biocatalytic transamination for the synthesis of chiral amines. However, very few reports are available in the scientific literature determining the equilibrium constant (K) for the transamination of ketones. Various methods for determining (or estimating) equilibrium have previously been suggested, both experimental as well as computational (based on group contribution methods). However, none of these were found suitable for determining the equilibrium constant for the transamination of ketones. Therefore, in this communication we suggest a simple experimental methodology which we hope will stimulate more accurate determination of thermodynamic equilibria when reporting the results of transaminase-catalyzed reactions in order to increase understanding of the relationship between substrate and product molecular structure on reaction thermodynamics. Copyright © 2012 Wiley Periodicals, Inc.

  15. Non-equilibrium phase transitions in a liquid crystal

    NASA Astrophysics Data System (ADS)

    Dan, K.; Roy, M.; Datta, A.

    2015-09-01

    The present manuscript describes kinetic behaviour of the glass transition and non-equilibrium features of the "Nematic-Isotropic" (N-I) phase transition of a well known liquid crystalline material N-(4-methoxybenzylidene)-4-butylaniline from the effects of heating rate and initial temperature on the transitions, through differential scanning calorimetry (DSC), Fourier transform infrared and fluorescence spectroscopy. Around the vicinity of the glass transition temperature (Tg), while only a change in the baseline of the ΔCp vs T curve is observed for heating rate (β) > 5 K min-1, consistent with a glass transition, a clear peak for β ≤ 5 K min-1 and the rapid reduction in the ΔCp value from the former to the latter rate correspond to an order-disorder transition and a transition from ergodic to non-ergodic behaviour. The ln β vs 1000/T curve for the glass transition shows convex Arrhenius behaviour that can be explained very well by a purely entropic activation barrier [Dan et al., Eur. Phys. Lett. 108, 36007 (2014)]. Fourier transform infrared spectroscopy indicates sudden freezing of the out-of-plane distortion vibrations of the benzene rings around the glass transition temperature and a considerable red shift indicating enhanced coplanarity of the benzene rings and, consequently, enhancement in the molecular ordering compared to room temperature. We further provide a direct experimental evidence of the non-equilibrium nature of the N-I transition through the dependence of this transition temperature (TNI) and associated enthalpy change (ΔH) on the initial temperature (at fixed β-values) for the DSC scans. A plausible qualitative explanation based on Mesquita's extension of Landau-deGennes theory [O. N. de Mesquita, Braz. J. Phys. 28, 257 (1998)] has been put forward. The change in the molecular ordering from nematic to isotropic phase has been investigated through fluorescence anisotropy measurements where the order parameter, quantified by the

  16. Non-equilibrium phase transitions in a driven-dissipative system of interacting bosons

    NASA Astrophysics Data System (ADS)

    Young, Jeremy T.; Foss-Feig, Michael; Gorshkov, Alexey V.; Maghrebi, Mohammad F.

    2017-04-01

    Atomic, molecular, and optical systems provide unique opportunities to study simple models of driven-dissipative many-body quantum systems. Typically, one is interested in the resultant steady state, but the non-equilibrium nature of the physics involved presents several problems in understanding its behavior theoretically. Recently, it has been shown that in many of these models, it is possible to map the steady-state phase transitions onto classical equilibrium phase transitions. In the language of Keldysh field theory, this relation typically only becomes apparent after integrating out massive fields near the critical point, leaving behind a single massless field undergoing near-equilibrium dynamics. In this talk, we study a driven-dissipative XXZ bosonic model and discover critical points at which two fields become gapless. Each critical point separates three different possible phases: a uniform phase, an anti-ferromagnetic phase, and a limit cycle phase. Furthermore, a description in terms of an equilibrium phase transition does not seem possible, so the associated phase transitions appear to be inherently non-equilibrium.

  17. Phase Equilibrium Investigation on 2-Phenylethanol in Binary and Ternary Systems: Influence of High Pressure on Density and Solid-Liquid Phase Equilibrium.

    PubMed

    Domańska, Urszula; Królikowski, Marek; Wlazło, Michał; Więckowski, Mikołaj

    2018-05-30

    Ionic liquids (ILs) are important new solvents proposed for applications in different separation processes. Herein, an idea of possible use of high pressure in a general strategy of production of 2-phenylethanol (PEA) is discussed. In this work, we present the influence of pressure on the density in binary systems of {1-hexyl-1-methylpyrrolidynium bis{(trifluoromethyl)sulfonyl}imide, [HMPYR][NTf 2 ], or 1-dodecyl-3-methylimidazolium bis{(trifluoromethyl)sulfonyl}imide, [DoMIM][NTf 2 ] + PEA} in a wide range of temperatures (298.15-348.15 K) and pressures (0.1-40 MPa). The densities at ambient and high pressures are measured to present the physicochemical properties of the ILs used in the process of separation of PEA from aqueous phase. The Tait equation was used for the correlation of density of one-component and two-component systems as a function of mole fraction, temperature, and pressure. The influence of pressure is not significant. These systems exhibit mainly negative molar excess volumes, V E . The solid-liquid phase equilibrium (SLE) of [DoMIM][NTf 2 ] in PEA at atmospheric pressure was measured and compared to the SLE high-pressure results. Additionally, the ternary liquid-liquid phase equilibrium (LLE) at ambient pressure in the {[DoMIM][NTf 2 ] (1) + PEA (2) + water (3)} at temperature T = 308.15 K was investigated. The solubility of water in the [DoMIM][NTf 2 ] is quite high in comparison with that measured by us earlier for ILs ( x 3 = 0.403) at T = 308.15 K, which results in not very successful average selectivity of extraction of PEA from the aqueous phase. The [DoMIM][NTf 2 ] has shown strong interaction with PEA without the immiscibility region. The ternary system revealed Treybal's type phase equilibrium in which two partially miscible binaries ([DoMIM][NTf 2 ] + water) and (PEA + water) exist. From the results of LLE in the ternary system, the selectivity and the solute distribution ratio of separation of water/PEA were calculated and compared

  18. Solution properties of almandine-pyrope garnet as determined by phase equilibrium experiments

    USGS Publications Warehouse

    Koziol, A.M.; Bohlen, S.R.

    1992-01-01

    The thermodynamic mixing properties of almandine-pyrope garnet were derived from phase equilibrium experiments at temperatures of 900 and 1000??C and pressures from 8 to 14 kbar. Almandine has essentially ideal behavior in almandine-pyrope garnet over the composition range Alm89-Alm61 at the above experimental conditions. In all experimental products a systematic partitioning of Fe and Mg between garnet and ilmenite was seen with ln Kd ??? 1.59 which was not temperature sensitive. The results support the use of garnet mixing models that incorporate ideal or nearly ideal Fe-Mg parameters. -from Authors

  19. Evaluating measurement uncertainty in fluid phase equilibrium calculations

    NASA Astrophysics Data System (ADS)

    van der Veen, Adriaan M. H.

    2018-04-01

    The evaluation of measurement uncertainty in accordance with the ‘Guide to the expression of uncertainty in measurement’ (GUM) has not yet become widespread in physical chemistry. With only the law of the propagation of uncertainty from the GUM, many of these uncertainty evaluations would be cumbersome, as models are often non-linear and require iterative calculations. The methods from GUM supplements 1 and 2 enable the propagation of uncertainties under most circumstances. Experimental data in physical chemistry are used, for example, to derive reference property data and support trade—all applications where measurement uncertainty plays an important role. This paper aims to outline how the methods for evaluating and propagating uncertainty can be applied to some specific cases with a wide impact: deriving reference data from vapour pressure data, a flash calculation, and the use of an equation-of-state to predict the properties of both phases in a vapour-liquid equilibrium. The three uncertainty evaluations demonstrate that the methods of GUM and its supplements are a versatile toolbox that enable us to evaluate the measurement uncertainty of physical chemical measurements, including the derivation of reference data, such as the equilibrium thermodynamical properties of fluids.

  20. Phase equilibrium modeling for high temperature metallization on GaAs solar cells

    NASA Technical Reports Server (NTRS)

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

    1991-01-01

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

  1. Effect of organic matter on CO(2) hydrate phase equilibrium in phyllosilicate suspensions.

    PubMed

    Park, Taehyung; Kyung, Daeseung; Lee, Woojin

    2014-06-17

    In this study, we examined various CO2 hydrate phase equilibria under diverse, heterogeneous conditions, to provide basic knowledge for successful ocean CO2 sequestration in offshore marine sediments. We investigated the effect of geochemical factors on CO2 hydrate phase equilibrium. The three-phase (liquid-hydrate-vapor) equilibrium of CO2 hydrate in the presence of (i) organic matter (glycine, glucose, and urea), (ii) phyllosilicates [illite, kaolinite, and Na-montmorillonite (Na-MMT)], and (iii) mixtures of them was measured in the ranges of 274.5-277.0 K and 14-22 bar. Organic matter inhibited the phase equilibrium of CO2 hydrate by association with water molecules. The inhibition effect decreased in the order: urea < glycine < glucose. Illite and kaolinite (unexpandable clays) barely affected the CO2 hydrate phase equilibrium, while Na-MMT (expandable clay) affected the phase equilibrium because of its interlayer cations. The CO2 hydrate equilibrium conditions, in the illite and kaolinite suspensions with organic matter, were very similar to those in the aqueous organic matter solutions. However, the equilibrium condition in the Na-MMT suspension with organic matter changed because of reduction of its inhibition effect by intercalated organic matter associated with cations in the Na-MMT interlayer.

  2. Experimental Phase Equilibria Studies of the Pb-Fe-O System in Air, in Equilibrium with Metallic Lead and at Intermediate Oxygen Potentials

    NASA Astrophysics Data System (ADS)

    Shevchenko, M.; Jak, E.

    2017-12-01

    The phase equilibria information on the Pb-Fe-O system is of practical importance for the improvement of the existing thermodynamic database of lead-containing slag systems (Pb-Zn-Fe-Cu-Si-Ca-Al-Mg-O). Phase equilibria of the Pb-Fe-O system have been investigated: (a) in air at temperatures between 1053 K and 1373 K (780 °C and 1100 °C); (b) in equilibrium with metallic lead at temperatures between 1053 K and 1373 K (780 °C and 1100 °C); and (c) at intermediate oxidation conditions for the liquid slag in equilibrium with two solids (spinel + magnetoplumbite), at temperatures between 1093 K and 1373 K (820 °C and 1100 °C). The high-temperature equilibration/quenching/electron probe X-ray microanalysis technique has been used to accurately determine the compositions of the phases in equilibrium in the system. The Pb and Fe concentrations in the phases were determined directly; preliminary thermodynamic modeling with FactSage was used to estimate the ferrous-to-ferric ratios and to present the results in the ternary diagram.

  3. Demonstration of the Kibble-Zurek mechanism in a non-equilibrium phase transition

    NASA Astrophysics Data System (ADS)

    Patil, Yogesh S.; Cheung, Hil F. H.; Date, Aditya G.; Vengalattore, Mukund

    2017-04-01

    We describe the experimental realization of a driven-dissipative phase transition (DPT) in a mechanical parametric amplifier and demonstrate key signatures of a critical point in the system, where the susceptibilities and relaxation time scales diverge and coincide with the spontaneous breaking of symmetry and the emergence of macroscopic order. While these observations are reminiscent of equilibrium phase transitions, it is presently an open question whether such DPTs are amenable to the conventional Landau-Ginsburg-Wilson paradigm that relies on concepts of scale invariance and universality - Indeed, recent theoretical work has predicted that DPTs can exhibit phenomenology that departs from these conventional paradigms. By quenching the system past the critical point, we measure the dynamics of the emergent ordered phase and its departure from adiabaticity, and find that our measurements are in excellent agreement with the Kibble-Zurek hypothesis. In addition to validating the KZ mechanism in a DPT for the first time, we also uniquely show that the measured critical exponents accurately reflect the interplay between the intrinsic coherent dynamics and the environmental correlations, with a clear departure from mean field exponents in the case of non-Markovian system-bath interactions. We also discuss how the techniques of reservoir engineering and the imposition of artificial environmental correlations can result in the stabilization of novel many-body quantum phases and exotic non-equilibrium states of matter.

  4. The calculation of the phase equilibrium of the multicomponent hydrocarbon systems

    NASA Astrophysics Data System (ADS)

    Molchanov, D. A.

    2018-01-01

    Hydrocarbon mixtures filtration process simulation development has resulted in use of cubic equations of state of the van der Waals type to describe the thermodynamic properties of natural fluids under real thermobaric conditions. Binary hydrocarbon systems allow to simulate the fluids of different types of reservoirs qualitatively, what makes it possible to carry out the experimental study of their filtration features. Exploitation of gas-condensate reservoirs shows the possibility of existence of various two-phase filtration regimes, including self-oscillatory one, which occurs under certain values of mixture composition, temperature and pressure drop. Plotting of the phase diagram of the model mixture is required to determine these values. A software package to calculate the vapor-liquid equilibrium of binary systems using cubic equation of state of the van der Waals type has been created. Phase diagrams of gas-condensate model mixtures have been calculated.

  5. Out-of-equilibrium Sm Fe based phases

    NASA Astrophysics Data System (ADS)

    Djéga-Mariadassou, C.; Bessais, L.

    2008-02-01

    Structure and magnetic properties of nanocrystalline P6/mmm out-of-equilibrium precursors of hard magnetic R-3m Sm2(Fe,M)17C (M=Ga,Si,) and I4/mmm Sm(Fe,Co,Ti)11 equilibrium phases, are presented. Their structure is explained with a model ground on the R1 - s T5 + 2 s formula (R=rare-earth, s=vacancy rate, T=transition metal) where s Sm atoms are statistically substituted by s transition metal pairs. The Rietveld analysis (RA) provides the stoichiometry of the precursors, 1:9 and 1:10, respectively precursor of 2:17 and 1:12 phases. The interpretation of the Mössbauer spectra of the 1:9 and 1:10 phases, is based on the correlation between δ and the Wigner Seitz Cell volumes, calculated from the structural parameters. The δ behaviour of each crystallographic site versus Co content, defines the Co location while it confirms that of Si and Ga obtained by RA. Substitution occurs in 3 g site, whatever Co or M. The Sm(Fe,Co,Ti)10 and Sm(Fe,M)9C Curie temperature (Tc) are compared to those of the equilibrium phases, the effects of Fe substitution and C addition are discussed. The maximum μ 0Hc is obtained for low M or Co content, for auto-coherent diffraction domain size ˜30 nm. SmFe8.75Ga0.25C and SmFe8.75Si0.25C with Tc of 680 and 690 K, show respectively Mr and μ 0Hc of 58 emu/g, 27 kOe and 95 emu/g, 15 kOe, values higher than those obtained for Sm2(Fe,M)17 carbides.

  6. A modified experimental setup for sedimentation equilibrium experiments with gels. Part 2: Technical developments.

    PubMed

    Cölfen, H; Borchard, W

    1994-06-01

    This part of the paper trilogy describes technical developments for an efficient experimental setup to investigate gels with equilibrium analytical ultracentrifugation. New 10-channel centerpieces for the Schlieren optics, a new programmable multiplexer, a modified Schlieren optical system, and a photo pickup with impulse transformer are introduced as major developments. Also, some new centerpieces suitable for equilibrium experiments with solutions using the Rayleigh interference and the uv-absorption optics are presented. These centerpieces allow the investigation of 10, 12, or even 26 samples per centerpiece. The problem to find suitable materials for cell centerpieces and windows in the case of adhering samples is discussed for the system gelatin/water. A phase volume calculation for circular sample channels as a correction for the case of broadened menisci is presented. The method described allows an accurate measurement of up to 70 samples simultaneously in an equilibrium experiment if the 8-hole rotor presented in part 1 of the trilogy is used. The number of samples is sufficient to characterize a gel/solvent system in the experimentally accessible range under identical conditions, which is not possible by means of any of the methods known before. All parts described are also applicable for the investigation of solutions.

  7. Analysis of three-phase equilibrium conditions for methane hydrate by isometric-isothermal molecular dynamics simulations.

    PubMed

    Yuhara, Daisuke; Brumby, Paul E; Wu, David T; Sum, Amadeu K; Yasuoka, Kenji

    2018-05-14

    To develop prediction methods of three-phase equilibrium (coexistence) conditions of methane hydrate by molecular simulations, we examined the use of NVT (isometric-isothermal) molecular dynamics (MD) simulations. NVT MD simulations of coexisting solid hydrate, liquid water, and vapor methane phases were performed at four different temperatures, namely, 285, 290, 295, and 300 K. NVT simulations do not require complex pressure control schemes in multi-phase systems, and the growth or dissociation of the hydrate phase can lead to significant pressure changes in the approach toward equilibrium conditions. We found that the calculated equilibrium pressures tended to be higher than those reported by previous NPT (isobaric-isothermal) simulation studies using the same water model. The deviations of equilibrium conditions from previous simulation studies are mainly attributable to the employed calculation methods of pressure and Lennard-Jones interactions. We monitored the pressure in the methane phase, far from the interfaces with other phases, and confirmed that it was higher than the total pressure of the system calculated by previous studies. This fact clearly highlights the difficulties associated with the pressure calculation and control for multi-phase systems. The treatment of Lennard-Jones interactions without tail corrections in MD simulations also contributes to the overestimation of equilibrium pressure. Although improvements are still required to obtain accurate equilibrium conditions, NVT MD simulations exhibit potential for the prediction of equilibrium conditions of multi-phase systems.

  8. Analysis of three-phase equilibrium conditions for methane hydrate by isometric-isothermal molecular dynamics simulations

    NASA Astrophysics Data System (ADS)

    Yuhara, Daisuke; Brumby, Paul E.; Wu, David T.; Sum, Amadeu K.; Yasuoka, Kenji

    2018-05-01

    To develop prediction methods of three-phase equilibrium (coexistence) conditions of methane hydrate by molecular simulations, we examined the use of NVT (isometric-isothermal) molecular dynamics (MD) simulations. NVT MD simulations of coexisting solid hydrate, liquid water, and vapor methane phases were performed at four different temperatures, namely, 285, 290, 295, and 300 K. NVT simulations do not require complex pressure control schemes in multi-phase systems, and the growth or dissociation of the hydrate phase can lead to significant pressure changes in the approach toward equilibrium conditions. We found that the calculated equilibrium pressures tended to be higher than those reported by previous NPT (isobaric-isothermal) simulation studies using the same water model. The deviations of equilibrium conditions from previous simulation studies are mainly attributable to the employed calculation methods of pressure and Lennard-Jones interactions. We monitored the pressure in the methane phase, far from the interfaces with other phases, and confirmed that it was higher than the total pressure of the system calculated by previous studies. This fact clearly highlights the difficulties associated with the pressure calculation and control for multi-phase systems. The treatment of Lennard-Jones interactions without tail corrections in MD simulations also contributes to the overestimation of equilibrium pressure. Although improvements are still required to obtain accurate equilibrium conditions, NVT MD simulations exhibit potential for the prediction of equilibrium conditions of multi-phase systems.

  9. Ordered phase and non-equilibrium fluctuation in stock market

    NASA Astrophysics Data System (ADS)

    Maskawa, Jun-ichi

    2002-08-01

    We analyze the statistics of daily price change of stock market in the framework of a statistical physics model for the collective fluctuation of stock portfolio. In this model the time series of price changes are coded into the sequences of up and down spins, and the Hamiltonian of the system is expressed by spin-spin interactions as in spin glass models of disordered magnetic systems. Through the analysis of Dow-Jones industrial portfolio consisting of 30 stock issues by this model, we find a non-equilibrium fluctuation mode on the point slightly below the boundary between ordered and disordered phases. The remaining 29 modes are still in disordered phase and well described by Gibbs distribution. The variance of the fluctuation is outlined by the theoretical curve and peculiarly large in the non-equilibrium mode compared with those in the other modes remaining in ordinary phase.

  10. Aromatherapy: composition of the gaseous phase at equilibrium with liquid bergamot essential oil.

    PubMed

    Leggio, Antonella; Leotta, Vanessa; Belsito, Emilia Lucia; Di Gioia, Maria Luisa; Romio, Emanuela; Santoro, Ilaria; Taverna, Domenico; Sindona, Giovanni; Liguori, Angelo

    2017-11-02

    This work compares the composition at different temperatures of gaseous phase of bergamot essential oil at equilibrium with the liquid phase. A new GC-MS methodology to determine quantitatively the volatile aroma compounds was developed. The adopted methodology involved the direct injection of headspace gas into injection port of GC-MS system and of known amounts of the corresponding authentic volatile compounds. The methodology was validated. This study showed that gaseous phase composition is different from that of the liquid phase at equilibrium with it.

  11. Phase Transitions and Scaling in Systems Far from Equilibrium

    NASA Astrophysics Data System (ADS)

    Täuber, Uwe C.

    2017-03-01

    Scaling ideas and renormalization group approaches proved crucial for a deep understanding and classification of critical phenomena in thermal equilibrium. Over the past decades, these powerful conceptual and mathematical tools were extended to continuous phase transitions separating distinct nonequilibrium stationary states in driven classical and quantum systems. In concordance with detailed numerical simulations and laboratory experiments, several prominent dynamical universality classes have emerged that govern large-scale, long-time scaling properties both near and far from thermal equilibrium. These pertain to genuine specific critical points as well as entire parameter space regions for steady states that display generic scale invariance. The exploration of nonstationary relaxation properties and associated physical aging scaling constitutes a complementary potent means to characterize cooperative dynamics in complex out-of-equilibrium systems. This review describes dynamic scaling features through paradigmatic examples that include near-equilibrium critical dynamics, driven lattice gases and growing interfaces, correlation-dominated reaction-diffusion systems, and basic epidemic models.

  12. Cation disorder and gas phase equilibrium in an YBa 2Cu 3O 7- x superconducting thin film

    NASA Astrophysics Data System (ADS)

    Shin, Dong Chan; Ki Park, Yong; Park, Jong-Chul; Kang, Suk-Joong L.; Yong Yoon, Duk

    1997-02-01

    YBa 2Cu 3O 7- x superconducting thin films have been grown by in situ off-axis rf sputtering with varying oxygen pressure, Ba/Y ratio in a target, and deposition temperature. With decreasing oxygen pressure, increasing Ba/Y ratio, increasing deposition temperature, the critical temperature of the thin films decreased and the c-axis length increased. The property change of films with the variation of deposition variables has been explained by a gas phase equilibrium of the oxidation reaction of Ba and Y. Applying Le Chatelier's principle to the oxidation reaction, we were able to predict the relation of deposition variables and the resultant properties of thin films; the prediction was in good agreement with the experimental results. From the relation between the three deposition variables and gas phase equilibrium, a 3-dimensional processing diagram was introduced. This diagram has shown that the optimum deposition condition of YBa 2Cu 3O 7- x thin films is not a fixed point but can be varied. The gas phase equilibrium can also be applied to the explanation of previous results that good quality films were obtained at low deposition temperature using active species, such as O, O 3, and O 2+.

  13. Condition of Mechanical Equilibrium at the Phase Interface with Arbitrary Geometry

    NASA Astrophysics Data System (ADS)

    Zubkov, V. V.; Zubkova, A. V.

    2017-09-01

    The authors produced an expression for the mechanical equilibrium condition at the phase interface within the force definition of surface tension. This equilibrium condition is the most general one from the mathematical standpoint and takes into account the three-dimensional aspect of surface tension. Furthermore, the formula produced allows describing equilibrium on the fractal surface of the interface. The authors used the fractional integral model of fractal distribution and took the fractional order integrals over Euclidean space instead of integrating over the fractal set.

  14. Phase equilibrium of methane and nitrogen at low temperatures - Application to Titan

    NASA Technical Reports Server (NTRS)

    Kouvaris, Louis C.; Flasar, F. M.

    1991-01-01

    Since the vapor phase composition of Titan's methane-nitrogen lower atmosphere is uniquely determined as a function of the Gibbs phase rule, these data are presently computed via integration of the Gibbs-Duhem equation. The thermodynamic consistency of published measurements and calculations of the vapor phase composition is then examined, and the saturated mole fraction of gaseous methane is computed as a function of altitude up to the 700-mbar level. The mole fraction is found to lie approximately halfway between that computed from Raoult's law, for a gas in equilibrium with an ideal solution of liquid nitrogen and methane, and that for a gas in equilibrium with pure liquid methane.

  15. Non-equilibrium quantum phase transition via entanglement decoherence dynamics.

    PubMed

    Lin, Yu-Chen; Yang, Pei-Yun; Zhang, Wei-Min

    2016-10-07

    We investigate the decoherence dynamics of continuous variable entanglement as the system-environment coupling strength varies from the weak-coupling to the strong-coupling regimes. Due to the existence of localized modes in the strong-coupling regime, the system cannot approach equilibrium with its environment, which induces a nonequilibrium quantum phase transition. We analytically solve the entanglement decoherence dynamics for an arbitrary spectral density. The nonequilibrium quantum phase transition is demonstrated as the system-environment coupling strength varies for all the Ohmic-type spectral densities. The 3-D entanglement quantum phase diagram is obtained.

  16. Nematic-like stable glasses without equilibrium liquid crystal phases

    DOE Data Explorer

    Gomez, Jaritza [Department of Chemistry, University of Wisconsin-Madison, Madison, Wisconsin 53706, USA; Gujral, Ankit [Department of Chemistry, University of Wisconsin-Madison, Madison, Wisconsin 53706, USA; Huang, Chengbin [School of Pharmacy, University of Wisconsin-Madison, 777 Highland Avenue, Madison, Wisconsin 53705-2222, USA; Bishop, Camille [Department of Chemistry, University of Wisconsin-Madison, Madison, Wisconsin 53706, USA; Yu, Lian [School of Pharmacy, University of Wisconsin-Madison, 777 Highland Avenue, Madison, Wisconsin 53705-2222, USA; Ediger, Mark [Department of Chemistry, University of Wisconsin-Madison, Madison, Wisconsin 53706, USA

    2017-02-01

    We report the thermal and structural properties of glasses of posaconazole, a rod-like molecule, prepared using physical vapor deposition (PVD). PVD glasses of posaconazole can show substantial molecular orientation depending upon the choice of substrate temperature, Tsubstrate, during deposition.Ellipsometry and IR measurements indicate that glasses prepared at Tsubstrate very near the glass transition temperature (Tg) are highly ordered. For these posaconazole glasses, the orientation order parameter is similar to that observed in macroscopically aligned nematic liquid crystals, indicating that the molecules are mostly parallel to one another and perpendicular to the interface. To our knowledge, these are the most anisotropic glasses ever prepared by PVD from a molecule that does not form equilibrium liquid crystal phases. These results are consistent with a previously proposed mechanism in which molecular orientation in PVD glasses is inherited from the orientation present at the free surface of the equilibrium liquid. This mechanism suggests that molecular orientation at the surface of the equilibrium liquid of posaconazole is nematic-like. Posaconazole glasses can show very high kinetic stability; the isothermal transformation of a 400 nm glass into the supercooled liquid occurs via a propagating front that originates at the free surface and requires ~105 times the structural relaxation time of the liquid (τα). We also studied the kinetic stability of PVD glasses of itraconazole, which is a structurally similar molecule with equilibrium liquid crystal phases. While itraconazole glasses can be even more anisotropic than posaconazole glasses, they exhibit lower kinetic stability.

  17. A method of solid-solid phase equilibrium calculation by molecular dynamics

    NASA Astrophysics Data System (ADS)

    Karavaev, A. V.; Dremov, V. V.

    2016-12-01

    A method for evaluation of solid-solid phase equilibrium curves in molecular dynamics simulation for a given model of interatomic interaction is proposed. The method allows to calculate entropies of crystal phases and provides an accuracy comparable with that of the thermodynamic integration method by Frenkel and Ladd while it is much simpler in realization and less intense computationally. The accuracy of the proposed method was demonstrated in MD calculations of entropies for EAM potential for iron and for MEAM potential for beryllium. The bcc-hcp equilibrium curves for iron calculated for the EAM potential by the thermodynamic integration method and by the proposed one agree quite well.

  18. Shape characteristics of equilibrium and non-equilibrium fractal clusters.

    PubMed

    Mansfield, Marc L; Douglas, Jack F

    2013-07-28

    It is often difficult in practice to discriminate between equilibrium and non-equilibrium nanoparticle or colloidal-particle clusters that form through aggregation in gas or solution phases. Scattering studies often permit the determination of an apparent fractal dimension, but both equilibrium and non-equilibrium clusters in three dimensions frequently have fractal dimensions near 2, so that it is often not possible to discriminate on the basis of this geometrical property. A survey of the anisotropy of a wide variety of polymeric structures (linear and ring random and self-avoiding random walks, percolation clusters, lattice animals, diffusion-limited aggregates, and Eden clusters) based on the principal components of both the radius of gyration and electric polarizability tensor indicates, perhaps counter-intuitively, that self-similar equilibrium clusters tend to be intrinsically anisotropic at all sizes, while non-equilibrium processes such as diffusion-limited aggregation or Eden growth tend to be isotropic in the large-mass limit, providing a potential means of discriminating these clusters experimentally if anisotropy could be determined along with the fractal dimension. Equilibrium polymer structures, such as flexible polymer chains, are normally self-similar due to the existence of only a single relevant length scale, and are thus anisotropic at all length scales, while non-equilibrium polymer structures that grow irreversibly in time eventually become isotropic if there is no difference in the average growth rates in different directions. There is apparently no proof of these general trends and little theoretical insight into what controls the universal anisotropy in equilibrium polymer structures of various kinds. This is an obvious topic of theoretical investigation, as well as a matter of practical interest. To address this general problem, we consider two experimentally accessible ratios, one between the hydrodynamic and gyration radii, the other

  19. Non-equilibrium quantum phase transition via entanglement decoherence dynamics

    PubMed Central

    Lin, Yu-Chen; Yang, Pei-Yun; Zhang, Wei-Min

    2016-01-01

    We investigate the decoherence dynamics of continuous variable entanglement as the system-environment coupling strength varies from the weak-coupling to the strong-coupling regimes. Due to the existence of localized modes in the strong-coupling regime, the system cannot approach equilibrium with its environment, which induces a nonequilibrium quantum phase transition. We analytically solve the entanglement decoherence dynamics for an arbitrary spectral density. The nonequilibrium quantum phase transition is demonstrated as the system-environment coupling strength varies for all the Ohmic-type spectral densities. The 3-D entanglement quantum phase diagram is obtained. PMID:27713556

  20. Biological Implications of Dynamical Phases in Non-equilibrium Networks

    NASA Astrophysics Data System (ADS)

    Murugan, Arvind; Vaikuntanathan, Suriyanarayanan

    2016-03-01

    Biology achieves novel functions like error correction, ultra-sensitivity and accurate concentration measurement at the expense of free energy through Maxwell Demon-like mechanisms. The design principles and free energy trade-offs have been studied for a variety of such mechanisms. In this review, we emphasize a perspective based on dynamical phases that can explain commonalities shared by these mechanisms. Dynamical phases are defined by typical trajectories executed by non-equilibrium systems in the space of internal states. We find that coexistence of dynamical phases can have dramatic consequences for function vs free energy cost trade-offs. Dynamical phases can also provide an intuitive picture of the design principles behind such biological Maxwell Demons.

  1. Trace element partitioning behavior of coal gangue-fired CFB plant: experimental and equilibrium calculation.

    PubMed

    Zhang, Yingyi; Nakano, Jinichiro; Liu, Lili; Wang, Xidong; Zhang, Zuotai

    2015-10-01

    Energy recovery is a promising method for coal gangue utilization, during which the prevention of secondary pollution, especially toxic metal emission, is a significant issue in the development of coal gangue utilization. In the present study, investigation into trace element partitioning behavior from a coal gangue-fired power plant in Shanxi province, China, has been conducted. Besides the experimental analysis, thermodynamic equilibrium calculation was also conducted to help the further understanding on the effect of different parameters. Results showed that Hg, As, Be, and Cd were highly volatile elements in the combustion of coal gangue, which were notably enriched in fly ash and may be emitted into the environment via the gas phase. Cr and Mn were mostly non-volatile and were enriched in the bottom ash. Pb, Co, Zn, Cu, and Ni were semi-volatile elements and were enriched in the fly ash to varying degrees. Equilibrium calculations show that the air/fuel ratio and the presence of Cl highly affect the element volatility. The presence of mineral phases, such as aluminosilicates, depresses the volatility of elements by chemical immobilization and competition in Cl. The coal gangue, fly ash, and bottom ash all passed the toxicity characteristic leaching procedure (TCLP), and their alkalinity buffers the acidity of the solution and contributes to the low solubility of the trace elements.

  2. Metastable and equilibrium phase formation in sputter-deposited Ti/Al multilayer thin films

    NASA Astrophysics Data System (ADS)

    Lucadamo, G.; Barmak, K.; Lavoie, C.; Cabral, C., Jr.; Michaelsen, C.

    2002-06-01

    The sequence and kinetics of metastable and equilibrium phase formation in sputter deposited multilayer thin films was investigated by combining in situ synchrotron x-ray diffraction (XRD) with ex situ electron diffraction and differential scanning calorimetry (DSC). The sequence included both cubic and tetragonal modifications of the equilibrium TiAl3 crystal structure. Values for the formation activation energies of the various phases in the sequence were determined using the XRD and DSC data obtained here, as well as activation energy data reported in the literature.

  3. Phase diagram and structural evolution of tin/indium (Sn/In) nanosolder particles: from a non-equilibrium state to an equilibrium state.

    PubMed

    Shu, Yang; Ando, Teiichi; Yin, Qiyue; Zhou, Guangwen; Gu, Zhiyong

    2017-08-31

    A binary system of tin/indium (Sn/In) in the form of nanoparticles was investigated for phase transitions and structural evolution at different temperatures and compositions. The Sn/In nanosolder particles in the composition range of 24-72 wt% In were synthesized by a surfactant-assisted chemical reduction method under ambient conditions. The morphology and microstructure of the as-synthesized nanoparticles were analyzed by scanning electron microscopy (SEM), high resolution transmission electron microscopy (HRTEM), selected area electron diffraction (SAED) and X-ray diffraction (XRD). HRTEM and SAED identified InSn 4 and In, with some Sn being detected by XRD, but no In 3 Sn was observed. The differential scanning calorimetry (DSC) thermographs of the as-synthesized nanoparticles exhibited an endothermic peak at around 116 °C, which is indicative of the metastable eutectic melting of InSn 4 and In. When the nanosolders were subjected to heat treatment at 50-225 °C, the equilibrium phase In 3 Sn appeared while Sn disappeared. The equilibrium state was effectively attained at 225 °C. A Tammann plot of the DSC data of the as-synthesized nanoparticles indicated that the metastable eutectic composition is about 62% In, while that of the DSC data of the 225 °C heat-treated nanoparticles yielded a eutectic composition of 54% In, which confirmed the attainment of the equilibrium state at 225 °C. The phase boundaries estimated from the DSC data of heat-treated Sn/In nanosolder particles matched well with those in the established Sn-In equilibrium phase diagram. The phase transition behavior of Sn/In nanosolders leads to a new understanding of binary alloy particles at the nanoscale, and provides important information for their low temperature soldering processing and applications.

  4. Two-phase quasi-equilibrium in β-type Ti-based bulk metallic glass composites

    PubMed Central

    Zhang, L.; Pauly, S.; Tang, M. Q.; Eckert, J.; Zhang, H. F.

    2016-01-01

    The microstructural evolution of cast Ti/Zr-based bulk metallic glass composites (BMGCs) containing β-Ti still remains ambiguous. This is why to date the strategies and alloys suitable for producing such BMGCs with precisely controllable volume fractions and crystallite sizes are still rather limited. In this work, a Ti-based BMGC containing β-Ti was developed in the Ti-Zr-Cu-Co-Be system. The glassy matrix of this BMGC possesses an exceptional glass-forming ability and as a consequence, the volume fractions as well as the composition of the β-Ti dendrites remain constant over a wide range of cooling rates. This finding can be explained in terms of a two-phase quasi-equilibrium between the supercooled liquid and β-Ti, which the system attains on cooling. The two-phase quasi-equilibrium allows predicting the crystalline and glassy volume fractions by means of the lever rule and we succeeded in reproducing these values by slight variations in the alloy composition at a fixed cooling rate. The two-phase quasi-equilibrium could be of critical importance for understanding and designing the microstructures of BMGCs containing the β-phase. Its implications on the nucleation and growth of the crystalline phase are elaborated. PMID:26754315

  5. Computational studies of thermal and quantum phase transitions approached through non-equilibrium quenching

    NASA Astrophysics Data System (ADS)

    Liu, Cheng-Wei

    Phase transitions and their associated critical phenomena are of fundamental importance and play a crucial role in the development of statistical physics for both classical and quantum systems. Phase transitions embody diverse aspects of physics and also have numerous applications outside physics, e.g., in chemistry, biology, and combinatorial optimization problems in computer science. Many problems can be reduced to a system consisting of a large number of interacting agents, which under some circumstances (e.g., changes of external parameters) exhibit collective behavior; this type of scenario also underlies phase transitions. The theoretical understanding of equilibrium phase transitions was put on a solid footing with the establishment of the renormalization group. In contrast, non-equilibrium phase transition are relatively less understood and currently a very active research topic. One important milestone here is the Kibble-Zurek (KZ) mechanism, which provides a useful framework for describing a system with a transition point approached through a non-equilibrium quench process. I developed two efficient Monte Carlo techniques for studying phase transitions, one is for classical phase transition and the other is for quantum phase transitions, both are under the framework of KZ scaling. For classical phase transition, I develop a non-equilibrium quench (NEQ) simulation that can completely avoid the critical slowing down problem. For quantum phase transitions, I develop a new algorithm, named quasi-adiabatic quantum Monte Carlo (QAQMC) algorithm for studying quantum quenches. I demonstrate the utility of QAQMC quantum Ising model and obtain high-precision results at the transition point, in particular showing generalized dynamic scaling in the quantum system. To further extend the methods, I study more complex systems such as spin-glasses and random graphs. The techniques allow us to investigate the problems efficiently. From the classical perspective, using the

  6. Communication: Microphase equilibrium and assembly dynamics.

    PubMed

    Zhuang, Yuan; Charbonneau, Patrick

    2017-09-07

    Despite many attempts, ordered equilibrium microphases have yet to be obtained in experimental colloidal suspensions. The recent computation of the equilibrium phase diagram of a microscopic, particle-based microphase former [Zhuang et al., Phys. Rev. Lett. 116, 098301 (2016)] has nonetheless found such mesoscale assemblies to be thermodynamically stable. Here, we consider their equilibrium and assembly dynamics. At intermediate densities above the order-disorder transition, we identify four different dynamical regimes and the structural changes that underlie the dynamical crossovers from one disordered regime to the next. Below the order-disorder transition, we also find that periodic lamellae are the most dynamically accessible of the periodic microphases. Our analysis thus offers a comprehensive view of the dynamics of disordered microphases and a route to the assembly of periodic microphases in a putative well-controlled, experimental system.

  7. Equilibrium Phase Behavior of a Continuous-Space Microphase Former.

    PubMed

    Zhuang, Yuan; Zhang, Kai; Charbonneau, Patrick

    2016-03-04

    Periodic microphases universally emerge in systems for which short-range interparticle attraction is frustrated by long-range repulsion. The morphological richness of these phases makes them desirable material targets, but our relatively coarse understanding of even simple models hinders controlling their assembly. We report here the solution of the equilibrium phase behavior of a microscopic microphase former through specialized Monte Carlo simulations. The results for cluster crystal, cylindrical, double gyroid, and lamellar ordering qualitatively agree with a Landau-type free energy description and reveal the nontrivial interplay between cluster, gel, and microphase formation.

  8. Experimental validation of coil phase parametrisation on ASDEX Upgrade, and extension to ITER

    NASA Astrophysics Data System (ADS)

    Ryan, D. A.; Liu, Y. Q.; Kirk, A.; Suttrop, W.; Dudson, B.; Dunne, M.; Willensdorfer, M.; the ASDEX Upgrade team; the EUROfusion MST1 team

    2018-06-01

    It has been previously demonstrated in Li et al (2016 Nucl. Fusion 56 126007) that the optimum upper/lower coil phase shift ΔΦopt for alignment of RMP coils for ELM mitigation depends sensitively on q 95, and other equilibrium plasma parameters. Therefore, ΔΦopt is expected to vary widely during the current ramp of ITER plasmas, with negative implications for ELM mitigation during this period. A previously derived and numerically benchmarked parametrisation of the coil phase for optimal ELM mitigation on ASDEX Upgrade (Ryan et al 2017 Plasma Phys. Control. Fusion 59 024005) is validated against experimental measurements of ΔΦopt, made by observing the changes to the ELM frequency as the coil phase is scanned. It is shown that the parametrisation may predict the optimal coil phase to within 32° of the experimental measurement for n = 2 applied perturbations. It is explained that this agreement is sufficient to ensure that the ELM mitigation is not compromised by poor coil alignment. It is also found that the phase which maximises ELM mitigation is shifted from the phase which maximizes density pump-out, in contrast to theoretical expectations that ELM mitigation and density pump out have the same ΔΦ ul dependence. A time lag between the ELM frequency response and density response to the RMP is suggested as the cause. The method for numerically deriving the parametrisation is repeated for the ITER coil set, using the baseline scenario as a reference equilibrium, and the parametrisation coefficients given for future use in a feedback coil alignment system. The relative merits of square or sinusoidal toroidal current waveforms for ELM mitigation are briefly discussed.

  9. Immunodominance: a new hypothesis to explain parasite escape and host/parasite equilibrium leading to the chronic phase of Chagas' disease?

    PubMed

    Rodrigues, M M; Alencar, B C G de; Claser, C; Tzelepis, F

    2009-03-01

    Intense immune responses are observed during human or experimental infection with the digenetic protozoan parasite Trypanosoma cruzi. The reasons why such immune responses are unable to completely eliminate the parasites are unknown. The survival of the parasite leads to a parasite-host equilibrium found during the chronic phase of chagasic infection in most individuals. Parasite persistence is recognized as the most likely cause of the chagasic chronic pathologies. Therefore, a key question in Chagas' disease is to understand how this equilibrium is established and maintained for a long period. Understanding the basis for this equilibrium may lead to new approaches to interventions that could help millions of individuals at risk for infection or who are already infected with T. cruzi. Here, we propose that the phenomenon of immunodominance may be significant in terms of regulating the host-parasite equilibrium observed in Chagas' disease. T. cruzi infection restricts the repertoire of specific T cells generating, in some cases, an intense immunodominant phenotype and in others causing a dramatic interference in the response to distinct epitopes. This immune response is sufficiently strong to maintain the host alive during the acute phase carrying them to the chronic phase where transmission usually occurs. At the same time, immunodominance interferes with the development of a higher and broader immune response that could be able to completely eliminate the parasite. Based on this, we discuss how we can interfere with or take advantage of immunodominance in order to provide an immunotherapeutic alternative for chagasic individuals.

  10. Infinite-mode squeezed coherent states and non-equilibrium statistical mechanics (phase-space-picture approach)

    NASA Technical Reports Server (NTRS)

    Yeh, Leehwa

    1993-01-01

    The phase-space-picture approach to quantum non-equilibrium statistical mechanics via the characteristic function of infinite-mode squeezed coherent states is introduced. We use quantum Brownian motion as an example to show how this approach provides an interesting geometrical interpretation of quantum non-equilibrium phenomena.

  11. Non-equilibrium phase transition in mesoscopic biochemical systems: from stochastic to nonlinear dynamics and beyond

    PubMed Central

    Ge, Hao; Qian, Hong

    2011-01-01

    A theory for an non-equilibrium phase transition in a driven biochemical network is presented. The theory is based on the chemical master equation (CME) formulation of mesoscopic biochemical reactions and the mathematical method of large deviations. The large deviations theory provides an analytical tool connecting the macroscopic multi-stability of an open chemical system with the multi-scale dynamics of its mesoscopic counterpart. It shows a corresponding non-equilibrium phase transition among multiple stochastic attractors. As an example, in the canonical phosphorylation–dephosphorylation system with feedback that exhibits bistability, we show that the non-equilibrium steady-state (NESS) phase transition has all the characteristics of classic equilibrium phase transition: Maxwell construction, a discontinuous first-derivative of the ‘free energy function’, Lee–Yang's zero for a generating function and a critical point that matches the cusp in nonlinear bifurcation theory. To the biochemical system, the mathematical analysis suggests three distinct timescales and needed levels of description. They are (i) molecular signalling, (ii) biochemical network nonlinear dynamics, and (iii) cellular evolution. For finite mesoscopic systems such as a cell, motions associated with (i) and (iii) are stochastic while that with (ii) is deterministic. Both (ii) and (iii) are emergent properties of a dynamic biochemical network. PMID:20466813

  12. THE ROLE OF METASTABLE STATES IN POLYMER PHASE TRANSITIONS: Concepts, Principles, and Experimental Observations

    NASA Astrophysics Data System (ADS)

    Cheng, Stephen Z. D.; Keller, Andrew

    1998-08-01

    Polymer phases can be described in the same way as phases in other condensed matter using a number density operator and its correlation functions. This description requires the understanding of symmetry operations and order at different atomic and molecular levels. Statistical mechanics provides a link between the microscopic description of the structure and motion and the macroscopic thermodynamic properties. Within the limits of the laws of thermodynamics, polymers exhibit a rich variety of phase transition behaviors. By definition, a first-order phase transition describes a transformation that involves a sudden change of thermodynamic properties at its transition temperature, whereas higher-order phase transitions are classified as critical phenomena. Of special interest is the role of metastability in phase and phase transition behaviors. Although a metastable state possesses a local free energy minimum, it is not at the global equilibrium. Furthermore, metastable states can also be associated with phase sizes. Metastable behavior is also observed in phase transformations that are impeded by kinetic limitations along the pathway to thermodynamic equilibrium. This is illustrated in structural and morphological investigations of crystallization and mesophase transitions, liquid-liquid phase separation, vitrification, and gel formation, as well as combinations of transformation processes. In these cases, the metastable state often becomes the dominant state for the entire system and is observed over a range of time and size scales. This review describes the general principles of metastability in polymer phases and phase transitions and provides illustrations from current experimental works in selected areas.

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

    NASA Astrophysics Data System (ADS)

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

    1990-12-01

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

  14. Predicting the growth of S i3N4 nanowires by phase-equilibrium-dominated vapor-liquid-solid mechanism

    NASA Astrophysics Data System (ADS)

    Zhang, Yongliang; Cai, Jing; Yang, Lijun; Wu, Qiang; Wang, Xizhang; Hu, Zheng

    2017-09-01

    Nanomaterial synthesis is experiencing a profound evolution from empirical science ("cook-and-look") to prediction and design, which depends on the deep insight into the growth mechanism. Herein, we report a generalized prediction of the growth of S i3N4 nanowires by nitriding F e28S i72 alloy particles across different phase regions based on our finding of the phase-equilibrium-dominated vapor-liquid-solid (PED-VLS) mechanism. All the predictions about the growth of S i3N4 nanowires, and the associated evolutions of lattice parameters and geometries of the coexisting Fe -Si alloy phases, are experimentally confirmed quantitatively. This progress corroborates the general validity of the PED-VLS mechanism, which could be applied to the design and controllable synthesis of various one-dimensional nanomaterials.

  15. The microstructure and composition of equilibrium phases formed in hypoeutectic Te-In alloy during solidification

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

    Wang, Baoguang

    As a key tellurium atoms evaporation source for ultraviolet detection photocathode, the hypoeutectic Te{sub 75}In{sub 25} alloy was prepared by employing a slow solidification speed of about 10{sup −2} K/s. The microstructure and chemical composition of the equilibrium phases formed in the as-prepared alloy were studied in this research work. The experimental results show that the as-prepared Te-In alloy was constituted by primary In{sub 2}Te{sub 5} phase and eutectic In{sub 2}Te{sub 5}/Te phases. The eutectic In{sub 2}Te{sub 5}/Te phases are distributed in the grain boundaries of primary In{sub 2}Te{sub 5} phase. With the slow solidification speed, a pure eutectic Temore » phase without any excessive indium solute was obtained, where Te content of eutectic Te phase is 100 mass%. Moreover, it can be considered that the stress between the In{sub 2}Te{sub 5} and Te phases plays an important role in reducing the tellurium vapor pressure in Te{sub 75}In{sub 25} alloy. - Highlights: • The microstructure of Te-In alloy as an evaporation source was analyzed. • A pure eutectic Te phase was obtained by using a slow solidification speed method. • The relation between vapor pressure and inner-stress in the alloy was discussed.« less

  16. Equilibrium Phase Behavior of the Square-Well Linear Microphase-Forming Model.

    PubMed

    Zhuang, Yuan; Charbonneau, Patrick

    2016-07-07

    We have recently developed a simulation approach to calculate the equilibrium phase diagram of particle-based microphase formers. Here, this approach is used to calculate the phase behavior of the square-well linear model for different strengths and ranges of the linear long-range repulsive component. The results are compared with various theoretical predictions for microphase formation. The analysis further allows us to better understand the mechanism for microphase formation in colloidal suspensions.

  17. Phase Equilibria in the ZnO-"FeO"-SiO2 System in Reducing Atmosphere and in the ZnO-"FeO"-SiO2-"Cu2O" System in Equilibrium with Liquid Copper Metal at 1250 °C (1523 K)

    NASA Astrophysics Data System (ADS)

    Hidayat, Taufiq; Hayes, Peter C.; Jak, Evgueni

    2018-05-01

    Recent experimental studies in the ZnO-"FeO"-SiO2 system in reducing atmosphere demonstrated significant discrepancies with the current FactSage thermodynamic model developed using previous experimental data in this system in equilibrium with metallic iron and air. The present experimental study on phase equilibria in the ZnO-"FeO"-SiO2-"Cu2O" system in equilibrium with liquid copper at 1250 °C (1523 K) at low copper oxide concentrations in slag was initiated and undertaken to resolve these discrepancies. A high-temperature equilibration-rapid quenching-electron-probe X-ray microanalysis (EPMA) technique using a primary phase substrate support and closed system approach with Cu metal introduced to determine effective equilibrium oxygen partial pressure from the Cumetal/Cu2Oslag equilibria was applied to provide accurate information on the liquidus and corresponding solid compositions in the spinel, willemite, and tridymite primary phase fields. The present results confirmed the accuracy of the FactSage model, resolved discrepancies, and demonstrated significant uncertainties in the recent studies by other authors on the system in the open reducing atmosphere. The present study shows how this closed system approach can be used to obtain key thermodynamic data on phase equilibria in systems containing volatile metal species, overcoming the limitations and uncertainties encountered in conventional open gas/condensed phase equilibration with these systems. The study highlights the importance of the focus on obtaining accurate experimental data and the risks of misleading information from inadequate experimental control and analysis. The study also demonstrates that continuing in-depth critical review and analysis of the elemental reactions taking place in complex systems is an essential step in phase equilibrium research.

  18. On the Effectiveness of Nature-Inspired Metaheuristic Algorithms for Performing Phase Equilibrium Thermodynamic Calculations

    PubMed Central

    Fateen, Seif-Eddeen K.; Bonilla-Petriciolet, Adrian

    2014-01-01

    The search for reliable and efficient global optimization algorithms for solving phase stability and phase equilibrium problems in applied thermodynamics is an ongoing area of research. In this study, we evaluated and compared the reliability and efficiency of eight selected nature-inspired metaheuristic algorithms for solving difficult phase stability and phase equilibrium problems. These algorithms are the cuckoo search (CS), intelligent firefly (IFA), bat (BA), artificial bee colony (ABC), MAKHA, a hybrid between monkey algorithm and krill herd algorithm, covariance matrix adaptation evolution strategy (CMAES), magnetic charged system search (MCSS), and bare bones particle swarm optimization (BBPSO). The results clearly showed that CS is the most reliable of all methods as it successfully solved all thermodynamic problems tested in this study. CS proved to be a promising nature-inspired optimization method to perform applied thermodynamic calculations for process design. PMID:24967430

  19. On the effectiveness of nature-inspired metaheuristic algorithms for performing phase equilibrium thermodynamic calculations.

    PubMed

    Fateen, Seif-Eddeen K; Bonilla-Petriciolet, Adrian

    2014-01-01

    The search for reliable and efficient global optimization algorithms for solving phase stability and phase equilibrium problems in applied thermodynamics is an ongoing area of research. In this study, we evaluated and compared the reliability and efficiency of eight selected nature-inspired metaheuristic algorithms for solving difficult phase stability and phase equilibrium problems. These algorithms are the cuckoo search (CS), intelligent firefly (IFA), bat (BA), artificial bee colony (ABC), MAKHA, a hybrid between monkey algorithm and krill herd algorithm, covariance matrix adaptation evolution strategy (CMAES), magnetic charged system search (MCSS), and bare bones particle swarm optimization (BBPSO). The results clearly showed that CS is the most reliable of all methods as it successfully solved all thermodynamic problems tested in this study. CS proved to be a promising nature-inspired optimization method to perform applied thermodynamic calculations for process design.

  20. Critical behavior within 20 fs drives the out-of-equilibrium laser-induced magnetic phase transition in nickel

    PubMed Central

    Tengdin, Phoebe; You, Wenjing; Chen, Cong; Shi, Xun; Zusin, Dmitriy; Zhang, Yingchao; Gentry, Christian; Blonsky, Adam; Keller, Mark; Oppeneer, Peter M.; Kapteyn, Henry C.; Tao, Zhensheng; Murnane, Margaret M.

    2018-01-01

    It has long been known that ferromagnets undergo a phase transition from ferromagnetic to paramagnetic at the Curie temperature, associated with critical phenomena such as a divergence in the heat capacity. A ferromagnet can also be transiently demagnetized by heating it with an ultrafast laser pulse. However, to date, the connection between out-of-equilibrium and equilibrium phase transitions, or how fast the out-of-equilibrium phase transitions can proceed, was not known. By combining time- and angle-resolved photoemission with time-resolved transverse magneto-optical Kerr spectroscopies, we show that the same critical behavior also governs the ultrafast magnetic phase transition in nickel. This is evidenced by several observations. First, we observe a divergence of the transient heat capacity of the electron spin system preceding material demagnetization. Second, when the electron temperature is transiently driven above the Curie temperature, we observe an extremely rapid change in the material response: The spin system absorbs sufficient energy within the first 20 fs to subsequently proceed through the phase transition, whereas demagnetization and the collapse of the exchange splitting occur on much longer, fluence-independent time scales of ~176 fs. Third, we find that the transient electron temperature alone dictates the magnetic response. Our results are important because they connect the out-of-equilibrium material behavior to the strongly coupled equilibrium behavior and uncover a new time scale in the process of ultrafast demagnetization. PMID:29511738

  1. Critical behavior within 20 fs drives the out-of-equilibrium laser-induced magnetic phase transition in nickel.

    PubMed

    Tengdin, Phoebe; You, Wenjing; Chen, Cong; Shi, Xun; Zusin, Dmitriy; Zhang, Yingchao; Gentry, Christian; Blonsky, Adam; Keller, Mark; Oppeneer, Peter M; Kapteyn, Henry C; Tao, Zhensheng; Murnane, Margaret M

    2018-03-01

    It has long been known that ferromagnets undergo a phase transition from ferromagnetic to paramagnetic at the Curie temperature, associated with critical phenomena such as a divergence in the heat capacity. A ferromagnet can also be transiently demagnetized by heating it with an ultrafast laser pulse. However, to date, the connection between out-of-equilibrium and equilibrium phase transitions, or how fast the out-of-equilibrium phase transitions can proceed, was not known. By combining time- and angle-resolved photoemission with time-resolved transverse magneto-optical Kerr spectroscopies, we show that the same critical behavior also governs the ultrafast magnetic phase transition in nickel. This is evidenced by several observations. First, we observe a divergence of the transient heat capacity of the electron spin system preceding material demagnetization. Second, when the electron temperature is transiently driven above the Curie temperature, we observe an extremely rapid change in the material response: The spin system absorbs sufficient energy within the first 20 fs to subsequently proceed through the phase transition, whereas demagnetization and the collapse of the exchange splitting occur on much longer, fluence-independent time scales of ~176 fs. Third, we find that the transient electron temperature alone dictates the magnetic response. Our results are important because they connect the out-of-equilibrium material behavior to the strongly coupled equilibrium behavior and uncover a new time scale in the process of ultrafast demagnetization.

  2. Bose-Einstein Condensation of Long-Lifetime Polaritons in Thermal Equilibrium.

    PubMed

    Sun, Yongbao; Wen, Patrick; Yoon, Yoseob; Liu, Gangqiang; Steger, Mark; Pfeiffer, Loren N; West, Ken; Snoke, David W; Nelson, Keith A

    2017-01-06

    The experimental realization of Bose-Einstein condensation (BEC) with atoms and quasiparticles has triggered wide exploration of macroscopic quantum effects. Microcavity polaritons are of particular interest because quantum phenomena such as BEC and superfluidity can be observed at elevated temperatures. However, polariton lifetimes are typically too short to permit thermal equilibration. This has led to debate about whether polariton condensation is intrinsically a nonequilibrium effect. Here we report the first unambiguous observation of BEC of optically trapped polaritons in thermal equilibrium in a high-Q microcavity, evidenced by equilibrium Bose-Einstein distributions over broad ranges of polariton densities and bath temperatures. With thermal equilibrium established, we verify that polariton condensation is a phase transition with a well-defined density-temperature phase diagram. The measured phase boundary agrees well with the predictions of basic quantum gas theory.

  3. Analytical Study on the Saturated Polarization Under Electric Field and Phase Equilibrium of Three-Phase Polycrystalline Ferroelectrics by Using the Generalized Inverse-Pole-Figure Model

    NASA Astrophysics Data System (ADS)

    Ju, Kyong-Sik; Ryo, Hyok-Su; Pak, Sung-Nam; Pak, Chang-Su; Ri, Sung-Guk; Ri, Dok-Hwan

    2018-07-01

    By using the generalized inverse-pole-figure model, the numbers of crystalline particles involved in different domain-switching near the triple tetragonal-rhombohedral-orthorhombic (T-R-O) points of three-phase polycrystalline ferroelectrics have been analytically calculated and domain-switching which can bring out phase transformations has been considered. Through polarization by an electric field, different numbers of crystalline particles can be involved in different phase transformations. According to the phase equilibrium conditions, the phase equilibrium compositions of the three phases coexisting near the T-R-O triple point have been evaluated from the results of the numbers of crystalline particles involved in different phase transformations.

  4. Optical Properties in Non-equilibrium Phase Transitions

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

    Ao, T; Ping, Y; Widmann, K

    An open question about the dynamical behavior of materials is how phase transition occurs in highly non-equilibrium systems. One important class of study is the excitation of a solid by an ultrafast, intense laser. The preferential heating of electrons by the laser field gives rise to initial states dominated by hot electrons in a cold lattice. Using a femtosecond laser pump-probe approach, we have followed the temporal evolution of the optical properties of such a system. The results show interesting correlation to non-thermal melting and lattice disordering processes. They also reveal a liquid-plasma transition when the lattice energy density reachesmore » a critical value.« less

  5. Reentrant equilibrium disordering in nanoparticle–polymer mixtures

    DOE PAGES

    Meng, Dong; Kumar, Sanat K.; Grest, Gary S.; ...

    2017-01-31

    A large body of experimental work has established that athermal colloid/polymer mixtures undergo a sequence of transitions from a disordered fluid state to a colloidal crystal to a second disordered phase with increasing polymer concentration. These transitions are driven by polymer-mediated interparticle attraction, which is a function of both the polymer density and size. It has been posited that the disordered state at high polymer density is a consequence of strong interparticle attractions that kinetically inhibit the formation of the colloidal crystal, i.e., the formation of a non-equilibrium gel phase interferes with crystallization. Here we use molecular dynamics simulations andmore » density functional theory on polymers and nanoparticles (NPs) of comparable size and show that the crystal-disordered phase coexistence at high polymer density for sufficiently long chains corresponds to an equilibrium thermodynamic phase transition. While the crystal is, indeed, stabilized at intermediate polymer density by polymer-induced intercolloid attractions, it is destabilized at higher densities because long chains lose significant configurational entropy when they are forced to occupy all of the crystal voids. Finally, our results are in quantitative agreement with existing experimental data and show that, at least in the nanoparticle limit of sufficiently small colloidal particles, the crystal phase only has a modest range of thermodynamic stability.« less

  6. Observation of dynamic equilibrium cluster phase in nanoparticle-polymer system

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

    Kumar, Sugam, E-mail: sugam@barc.gov.in; Mehan, S.; Aswal, V. K.

    2016-05-23

    Small-angle neutron scattering (SANS) and dynamic light scattering (DLS) have been used to investigate the existence of a cluster phase in a nanoparticle-polymer system. The nanoparticle-polymer system shows an interesting reentrant phase behavior where the charge stabilized silica nanoparticles undergo particle clustering and back to individual nanoparticles as a function of polymer concentration. This kind of phase behavior is believed to be directed by opposing attractive and repulsive interactions present in the system. The phase behavior shows two narrow regions of polymer concentration immediately before and after the two-phase formation indicating the possibility of the existence of some equilibrium clusters.more » DLS results show a much higher size of particles than individuals in these two regions which remains unchanged even after dilution. The SANS data show the evolution of attraction with increased volume fraction of the particles supporting the dynamic nature of these clusters.« less

  7. Gas-phase water-mediated equilibrium between methylglyoxal and its geminal diol

    PubMed Central

    Axson, Jessica L.; Takahashi, Kaito; De Haan, David O.; Vaida, Veronica

    2010-01-01

    In aqueous solution, aldehydes, and to a lesser extent ketones, hydrate to form geminal diols. We investigate the hydration of methylglyoxal (MG) in the gas phase, a process not previously considered to occur in water-restricted environments. In this study, we spectroscopically identified methylglyoxal diol (MGD) and obtained the gas-phase partial pressures of MG and MGD. These results, in conjunction with the relative humidity, were used to obtain the equilibrium constant, KP, for the water-mediated hydration of MG in the gas phase. The Gibbs free energy for this process, ΔG°, obtained as a result, suggests a larger than expected gas-phase diol concentration. This may have significant implications for understanding the role of organics in atmospheric chemistry. PMID:20142510

  8. [Developments in preparation and experimental method of solid phase microextraction fibers].

    PubMed

    Yi, Xu; Fu, Yujie

    2004-09-01

    Solid phase microextraction (SPME) is a simple and effective adsorption and desorption technique, which concentrates volatile or nonvolatile compounds from liquid samples or headspace of samples. SPME is compatible with analyte separation and detection by gas chromatography, high performance liquid chromatography, and other instrumental methods. It can provide many advantages, such as wide linear scale, low solvent and sample consumption, short analytical times, low detection limits, simple apparatus, and so on. The theory of SPME is introduced, which includes equilibrium theory and non-equilibrium theory. The novel development of fiber preparation methods and relative experimental techniques are discussed. In addition to commercial fiber preparation, different newly developed fabrication techniques, such as sol-gel, electronic deposition, carbon-base adsorption, high-temperature epoxy immobilization, are presented. Effects of extraction modes, selection of fiber coating, optimization of operating conditions, method sensitivity and precision, and systematical automation, are taken into considerations in the analytical process of SPME. A simple perspective of SPME is proposed at last.

  9. Under What Conditions Can Equilibrium Gas-Particle Partitioning Be Expected to Hold in the Atmosphere?

    PubMed

    Mai, Huajun; Shiraiwa, Manabu; Flagan, Richard C; Seinfeld, John H

    2015-10-06

    The prevailing treatment of secondary organic aerosol formation in atmospheric models is based on the assumption of instantaneous gas-particle equilibrium for the condensing species, yet compelling experimental evidence indicates that organic aerosols can exhibit the properties of highly viscous, semisolid particles, for which gas-particle equilibrium may be achieved slowly. The approach to gas-particle equilibrium partitioning is controlled by gas-phase diffusion, interfacial transport, and particle-phase diffusion. Here we evaluate the controlling processes and the time scale to achieve gas-particle equilibrium as a function of the volatility of the condensing species, its surface accommodation coefficient, and its particle-phase diffusivity. For particles in the size range of typical atmospheric organic aerosols (∼50-500 nm), the time scale to establish gas-particle equilibrium is generally governed either by interfacial accommodation or particle-phase diffusion. The rate of approach to equilibrium varies, depending on whether the bulk vapor concentration is constant, typical of an open system, or decreasing as a result of condensation into the particles, typical of a closed system.

  10. Experimental Liquidus Studies of the Pb-Fe-Si-O System in Equilibrium with Metallic Pb

    NASA Astrophysics Data System (ADS)

    Shevchenko, M.; Jak, E.

    2018-02-01

    Phase equilibria of the Pb-Fe-Si-O system have been investigated at 943 K to 1773 K (670 °C to 1500 °C) for oxide liquid in equilibrium with liquid Pb metal and solid oxide phases: (a) quartz, tridymite, or cristobalite; (b) (fayalite + tridymite) or (fayalite + spinel); (c) spinel (Fe3O4); (d) complex lead-iron silicates (melanotekite PbO·FeO1.5·SiO2, barysilite 8PbO·FeO·6SiO2, 5PbO·FeO1.5·SiO2, and 6PbO·FeO1.5·SiO2); (e) lead silicates (Pb2SiO4, Pb11Si3O17); (f) lead ferrites (magnetoplumbite Pb1+ x Fe12- x O19- x solid solution range); and (g) lead oxide (PbO, massicot). High-temperature equilibration on primary phase or iridium substrates, followed by quenching and direct measurement of Pb, Fe, and Si concentrations in the phases with the electron probe X-ray microanalysis, has been used to accurately characterize the system in equilibrium with Pb metal. All results are projected onto the PbO-"FeO"-SiO2 plane for presentation purposes. The present study is the first systematic characterization of liquidus over a wide range of compositions in this system in equilibrium with metallic Pb.

  11. Droplet formation at the non-equilibrium water/water (w/w) interface

    NASA Astrophysics Data System (ADS)

    Chao, Youchuang; Mak, Sze Yi; Kong, Tiantian; Ding, Zijing; Shum, Ho Cheung

    2017-11-01

    The interfacial instability at liquid-liquid interfaces has been intensively studied in recent years due to their important role in nature and technology. Among them, two classic instabilities are Rayleigh-Taylor (RT) and double diffusive (DD) instabilities, which are practically relevant to many industrial processes, such as geologic CO2 sequestration. Most experimental and theoretical works have focused on RT or DD instability in binary systems. However, the study of such instability in complex systems, such as non-equilibrium ternary systems that involves mass-transfer-induced phase separation, has received less attention. Here, by using a ternary system known as the aqueous two-phase system (ATPS), we investigate experimentally the behavior of non-equilibrium water/water (w/w) interfaces in a vertically orientated Hele-Shaw cell. We observe that an array of fingers emerge at the w/w interface, and then break into droplets. We explore the instability using different concentrations of two aqueous phases. Our experimental findings are expected to inspire the mass production of all-aqueous emulsions in a simple setup.

  12. Equilibrium magnetic states in individual hemispherical permalloy caps

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

    Streubel, Robert; Schmidt, Oliver G.; Material Systems for Nanoelectronics, Chemnitz University of Technology, 09107 Chemnitz

    2012-09-24

    The magnetization distributions in individual soft magnetic permalloy caps on non-magnetic spherical particles with sizes ranging from 50 to 800 nm are investigated. We experimentally visualize the magnetic structures at the resolution limit of the x-ray magnetic circular dichroism photoelectron emission microscopy (XMCD-PEEM). By analyzing the so-called tail contrast in XMCD-PEEM, the spatial resolution is significantly enhanced, which allowed us to explore magnetic vortices and their displacement on curved surfaces. Furthermore, cap nanostructures are modeled as extruded hemispheres to determine theoretically the phase diagram of equilibrium magnetic states. The calculated phase diagram agrees well with the experimental observations.

  13. Thermodynamically equilibrium roton states of nanoparticles in molten and vapour phases

    NASA Astrophysics Data System (ADS)

    Karasevskii, A. I.

    2015-05-01

    We show a possibility for a thermodynamically equilibrium nanocrystalline structure consisting of nanosized solid inclusions to appear in a melt just beyond the melting curve. Thermodynamic stability of the nanocrystalline structure in the melt results from the free energy lowering due to rotational motion of nanoparticles. The main contribution to the reduction of the free energy of the system is due to an increase in the rotational entropy and change in formation energy of nanocrystals, i.e. the nanocrystalline structure in the melt, like vacancies in a crystal, is an equilibrium defect structure of the melt. It is demonstrated that similar nanocrystalline structures can also appear in the vapour phase in the form of liquid nanodrops and in liquid solutions, e.g. in He II.

  14. An experimental study of trace element partitioning between perovskite, hibonite and melt: Equilibrium values

    NASA Technical Reports Server (NTRS)

    Kennedy, A. K.; Lofgren, G. E.; Wasserburg, G. J.

    1993-01-01

    The presence of perovskite (CATiO3) and hibonite (Ca Al12O19) within different regions of Calcium-, Aluminum-rich Inclusions (CAI) and the trace element concentrations of these minerals in each circumstance, constrain models of precursor formation, nebular condensation, the thermal history of inclusions with relict perovskite and hibonite, and the formation of the Wark-Lovering rim. At present mineral/melt partition coefficient data for hibonite are limited to a few elements in simple experimental systems, or to those derived from hibonite-glass pairs in hibonite/glass microspherules. Similarly, there is only limited data on perovskite D that are applicable to meteorite compositions. Apart from the importance of partitioning studies to meteorite research, D values also are invaluable in the development of thermodynamic models, especially when data is available for a large number of elements that have different ionic charge and radii. In addition, study of the effect of rapid cooling on partitioning is crucial to our understanding of meteorite inclusions. To expand our knowledge of mineral/melt D for perovskite and hibonite, a study was instituted where D values are obtained in both equilibrium and dynamic cooling experiments. As an initial phase of this study mineral/melt D was measured for major elements (Ca, Mg, Al, Ti, and Si), 15 rare earth elements (La-Lu) and 8 other elements (Ba, Sr, U, Th, Nb, Zr, Hf, and Ge) in perovskite and hibonite grown under equilibrium conditions, in bulk compositions that are respectively similar to Compact Type A (CTA) CAI and to a hibonite/glass microspherule. Experimental mixes were doped with REE at 20-50x chondritic (ch) abundances, Ba at 50 ppm, Sr, Hf, Nb, and Zr at 100 ppm and, U and Th at 200 ppm. Trace element abundances were measured with the PANURGE ion microprobe. Major element compositions were obtained by electron microprobe analysis.

  15. Influence of Al content on non-equilibrium solidification behavior of Ni-Al-Ta model single crystal alloys

    NASA Astrophysics Data System (ADS)

    Ai, Cheng; Zhou, Jian; Zhang, Heng; Zhao, Xinbao; Pei, Yanling; Li, Shusuo; Gong, Shengkai

    2016-01-01

    The non-equilibrium solidification behaviors of five Ni-Al-Ta ternary model single crystal alloys with different Al contents were investigated by experimental analysis and theoretical calculation (by JMatPro) in this study. These model alloys respectively represented the γ' phase with various volume fractions (100%, 75%, 50%, 25% and 0%) at 900 °C. It was found that with decreasing Al content, liquidus temperature of experimental alloys first decreased and then increased. Meanwhile, the solidification range showed a continued downward trend. In addition, with decreasing Al content, the primary phases of non-equilibrium solidified model alloys gradually transformed from γ' phase to γ phase, and the area fraction of which first decreased and then increased. Moreover, the interdendritic/intercellular precipitation of model alloys changed from β phase (for 100% γ') to (γ+γ')Eutectic (for 75% γ'), (γ+γ')Eutectic+γ' (for 50% γ' and 25% γ') and none interdendritic precipitation (for 0% γ'), and the last stage non-equilibrium solidification sequence of model alloys was determined by the nominal Al content and different microsegregation behaviors of Al element.

  16. Characterization of Low-Symmetry Structures from Phase Equilibrium of Fe-Al System-Microstructures and Mechanical Properties.

    PubMed

    Matysik, Piotr; Jóźwiak, Stanisław; Czujko, Tomasz

    2015-03-04

    Fe-Al intermetallic alloys with aluminum content over 60 at% are in the area of the phase equilibrium diagram that is considerably less investigated in comparison to the high-symmetry Fe₃Al and FeAl phases. Ambiguous crystallographic information and incoherent data referring to the phase equilibrium diagrams placed in a high-aluminum range have caused confusions and misinformation. Nowadays unequivocal material properties description of FeAl₂, Fe₂Al₅ and FeAl₃ intermetallic alloys is still incomplete. In this paper, the influence of aluminum content and processing parameters on phase composition is presented. The occurrence of low-symmetry FeAl₂, Fe₂Al₅ and FeAl₃ structures determined by chemical composition and phase transformations was defined by scanning electron microscopy (SEM) and energy-dispersive X-ray spectroscopy (EDS) examinations. These results served to verify diffraction investigations (XRD) and to explain the mechanical properties of cast materials such as: hardness, Young's modulus and fracture toughness evaluated using the nano-indentation technique.

  17. Ultrafast evolution and transient phases of a prototype out-of-equilibrium Mott–Hubbard material

    DOE PAGES

    Lantz, G.; Mansart, B.; Grieger, D.; ...

    2017-01-09

    Photoexcited strongly correlated materials is attracting growing interest since their rich phase diagram often translates into an equally rich out-of-equilibrium behavior, including non-thermal phases and photoinduced phase transitions. With femtosecond optical pulses, electronic and lattice degrees of freedom can be transiently decoupled, giving the opportunity of stabilizing new states of matter inaccessible by quasi-adiabatic pathways. We present a study of the ultrafast non-equilibrium evolution of the prototype Mott-Hubbard material V 2O 3, which presents a transient non-thermal phase developing immediately after photoexcitation and lasting few picoseconds. For both the insulating and the metallic phase, the formation of the transient configurationmore » is triggered by the excitation of electrons into the bonding a 1g orbital, and is then stabilized by a lattice distortion characterized by a marked hardening of the A 1g coherent phonon. Furthermore, this configuration is in stark contrast with the thermally accessible ones - the A 1g phonon frequency actually softens when heating the material. Our results show the importance of selective electron-lattice interplay for the ultrafast control of material parameters, and are of particular relevance for the optical manipulation of strongly correlated systems, whose electronic and structural properties are often strongly intertwinned.« less

  18. Ultrafast evolution and transient phases of a prototype out-of-equilibrium Mott–Hubbard material

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

    Lantz, G.; Mansart, B.; Grieger, D.

    Photoexcited strongly correlated materials is attracting growing interest since their rich phase diagram often translates into an equally rich out-of-equilibrium behavior, including non-thermal phases and photoinduced phase transitions. With femtosecond optical pulses, electronic and lattice degrees of freedom can be transiently decoupled, giving the opportunity of stabilizing new states of matter inaccessible by quasi-adiabatic pathways. We present a study of the ultrafast non-equilibrium evolution of the prototype Mott-Hubbard material V 2O 3, which presents a transient non-thermal phase developing immediately after photoexcitation and lasting few picoseconds. For both the insulating and the metallic phase, the formation of the transient configurationmore » is triggered by the excitation of electrons into the bonding a 1g orbital, and is then stabilized by a lattice distortion characterized by a marked hardening of the A 1g coherent phonon. Furthermore, this configuration is in stark contrast with the thermally accessible ones - the A 1g phonon frequency actually softens when heating the material. Our results show the importance of selective electron-lattice interplay for the ultrafast control of material parameters, and are of particular relevance for the optical manipulation of strongly correlated systems, whose electronic and structural properties are often strongly intertwinned.« less

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

    NASA Astrophysics Data System (ADS)

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

    2014-09-01

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

  20. Changes in apple liquid phase concentration throughout equilibrium in osmotic dehydration.

    PubMed

    Barat, J M; Barrera, C; Frías, J M; Fito, P

    2007-03-01

    Previous results on apple tissue equilibration during osmotic dehydration showed that, at very long processing times, the solute concentrations of the fruit liquid phase and the osmotic solution were the same. In the present study, changes in apple liquid phase composition throughout equilibrium in osmotic dehydration were analyzed and modeled. Results showed that, by the time osmosed samples reached the maximum weight and volume loss, solute concentration of the fruit liquid phase was higher than that of the osmotic solution. The reported overconcentration could be explained in terms of the apple structure shrinkage that occurred during the osmotic dehydration with highly concentrated osmotic solutions due to the elastic response of the food structure to the loss of water and intake of solutes. The fruit liquid phase overconcentration rate was observed to depend on the concentration of the osmotic solution, the processing temperature, the sample size, and shape of the cellular tissue.

  1. A comparison of homogeneous equilibrium and relaxation model for CO2 expansion inside the two-phase ejector

    NASA Astrophysics Data System (ADS)

    Palacz, M.; Haida, M.; Smolka, J.; Nowak, A. J.; Hafner, A.

    2016-09-01

    In this study, the comparison of the accuracy of the homogeneous equilibrium model (HEM) and homogeneous relaxation model (HRM) is presented. Both models were applied to simulate the CO2 expansion inside the two-phase ejectors. Moreover, the mentioned models were implemented in the robust and efficient computational tool ejectorPL. That tool guarantees the fully automated computational process and the repeatable computations for the various ejector shapes and operating conditions. The simulated motive nozzle mass flow rates were compared to the experimentally measured mass flow rates. That comparison was made for both, HEM and HRM. The results showed the unsatisfying fidelity of the HEM for the operating regimes far from the carbon dioxide critical point. On the other hand, the HRM accuracy for such conditions was slightly higher. The approach presented in this paper, showed the limitation of applicability of both two-phase models for the expansion phenomena inside the ejectors.

  2. Experimental investigation on V isotope equilibrium fractionation factor between metal and silicate melt

    NASA Astrophysics Data System (ADS)

    Zhang, S.; Zhang, H.; Huang, F.

    2017-12-01

    Equilibrium fractionation factors of stable isotopes between metal and silicate melt are of vital importance for understanding the isotope variations within meteorites and planetary bodies. The V isotope composition (reported as δ51V = 1000 × [(51V/50Vsample/51V/50VAA)-1] ) of the bulk silicate Earth (BSE) has been estimated as δ51V = -0.7 ± 0.2‰ (2sd) [1], which is significantly heavier than most meteorites by 1‰ [2]. Such isotopic offset may provide insights for the core formation and core-mantle segregation. Therefore, it is important to understand V isotope equilibrium fractionation factor between silicate melt and metal. Nielsen et al. (2014) [2] had performed 3 experiments using starting materials of pure Fe metal and An50Di28Fo22 composition, revealing no resolvable V isotope fractionation. However, it is not clear whether chemical compositions in the melts can affect V isotope fractionations. Therefore, we experimentally calibrated equilibrium V isotope fractionation between Fe metallic and basaltic melt, with particular focus on the effect of Ni and other light elements. Experiments were performed at 1 GPa and 1600 oC using a 3/4″ end-loaded piston cylinder. The starting materials consisted of 1:1 mixture of pure Fe metal and basaltic composition [3]. The isotope equilibrium was assessed using time series experiments combined with the reverse reaction method. Carbon saturation and C-free experiments were achieved by using graphite and silica capsules, respectively. The Ni series experiments were doped with 6 wt% Ni into the starting Fe metal. The metal and silicate phases of samples were mechanically separated, V was purified using a chromatographic technique, and V isotope ratios were measured using MC-ICP-MS [4]. Carbon saturation, C-free experiments and Ni series experiment all show non-resolvable V isotope fractionation between metal and basaltic melt, which indicates that the presence of C and Ni could not affect V isotope fractionation

  3. A CRDS approach to gas phase equilibrium constants: the case of N 2O 4 ↔ 2NO 2 at 283 K

    NASA Astrophysics Data System (ADS)

    Tuchler, Matthew F.; Schmidt, Kierstin L.; Morgan, Mackenzie

    2005-01-01

    We report a general technique for determining the gas phase equilibrium constant, KP, of the A ↔ 2C system using cavity ringdown spectroscopy (CRDS). Working at a constant temperature, the absorption of one of the equilibrium species is measured at two different total pressures. KP is determined from the total pressures of the equilibrium mixture and the ratio of the absorptions. Theoretical limits on sensitivity of this technique are described as a function of experimental conditions. We present results from the reaction N 2O 4 ↔ 2NO 2 measured at T = 283 K. KP measured in this experiment, 21 (±5) Torr, is found to be lower than that recommended by the NASA Panel for Data Evaluation, 32 Torr. [S.P. Sander, A.R. Ravishankara, D.M. Golden, C.E. Kolb, M.J. Kurylo, R.E. Huie, V.L. Orkin, M.J. Molina, G.K. Moortgat, B.J. Finlayson-Pitts, Chemical Kinetics and Photochemical Data for Use in Atmospheric Studies. Evaluation No. 14; Jet Propulsion Laboratory, Pasadena, CA, 2003].

  4. Non-equilibrium coherence dynamics in one-dimensional Bose gases.

    PubMed

    Hofferberth, S; Lesanovsky, I; Fischer, B; Schumm, T; Schmiedmayer, J

    2007-09-20

    Low-dimensional systems provide beautiful examples of many-body quantum physics. For one-dimensional (1D) systems, the Luttinger liquid approach provides insight into universal properties. Much is known of the equilibrium state, both in the weakly and strongly interacting regimes. However, it remains a challenge to probe the dynamics by which this equilibrium state is reached. Here we present a direct experimental study of the coherence dynamics in both isolated and coupled degenerate 1D Bose gases. Dynamic splitting is used to create two 1D systems in a phase coherent state. The time evolution of the coherence is revealed through local phase shifts of the subsequently observed interference patterns. Completely isolated 1D Bose gases are observed to exhibit universal sub-exponential coherence decay, in excellent agreement with recent predictions. For two coupled 1D Bose gases, the coherence factor is observed to approach a non-zero equilibrium value, as predicted by a Bogoliubov approach. This coupled-system decay to finite coherence is the matter wave equivalent of phase-locking two lasers by injection. The non-equilibrium dynamics of superfluids has an important role in a wide range of physical systems, such as superconductors, quantum Hall systems, superfluid helium and spin systems. Our experiments studying coherence dynamics show that 1D Bose gases are ideally suited for investigating this class of phenomena.

  5. Multi-Phase Equilibrium and Solubilities of Aromatic Compounds and Inorganic Compounds in Sub- and Supercritical Water: A Review.

    PubMed

    Liu, Qinli; Ding, Xin; Du, Bowen; Fang, Tao

    2017-11-02

    Supercritical water oxidation (SCWO), as a novel and efficient technology, has been applied to wastewater treatment processes. The use of phase equilibrium data to optimize process parameters can offer a theoretical guidance for designing SCWO processes and reducing the equipment and operating costs. In this work, high-pressure phase equilibrium data for aromatic compounds+water systems and inorganic compounds+water systems are given. Moreover, thermodynamic models, equations of state (EOS) and empirical and semi-empirical approaches are summarized and evaluated. This paper also lists the existing problems of multi-phase equilibria and solubility studies on aromatic compounds and inorganic compounds in sub- and supercritical water.

  6. Characterization of Low-Symmetry Structures from Phase Equilibrium of Fe-Al System—Microstructures and Mechanical Properties

    PubMed Central

    Matysik, Piotr; Jóźwiak, Stanisław; Czujko, Tomasz

    2015-01-01

    Fe-Al intermetallic alloys with aluminum content over 60 at% are in the area of the phase equilibrium diagram that is considerably less investigated in comparison to the high-symmetry Fe3Al and FeAl phases. Ambiguous crystallographic information and incoherent data referring to the phase equilibrium diagrams placed in a high-aluminum range have caused confusions and misinformation. Nowadays unequivocal material properties description of FeAl2, Fe2Al5 and FeAl3 intermetallic alloys is still incomplete. In this paper, the influence of aluminum content and processing parameters on phase composition is presented. The occurrence of low-symmetry FeAl2, Fe2Al5 and FeAl3 structures determined by chemical composition and phase transformations was defined by scanning electron microscopy (SEM) and energy-dispersive X-ray spectroscopy (EDS) examinations. These results served to verify diffraction investigations (XRD) and to explain the mechanical properties of cast materials such as: hardness, Young’s modulus and fracture toughness evaluated using the nano-indentation technique. PMID:28787979

  7. Theoretical Aspects of Differential Scanning Calorimetry as a Tool for the Studies of Equilibrium Thermodynamics in Pharmaceutical Solid Phase Transitions.

    PubMed

    Faroongsarng, Damrongsak

    2016-06-01

    Although differential scanning calorimetry (DSC) is a non-equilibrium technique, it has been used to gain energetic information that involves phase equilibria. DSC has been widely used to characterize the equilibrium melting parameters of small organic pharmaceutical compounds. An understanding of how DSC measures an equilibrium event could make for a better interpretation of the results. The aim of this mini-review was to provide a theoretical insight into the DSC measurement to obtain the equilibrium thermodynamics of a phase transition especially the melting process. It was demonstrated that the heat quantity obtained from the DSC thermogram (ΔH) was related to the thermodynamic enthalpy of the phase transition (ΔH (P) ) via: ΔH = ΔH (P) /(1 + K (- 1)) where K was the equilibrium constant. In melting, the solid and liquefied phases presumably coexist resulting in a null Gibbs free energy that produces an infinitely larger K. Thus, ΔH could be interpreted as ΔH (P). Issues of DSC investigations on melting behavior of crystalline solids including polymorphism, degradation impurity due to heating in situ, and eutectic melting were discussed. In addition, DSC has been a tool for determination of the impurity based on an ideal solution of the melt that is one of the official methods used to establish the reference standard.

  8. Theoretical and computational studies of non-equilibrium and non-statistical dynamics in the gas phase, in the condensed phase and at interfaces.

    PubMed

    Spezia, Riccardo; Martínez-Nuñez, Emilio; Vazquez, Saulo; Hase, William L

    2017-04-28

    In this Introduction, we show the basic problems of non-statistical and non-equilibrium phenomena related to the papers collected in this themed issue. Over the past few years, significant advances in both computing power and development of theories have allowed the study of larger systems, increasing the time length of simulations and improving the quality of potential energy surfaces. In particular, the possibility of using quantum chemistry to calculate energies and forces 'on the fly' has paved the way to directly study chemical reactions. This has provided a valuable tool to explore molecular mechanisms at given temperatures and energies and to see whether these reactive trajectories follow statistical laws and/or minimum energy pathways. This themed issue collects different aspects of the problem and gives an overview of recent works and developments in different contexts, from the gas phase to the condensed phase to excited states.This article is part of the themed issue 'Theoretical and computational studies of non-equilibrium and non-statistical dynamics in the gas phase, in the condensed phase and at interfaces'. © 2017 The Author(s).

  9. Experimental Liquidus Studies of the Pb-Cu-Si-O System in Equilibrium with Metallic Pb-Cu Alloys

    NASA Astrophysics Data System (ADS)

    Shevchenko, M.; Nicol, S.; Hayes, P. C.; Jak, E.

    2018-03-01

    Phase equilibria of the Pb-Cu-Si-O system have been investigated in the temperature range from 1073 K to 1673 K (800 °C to 1400 °C) for oxide liquid (slag) in equilibrium with solid Cu metal and/or liquid Pb-Cu alloy, and solid oxide phases: (a) quartz or tridymite (SiO2) and (b) cuprite (Cu2O). High-temperature equilibration on silica or copper substrates was performed, followed by quenching, and direct measurement of Pb, Cu, and Si concentrations in the liquid and solid phases using the electron probe X-ray microanalysis has been employed to accurately characterize the system in equilibrium with Cu or Pb-Cu metal. All results are projected onto the PbO-"CuO0.5"-SiO2 plane for presentation purposes. The present study is the first-ever systematic investigation of this system to describe the slag liquidus temperatures in the silica and cuprite primary phase fields.

  10. THE EFFECT OF METASTABLE EQUILIBRIUM STATES ON THE PARTITIONING OF NITRATE BETWEEN THE GAS AND AEROSOL PHASES. (R824793)

    EPA Science Inventory

    With the aid of three atmospheric aerosol equilibrium models, we quantify the effect of metastable equilibrium states (efflorescence branch) in comparison to stable (deliquescence branch) on the partitioning of total nitrate between the gas and aerosol phases. On average, efflore...

  11. Analytical Phase Equilibrium Function for Mixtures Obeying Raoult's and Henry's Laws

    NASA Astrophysics Data System (ADS)

    Hayes, Robert

    When a mixture of two substances exists in both the liquid and gas phase at equilibrium, Raoults and Henry's laws (ideal solution and ideal dilute solution approximations) can be used to estimate the gas and liquid mole fractions at the extremes of either very little solute or solvent. By assuming that a cubic polynomial can reasonably approximate the intermediate values to these extremes as a function of mole fraction, the cubic polynomial is solved and presented. A closed form equation approximating the pressure dependence on mole fraction of the constituents is thereby obtained. As a first approximation, this is a very simple and potentially useful means to estimate gas and liquid mole fractions of equilibrium mixtures. Mixtures with an azeotrope require additional attention if this type of approach is to be utilized. This work supported in part by federal Grant NRC-HQ-84-14-G-0059.

  12. Experimental station for ultrafast extreme ultraviolet spectroscopy for non-equilibrium dynamics in warm dense matter

    NASA Astrophysics Data System (ADS)

    Lee, Jong-won; Geng, Xiaotao; Jung, Jae Hyung; Cho, Min Sang; Yang, Seong Hyeok; Jo, Jawon; Lee, Chang-lyoul; Cho, Byoung Ick; Kim, Dong-Eon

    2018-07-01

    Recent interest in highly excited matter generated by intense femtosecond laser pulses has led to experimental methods that directly investigate ultrafast non-equilibrium electronic and structural dynamics. We present a tabletop experimental station for the extreme ultraviolet (EUV) spectroscopy used to trace L-edge dynamics in warm dense aluminum with a temporal resolution of a hundred femtoseconds. The system consists of the EUV probe generation part via a high-order harmonic generation process of femtosecond laser pulses with atomic clusters, a beamline with high-throughput optics and a sample-refreshment system of nano-foils utilizing the full repetition rate of the probe, and a flat-field EUV spectrograph. With the accumulation of an order of a hundred shots, a clear observation of the change in the aluminum L-shell absorption was achieved with a temporal resolution of 90 fs in a 600-fs window. The signature of a non-equilibrium electron distribution over a 10-eV range and its evolution to a 1-eV Fermi distribution are observed. This demonstrates the capability of this apparatus to capture the non-equilibrium electron-hole dynamics in highly excited warm dense matter conditions.

  13. Motility-Induced Phase Separation

    NASA Astrophysics Data System (ADS)

    Cates, Michael E.; Tailleur, Julien

    2015-03-01

    Self-propelled particles include both self-phoretic synthetic colloids and various microorganisms. By continually consuming energy, they bypass the laws of equilibrium thermodynamics. These laws enforce the Boltzmann distribution in thermal equilibrium: The steady state is then independent of kinetic parameters. In contrast, self-propelled particles tend to accumulate where they move more slowly. They may also slow down at high density for either biochemical or steric reasons. This creates positive feedback, which can lead to motility-induced phase separation (MIPS) between dense and dilute fluid phases. At leading order in gradients, a mapping relates variable-speed, self-propelled particles to passive particles with attractions. This deep link to equilibrium phase separation is confirmed by simulations but generally breaks down at higher order in gradients: New effects, with no equilibrium counterpart, then emerge. We give a selective overview of the fast-developing field of MIPS, focusing on theory and simulation but including a brief speculative survey of its experimental implications.

  14. Emergent equilibrium in many-body optical bistability

    NASA Astrophysics Data System (ADS)

    Foss-Feig, Michael; Niroula, Pradeep; Young, Jeremy; Hafezi, Mohammad; Gorshkov, Alexey; Wilson, Ryan; Maghrebi, Mohammad

    2017-04-01

    Many-body systems constructed of quantum-optical building blocks can now be realized in experimental platforms ranging from exciton-polariton fluids to Rydberg gases, establishing a fascinating interface between traditional many-body physics and the non-equilibrium setting of cavity-QED. At this interface the standard intuitions of both fields are called into question, obscuring issues as fundamental as the role of fluctuations, dimensionality, and symmetry on the nature of collective behavior and phase transitions. We study the driven-dissipative Bose-Hubbard model, a minimal description of atomic, optical, and solid-state systems in which particle loss is countered by coherent driving. Despite being a lattice version of optical bistability-a foundational and patently non-equilibrium model of cavity-QED-the steady state possesses an emergent equilibrium description in terms of an Ising model. We establish this picture by identifying a limit in which the quantum dynamics is asymptotically equivalent to non-equilibrium Langevin equations, which support a phase transition described by model A of the Hohenberg-Halperin classification. Simulations of the Langevin equations corroborate this picture, producing results consistent with the behavior of a finite-temperature Ising model. M.F.M., J.T.Y., and A.V.G. acknowledge support by ARL CDQI, ARO MURI, NSF QIS, ARO, NSF PFC at JQI, and AFOSR. R.M.W. acknowledges partial support from the NSF under Grant No. PHYS-1516421. M.H. acknowledges support by AFOSR-MURI, ONR and Sloan Foundation.

  15. Phase stability in nanoscale material systems: extension from bulk phase diagrams

    NASA Astrophysics Data System (ADS)

    Bajaj, Saurabh; Haverty, Michael G.; Arróyave, Raymundo; Goddard Frsc, William A., III; Shankar, Sadasivan

    2015-05-01

    Phase diagrams of multi-component systems are critical for the development and engineering of material alloys for all technological applications. At nano dimensions, surfaces (and interfaces) play a significant role in changing equilibrium thermodynamics and phase stability. In this work, it is shown that these surfaces at small dimensions affect the relative equilibrium thermodynamics of the different phases. The CALPHAD approach for material surfaces (also termed ``nano-CALPHAD'') is employed to investigate these changes in three binary systems by calculating their phase diagrams at nano dimensions and comparing them with their bulk counterparts. The surface energy contribution, which is the dominant factor in causing these changes, is evaluated using the spherical particle approximation. It is first validated with the Au-Si system for which experimental data on phase stability of spherical nano-sized particles is available, and then extended to calculate phase diagrams of similarly sized particles of Ge-Si and Al-Cu. Additionally, the surface energies of the associated compounds are calculated using DFT, and integrated into the thermodynamic model of the respective binary systems. In this work we found changes in miscibilities, reaction compositions of about 5 at%, and solubility temperatures ranging from 100-200 K for particles of sizes 5 nm, indicating the importance of phase equilibrium analysis at nano dimensions.Phase diagrams of multi-component systems are critical for the development and engineering of material alloys for all technological applications. At nano dimensions, surfaces (and interfaces) play a significant role in changing equilibrium thermodynamics and phase stability. In this work, it is shown that these surfaces at small dimensions affect the relative equilibrium thermodynamics of the different phases. The CALPHAD approach for material surfaces (also termed ``nano-CALPHAD'') is employed to investigate these changes in three binary systems by

  16. Equilibrium Propagation: Bridging the Gap between Energy-Based Models and Backpropagation

    PubMed Central

    Scellier, Benjamin; Bengio, Yoshua

    2017-01-01

    We introduce Equilibrium Propagation, a learning framework for energy-based models. It involves only one kind of neural computation, performed in both the first phase (when the prediction is made) and the second phase of training (after the target or prediction error is revealed). Although this algorithm computes the gradient of an objective function just like Backpropagation, it does not need a special computation or circuit for the second phase, where errors are implicitly propagated. Equilibrium Propagation shares similarities with Contrastive Hebbian Learning and Contrastive Divergence while solving the theoretical issues of both algorithms: our algorithm computes the gradient of a well-defined objective function. Because the objective function is defined in terms of local perturbations, the second phase of Equilibrium Propagation corresponds to only nudging the prediction (fixed point or stationary distribution) toward a configuration that reduces prediction error. In the case of a recurrent multi-layer supervised network, the output units are slightly nudged toward their target in the second phase, and the perturbation introduced at the output layer propagates backward in the hidden layers. We show that the signal “back-propagated” during this second phase corresponds to the propagation of error derivatives and encodes the gradient of the objective function, when the synaptic update corresponds to a standard form of spike-timing dependent plasticity. This work makes it more plausible that a mechanism similar to Backpropagation could be implemented by brains, since leaky integrator neural computation performs both inference and error back-propagation in our model. The only local difference between the two phases is whether synaptic changes are allowed or not. We also show experimentally that multi-layer recurrently connected networks with 1, 2, and 3 hidden layers can be trained by Equilibrium Propagation on the permutation-invariant MNIST task. PMID

  17. Ternary liquid-liquid equilibrium for eugenol + tert-butanol + water system at 303.15 and 323.15K and atmospheric pressure

    NASA Astrophysics Data System (ADS)

    Sucipto, Retno Kumala Hesti; Kuswandi, Wibawa, Gede

    2017-05-01

    The objective of this study was to determine ternary liquid-liquid equilibrium for eugenol + tert-butanol + water system at 303.15 and 323.15K and atmospheric pressure. Using 25 mL equilibrium cell equipped jacketted water connected to water bath to maintain equilibrium temperature constant. The procedure of this experiment was conducted by inserting mixture of eugenol + tert-butanol + water system at certain composition into equilibrium cell. The solution was stirred for 4 hours and then was allowed for 20 hours in order to separate aqueous and organic phases completely. The temperature equilibrium cell of and the atmosphere pressure were recorded as equilibrium temperature and pressure for each measurenment. The equilibrium compositions of each phase were analyzed using Gas Chromatography. The experimental data obtained in this work were correlated with NRTL and UNIQUAC models with root mean square deviation between esperimental and calculated equilibrium compositions of 0.03% and 0.04% respectively.

  18. THE EFFECT OF METASTABLE EQUILIBRIUM STATES ON THE PARTITIONING OF NITRATE BETWEEN THE GAS AND AEROSOL PHASES. (R826371C005)

    EPA Science Inventory

    With the aid of three atmospheric aerosol equilibrium models, we quantify the effect of metastable equilibrium states (efflorescence branch) in comparison to stable (deliquescence branch) on the partitioning of total nitrate between the gas and aerosol phases. On average, effl...

  19. Phase equilibrium constraints on the origin of basalts, picrites, and komatiites

    NASA Astrophysics Data System (ADS)

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

    1998-07-01

    Experimental phase equilibrium studies at pressures ranging from 1 atm to 10 GPa are sufficient to constrain the origin of igneous rocks formed along oceanic ridges and in hotspots. The major element geochemistry of MORB is dominated by partial crystallization at low pressures in the oceanic crust and uppermost mantle, forcing compliance with liquid compositions in low-pressure cotectic equilibrium with olivine, plagioclase and often augite too; parental magmas to MORB formed by partial melting, mixing, and pooling have not survived these effects. Similarly, picrites and komatiites can transform to basalts by partial crystallization in the crust and lithosphere. However, parental picrites and komatiites that were successful in erupting to the surface typically have compositions that can be matched to experimentally-observed anhydrous primary magmas in equilibrium with harzburgite [L+Ol+Opx] at 3.0 to 4.5 GPa. This pressure is likely to represent an average for pooled magmas that collected at the top of a plume head as it flattened below the lithosphere. There is substantial uniformity in the normative olivine content of primary magmas at all depths in a plume melt column, and this results in pooled komatiitic magmas that are equally uniform in normative olivine. However, the imposition of pressure above 3 GPa produces picrites and komatiites with variations in normative enstatite and Al 2O 3 that reveal plume potential temperature and depths of initial melting. Hotter plumes begin to melt deeper than cooler plumes, yielding picrites and komatiites that are enriched in normative enstatite and depleted in Al 2O 3 because of a deeper column within which orthopyroxene can dissolve during decompression. Pressures of initial melting span the 4 to 10 GPa range, increasing in the following order: Iceland, Hawaii, Gorgona, Belingwe, Barberton. Parental komatiites and picrites from a single plume also exhibit internal variability in normative enstatite and Al 2O 3

  20. Mixed-order phase transition in a colloidal crystal.

    PubMed

    Alert, Ricard; Tierno, Pietro; Casademunt, Jaume

    2017-12-05

    Mixed-order phase transitions display a discontinuity in the order parameter like first-order transitions yet feature critical behavior like second-order transitions. Such transitions have been predicted for a broad range of equilibrium and nonequilibrium systems, but their experimental observation has remained elusive. Here, we analytically predict and experimentally realize a mixed-order equilibrium phase transition. Specifically, a discontinuous solid-solid transition in a 2D crystal of paramagnetic colloidal particles is induced by a magnetic field [Formula: see text] At the transition field [Formula: see text], the energy landscape of the system becomes completely flat, which causes diverging fluctuations and correlation length [Formula: see text] Mean-field critical exponents are predicted, since the upper critical dimension of the transition is [Formula: see text] Our colloidal system provides an experimental test bed to probe the unconventional properties of mixed-order phase transitions.

  1. Mixed-order phase transition in a colloidal crystal

    NASA Astrophysics Data System (ADS)

    Alert, Ricard; Tierno, Pietro; Casademunt, Jaume

    2017-12-01

    Mixed-order phase transitions display a discontinuity in the order parameter like first-order transitions yet feature critical behavior like second-order transitions. Such transitions have been predicted for a broad range of equilibrium and nonequilibrium systems, but their experimental observation has remained elusive. Here, we analytically predict and experimentally realize a mixed-order equilibrium phase transition. Specifically, a discontinuous solid-solid transition in a 2D crystal of paramagnetic colloidal particles is induced by a magnetic field H. At the transition field Hs, the energy landscape of the system becomes completely flat, which causes diverging fluctuations and correlation length ξ∝|H2-Hs2|-1/2. Mean-field critical exponents are predicted, since the upper critical dimension of the transition is du=2. Our colloidal system provides an experimental test bed to probe the unconventional properties of mixed-order phase transitions.

  2. New phenomena in non-equilibrium quantum physics

    NASA Astrophysics Data System (ADS)

    Kitagawa, Takuya

    From its beginning in the early 20th century, quantum theory has become progressively more important especially due to its contributions to the development of technologies. Quantum mechanics is crucial for current technology such as semiconductors, and also holds promise for future technologies such as superconductors and quantum computing. Despite of the success of quantum theory, its applications have been mostly limited to equilibrium or static systems due to 1. lack of experimental controllability of non-equilibrium quantum systems 2. lack of theoretical frameworks to understand non-equilibrium dynamics. Consequently, physicists have not yet discovered too many interesting phenomena in non-equilibrium quantum systems from both theoretical and experimental point of view and thus, non-equilibrium quantum physics did not attract too much attentions. The situation has recently changed due to the rapid development of experimental techniques in condensed matter as well as cold atom systems, which now enables a better control of non-equilibrium quantum systems. Motivated by this experimental progress, we constructed theoretical frameworks to study three different non-equilibrium regimes of transient dynamics, steady states and periodically drives. These frameworks provide new perspectives for dynamical quantum process, and help to discover new phenomena in these systems. In this thesis, we describe these frameworks through explicit examples and demonstrate their versatility. Some of these theoretical proposals have been realized in experiments, confirming the applicability of the theories to realistic experimental situations. These studies have led to not only the improved fundamental understanding of non-equilibrium processes in quantum systems, but also suggested entirely different venues for developing quantum technologies.

  3. Experimental Determination of One-Atmosphere Phase Relations of Rhyodacite Pumice Erupted from Chaos Crags, Lassen Volcanic Center, California

    NASA Astrophysics Data System (ADS)

    Quinn, E. T.; Schwab, B. E.

    2012-12-01

    A series of one-atmosphere high-temperature anhydrous phase equilibrium melting experiments was performed on a natural rhyodacite pumice from the 1103±13 years BP pyroclastic flow from the Chaos Crags, Lassen Volcanic Center, California. The pumice (CCP) is the most silicic product known of the 1103 eruption of Chaos Crags. All experimental runs were performed in a Deltech VT-31 one-atmosphere gas-mixing furnace at the Experimental Petrology Lab, Humboldt State University, Arcata, California. Six ~90-99 hour runs were conducted at 35-55°C intervals, with target temperatures from 1000°C to 1200°C at the Ni-NiO buffer. The nominally anhydrous liquidus of the rhyodacite pumice is >1196°C and solidus is <998°C, outside the investigated temperature range. All experimental run products contain glass, plagioclase, quartz, and Fe-Ti oxides. Amphibole with breakdown textures is observed at temperatures ≤1159°C, and appears more stable in lower temperature runs. At 998°C, amphibole appears most stable, with only minor breakdown texture. Biotite, a major phase in starting material, is not observed in any run products. Based on comparison between experimental and natural phase assemblages and glass, plagioclase, and amphibole compositions, the Chaos Crags rhyodacite pumice erupted at a temperature <998°C, the lowest experimental run temperature investigated. Additional experimental runs at temperatures <998°C are currently being conducted.

  4. LEPER: Library of Experimental PhasE Relations

    NASA Astrophysics Data System (ADS)

    Davis, F.; Gordon, S.; Mukherjee, S.; Hirschmann, M.; Ghiorso, M.

    2006-12-01

    The Library of Experimental PhasE Relations (LEPER) seeks to compile published experimental determinations of magmatic phase equilibria and provide those data on the web with a searchable and downloadable interface. Compiled experimental data include the conditions and durations of experiments, the bulk compositions of experimental charges, and the identity, compositions and proportions of phases observed, and, where available, estimates of experimental and analytical uncertainties. Also included are metadata such as the type of experimental device, capsule material, and method(s) of quantitative analysis. The database may be of use to practicing experimentalists as well as the wider Earth science community. Experimentalists may find the data useful for planning new experiments and will easily be able to compare their results to the full body of previous experimentnal data. Geologists may use LEPER to compare rocks sampled in the field with experiments performed on similar bulk composition or with experiments that produced similar-composition product phases. Modelers may use LEPER to parameterize partial melting of various lithologies. One motivation for compiling LEPER is for calibration of updated and revised versions of MELTS, however, it is hoped that the availability of LEPER will facilitate formulation and calibration of additional thermodynamic or empirical models of magmatic phase relations and phase equilibria, geothermometers and more. Data entry for LEPER is occuring presently: As of August, 2006, >6200 experiments have been entered, chiefly from work published between 1997 and 2005. A prototype web interface has been written and beta release on the web is anticipated in Fall, 2006. Eventually, experimentalists will be able to submit their new experimental data to the database via the web. At present, the database contains only data pertaining to the phase equilibria of silicate melts, but extension to other experimental data involving other fluids or

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

    PubMed

    Wheeler, Tobias D; Stroock, Abraham D

    2009-07-07

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

  6. Phase equilibrium in system Ti-Si-C-B and synthesis of MAX phase layers in vacuum under the influence of electron beam

    NASA Astrophysics Data System (ADS)

    Smirnyagina, N. N.; Khaltanova, V. M.; Dasheev, D. E.; Lapina, A. E.

    2017-05-01

    Composite layers on the basis of carbides and borides the titan and silicon on titanic alloy VТ-1 are generated at diffused saturation by electron beam treatment in vacuum. Formation in a composite of MAX phase Ti3SiC2 is shown. Thermodynamic research of phase equilibrium in systems Ti-Si-C and Ti-B-C in the conditions of high vacuum is executed. The thermodynamics, formation mechanisms of superfirm layers borides and carbides of the titan and silicon are investigated.

  7. Mixed-order phase transition in a colloidal crystal

    PubMed Central

    Tierno, Pietro; Casademunt, Jaume

    2017-01-01

    Mixed-order phase transitions display a discontinuity in the order parameter like first-order transitions yet feature critical behavior like second-order transitions. Such transitions have been predicted for a broad range of equilibrium and nonequilibrium systems, but their experimental observation has remained elusive. Here, we analytically predict and experimentally realize a mixed-order equilibrium phase transition. Specifically, a discontinuous solid–solid transition in a 2D crystal of paramagnetic colloidal particles is induced by a magnetic field H. At the transition field Hs, the energy landscape of the system becomes completely flat, which causes diverging fluctuations and correlation length ξ∝|H2−Hs2|−1/2. Mean-field critical exponents are predicted, since the upper critical dimension of the transition is du=2. Our colloidal system provides an experimental test bed to probe the unconventional properties of mixed-order phase transitions. PMID:29158388

  8. Discontinuous non-equilibrium phase transition in a threshold Schloegl model for autocatalysis: Generic two-phase coexistence and metastability

    NASA Astrophysics Data System (ADS)

    Wang, Chi-Jen; Liu, Da-Jiang; Evans, James W.

    2015-04-01

    Threshold versions of Schloegl's model on a lattice, which involve autocatalytic creation and spontaneous annihilation of particles, can provide a simple prototype for discontinuous non-equilibrium phase transitions. These models are equivalent to so-called threshold contact processes. A discontinuous transition between populated and vacuum states can occur selecting a threshold of N ≥ 2 for the minimum number, N, of neighboring particles enabling autocatalytic creation at an empty site. Fundamental open questions remain given the lack of a thermodynamic framework for analysis. For a square lattice with N = 2, we show that phase coexistence occurs not at a unique value but for a finite range of particle annihilation rate (the natural control parameter). This generic two-phase coexistence also persists when perturbing the model to allow spontaneous particle creation. Such behavior contrasts both the Gibbs phase rule for thermodynamic systems and also previous analysis for this model. We find metastability near the transition corresponding to a non-zero effective line tension, also contrasting previously suggested critical behavior. Mean-field type analysis, extended to treat spatially heterogeneous states, further elucidates model behavior.

  9. Out-of-equilibrium dynamics driven by localized time-dependent perturbations at quantum phase transitions

    NASA Astrophysics Data System (ADS)

    Pelissetto, Andrea; Rossini, Davide; Vicari, Ettore

    2018-03-01

    We investigate the quantum dynamics of many-body systems subject to local (i.e., restricted to a limited space region) time-dependent perturbations. If the system crosses a quantum phase transition, an off-equilibrium behavior is observed, even for a very slow driving. We show that, close to the transition, time-dependent quantities obey scaling laws. In first-order transitions, the scaling behavior is universal, and some scaling functions can be computed exactly. For continuous transitions, the scaling laws are controlled by the standard critical exponents and by the renormalization-group dimension of the perturbation at the transition. Our protocol can be implemented in existing relatively small quantum simulators, paving the way for a quantitative probe of the universal off-equilibrium scaling behavior, without the need to manipulate systems close to the thermodynamic limit.

  10. Formation of metastable phases by spinodal decomposition

    PubMed Central

    Alert, Ricard; Tierno, Pietro; Casademunt, Jaume

    2016-01-01

    Metastable phases may be spontaneously formed from other metastable phases through nucleation. Here we demonstrate the spontaneous formation of a metastable phase from an unstable equilibrium by spinodal decomposition, which leads to a transient coexistence of stable and metastable phases. This phenomenon is generic within the recently introduced scenario of the landscape-inversion phase transitions, which we experimentally realize as a structural transition in a colloidal crystal. This transition exhibits a rich repertoire of new phase-ordering phenomena, including the coexistence of two equilibrium phases connected by two physically different interfaces. In addition, this scenario enables the control of sizes and lifetimes of metastable domains. Our findings open a new setting that broadens the fundamental understanding of phase-ordering kinetics, and yield new prospects of applications in materials science. PMID:27713406

  11. A Simple System for Observing Dynamic Phase Equilibrium via an Inquiry-Based Laboratory or Demonstration

    ERIC Educational Resources Information Center

    Cloonan, Carrie A.; Andrew, Julie A.; Nichol, Carolyn A.; Hutchinson, John S.

    2011-01-01

    This article describes an activity that can be used as an inquiry-based laboratory or demonstration for either high school or undergraduate chemistry students to provide a basis for understanding both vapor pressure and the concept of dynamic phase equilibrium. The activity includes a simple setup to create a closed system of only water liquid and…

  12. Spontaneous Time Symmetry Breaking in System with Mixed Strategy Nash Equilibrium: Evidences in Experimental Economics Data

    NASA Astrophysics Data System (ADS)

    Wang, Zhijian; Xu, Bin; Zhejiang Collaboration

    2011-03-01

    In social science, laboratory experiment with human subjects' interaction is a standard test-bed for studying social processes in micro level. Usually, as in physics, the processes near equilibrium are suggested as stochastic processes with time-reversal symmetry (TRS). To the best of our knowledge, near equilibrium, the breaking time symmetry, as well as the existence of robust time anti-symmetry processes, has not been reported clearly in experimental economics till now. By employing Markov transition method to analysis the data from human subject 2x2 Games with wide parameters and mixed Nash equilibrium, we study the time symmetry of the social interaction process near Nash equilibrium. We find that, the time symmetry is broken, and there exists a robust time anti-symmetry processes. We also report the weight of the time anti-symmetry processes in the total processes of each the games. Evidences in laboratory marketing experiments, at the same time, are provided as one-dimension cases. In these cases, time anti-symmetry cycles can also be captured. The proposition of time anti-symmetry processes is small, but the cycles are distinguishable.

  13. Rapid-Equilibrium Enzyme Kinetics

    ERIC Educational Resources Information Center

    Alberty, Robert A.

    2008-01-01

    Rapid-equilibrium rate equations for enzyme-catalyzed reactions are especially useful because if experimental data can be fit by these simpler rate equations, the Michaelis constants can be interpreted as equilibrium constants. However, for some reactions it is necessary to use the more complicated steady-state rate equations. Thermodynamics is…

  14. Iron Carbides in Fischer–Tropsch Synthesis: Theoretical and Experimental Understanding in Epsilon-Iron Carbide Phase Assignment

    DOE PAGES

    Liu, Xing-Wu; Cao, Zhi; Zhao, Shu; ...

    2017-09-11

    As active phases in low-temperature Fischer–Tropsch synthesis for liquid fuel production, epsilon iron carbides are critically important industrial materials. However, the precise atomic structure of epsilon iron carbides remains unclear, leading to a half-century of debate on the phase assignment of the ε-Fe 2C and ε’-Fe 2.2C. Here, we resolve this decades-long question by a combining theoretical and experimental investigation to assign the phases unambiguously. First, we have investigated the equilibrium structures and thermal stabilities of ε-Fe xC, (x = 1, 2, 2.2, 3, 4, 6, 8) by first-principles calculations. We have also acquired X-ray diffraction patterns and Mössbauer spectramore » for these epsilon iron carbides, and compared them with the simulated results. These analyses indicate that the unit cell of ε-Fe 2C contains only one type of chemical environment for Fe atoms, while ε’-Fe 2.2C has six sets of chemically distinct Fe atoms.« less

  15. Equilibrium-phase MR angiography: Comparison of unspecific extracellular and protein-binding gadolinium-based contrast media with respect to image quality.

    PubMed

    Erb-Eigner, Katharina; Taupitz, Matthias; Asbach, Patrick

    2016-01-01

    The purpose of this study was to compare contrast and image quality of whole-body equilibrium-phase high-spatial-resolution MR angiography using a non-protein-binding unspecific extracellular gadolinium-based contrast medium with that of two contrast media with different protein-binding properties. 45 patients were examined using either 15 mL of gadobutrol (non-protein-binding, n = 15), 32 mL of gadobenate dimeglumine (weakly protein binding, n = 15) or 11 mL gadofosveset trisodium (protein binding, n = 15) followed by equilibrium-phase high-spatial-resolution MR-angiography of four consecutive anatomic regions. The time elapsed between the contrast injection and the beginning of the equilibrium-phase image acquisition in the respective region was measured and was up to 21 min. Signal intensity was measured in two vessels per region and in muscle tissue. Relative contrast (RC) values were calculated. Vessel contrast, artifacts and image quality were rated by two radiologists in consensus on a five-point scale. Compared with gadobutrol, gadofosveset trisodium revealed significantly higher RC values only when acquired later than 15 min after bolus injection. Otherwise, no significant differences between the three contrast media were found regarding vascular contrast and image quality. Equilibrium-phase high-spatial-resolution MR-angiography using a weakly protein-binding or even non-protein-binding contrast medium is equivalent to using a stronger protein-binding contrast medium when image acquisition is within the first 15 min after contrast injection, and allows depiction of the vasculature with high contrast and image quality. The protein-binding contrast medium was superior for imaging only later than 15 min after contrast medium injection. Copyright © 2015 John Wiley & Sons, Ltd.

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

    NASA Astrophysics Data System (ADS)

    Schiffbauer, Jarrod; Luo, Tengfei

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

  17. Detecting temperature fluctuations at equilibrium.

    PubMed

    Dixit, Purushottam D

    2015-05-21

    The Gibbs and the Boltzmann definition of temperature agree only in the macroscopic limit. The ambiguity in identifying the equilibrium temperature of a finite-sized 'small' system exchanging energy with a bath is usually understood as a limitation of conventional statistical mechanics. We interpret this ambiguity as resulting from a stochastically fluctuating temperature coupled with the phase space variables giving rise to a broad temperature distribution. With this ansatz, we develop the equilibrium statistics and dynamics of small systems. Numerical evidence using an analytically tractable model shows that the effects of temperature fluctuations can be detected in the equilibrium and dynamical properties of the phase space of the small system. Our theory generalizes statistical mechanics to small systems relevant in biophysics and nanotechnology.

  18. Phase Equilibrium of TiO2 Nanocrystals in Flame-Assisted Chemical Vapor Deposition.

    PubMed

    Liu, Changran; Camacho, Joaquin; Wang, Hai

    2018-01-19

    Nano-scale titanium oxide (TiO 2 ) is a material useful for a wide range of applications. In a previous study, we showed that TiO 2 nanoparticles of both rutile and anatase crystal phases could be synthesized over the size range of 5 to 20 nm in flame-assisted chemical vapor deposition. Rutile was unexpectedly dominant in oxygen-lean synthesis conditions, whereas anatase is the preferred phase in oxygen-rich gases. The observation is in contrast to the 14 nm rutile-anatase crossover size derived from the existing crystal-phase equilibrium model. In the present work, we made additional measurements over a wider range of synthesis conditions; the results confirm the earlier observations. We propose an improved model for the surface energy that considers the role of oxygen desorption at high temperatures. The model successfully explains the observations made in the current and previous work. The current results provide a useful path to designing flame-assisted chemical vapor deposition of TiO 2 nanocrystals with controllable crystal phases. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. Modeling multicomponent ion exchange equilibrium utilizing hydrous crystalline silicotitanates by a multiple interactive ion exchange site model

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

    Zheng, Z.; Anthony, R.G.; Miller, J.E.

    1997-06-01

    An equilibrium multicomponent ion exchange model is presented for the ion exchange of group I metals by TAM-5, a hydrous crystalline silicotitanate. On the basis of the data from ion exchange and structure studies, the solid phase is represented as Na{sub 3}X instead of the usual form of NaX. By using this solid phase representation, the solid can be considered as an ideal phase. A set of model ion exchange reactions is proposed for ion exchange between H{sup +}, Na{sup +}, K{sup +}, Rb{sup +}, and Cs{sup +}. The equilibrium constants for these reactions were estimated from experiments with simplemore » ion exchange systems. Bromley`s model for activity coefficients of electrolytic solutions was used to account for liquid phase nonideality. Bromley`s model parameters for CsOH at high ionic strength and for NO{sub 2}{sup {minus}} and Al(OH){sub 4}{sup {minus}} were estimated in order to apply the model for complex waste simulants. The equilibrium compositions and distribution coefficients of counterions were calculated for complex simulants typical of DOE wastes by solving the equilibrium equations for the model reactions and material balance equations. The predictions match the experimental results within 10% for all of these solutions.« less

  20. Experimental testing of olivine-melt equilibrium models at high temperatures

    NASA Astrophysics Data System (ADS)

    Krasheninnikov, S. P.; Sobolev, A. V.; Batanova, V. G.; Kargaltsev, A. A.; Borisov, A. A.

    2017-08-01

    Data are presented on the equilibrium compositions of olivine and melts in the products of 101 experiments performed at 1300-1600°C, atmospheric pressure, and controlled oxygen fugacity by means of new equipment at the Vernadsky Institute. It was shown that the available models of the olivine-melt equilibrium describe with insufficient adequacy the natural systems at temperatures over 1400°C. The most adequate is the model by Ford et al. (1983). However, this model overestimates systematically the equilibrium temperature with underestimating by 20-40°C at 1450-1600°C. These data point to the need for developing a new, improved quantitative model of the olivine-melt equilibrium for high-temperature magnesian melts, as well as to the possibility of these studies on the basis of the equipment presented.

  1. Discontinuous non-equilibrium phase transition in a threshold Schloegl model for autocatalysis: Generic two-phase coexistence and metastability

    DOE PAGES

    Wang, Chi -Jen; Liu, Da -Jiang; Evans, James W.

    2015-04-28

    Threshold versions of Schloegl’s model on a lattice, which involve autocatalytic creation and spontaneous annihilation of particles, can provide a simple prototype for discontinuous non-equilibrium phase transitions. These models are equivalent to so-called threshold contact processes. A discontinuous transition between populated and vacuum states can occur selecting a threshold of N ≥ 2 for the minimum number, N, of neighboring particles enabling autocatalytic creation at an empty site. Fundamental open questions remain given the lack of a thermodynamic framework for analysis. For a square lattice with N = 2, we show that phase coexistence occurs not at a unique valuemore » but for a finite range of particle annihilation rate (the natural control parameter). This generic two-phase coexistence also persists when perturbing the model to allow spontaneous particle creation. Such behavior contrasts both the Gibbs phase rule for thermodynamic systems and also previous analysis for this model. We find metastability near the transition corresponding to a non-zero effective line tension, also contrasting previously suggested critical behavior. As a result, mean-field type analysis, extended to treat spatially heterogeneous states, further elucidates model behavior.« less

  2. Relaxation to a Phase-Locked Equilibrium State in a One-Dimensional Bosonic Josephson Junction

    NASA Astrophysics Data System (ADS)

    Pigneur, Marine; Berrada, Tarik; Bonneau, Marie; Schumm, Thorsten; Demler, Eugene; Schmiedmayer, Jörg

    2018-04-01

    We present an experimental study on the nonequilibrium tunnel dynamics of two coupled one-dimensional Bose-Einstein quasicondensates deep in the Josephson regime. Josephson oscillations are initiated by splitting a single one-dimensional condensate and imprinting a relative phase between the superfluids. Regardless of the initial state and experimental parameters, the dynamics of the relative phase and atom number imbalance shows a relaxation to a phase-locked steady state. The latter is characterized by a high phase coherence and reduced fluctuations with respect to the initial state. We propose an empirical model based on the analogy with the anharmonic oscillator to describe the effect of various experimental parameters. A microscopic theory compatible with our observations is still missing.

  3. Quantum-chemical calculations and electron diffraction study of the equilibrium molecular structure of vitamin K3

    NASA Astrophysics Data System (ADS)

    Khaikin, L. S.; Tikhonov, D. S.; Grikina, O. E.; Rykov, A. N.; Stepanov, N. F.

    2014-05-01

    The equilibrium molecular structure of 2-methyl-1,4-naphthoquinone (vitamin K3) having C s symmetry is experimentally characterized for the first time by means of gas-phase electron diffraction using quantum-chemical calculations and data on the vibrational spectra of related compounds.

  4. Extraction equilibrium of indium(III) from nitric acid solutions by di(2-ethylhexyl)phosphoric acid dissolved in kerosene.

    PubMed

    Tsai, Hung-Sheng; Tsai, Teh-Hua

    2012-01-04

    The extraction equilibrium of indium(III) from a nitric acid solution using di(2-ethylhexyl) phosphoric acid (D2EHPA) as an acidic extractant of organophosphorus compounds dissolved in kerosene was studied. By graphical and numerical analysis, the compositions of indium-D2EHPA complexes in organic phase and stoichiometry of the extraction reaction were examined. Nitric acid solutions with various indium concentrations at 25 °C were used to obtain the equilibrium constant of InR₃ in the organic phase. The experimental results showed that the extraction distribution ratios of indium(III) between the organic phase and the aqueous solution increased when either the pH value of the aqueous solution and/or the concentration of the organic phase extractant increased. Finally, the recovery efficiency of indium(III) in nitric acid was measured.

  5. Non-equilibrium phase behavior and friction of confined molecular films under shear: A non-equilibrium molecular dynamics study.

    PubMed

    Maćkowiak, Sz; Heyes, D M; Dini, D; Brańka, A C

    2016-10-28

    The phase behavior of a confined liquid at high pressure and shear rate, such as is found in elastohydrodynamic lubrication, can influence the traction characteristics in machine operation. Generic aspects of this behavior are investigated here using Non-equilibrium Molecular Dynamics (NEMD) simulations of confined Lennard-Jones (LJ) films under load with a recently proposed wall-driven shearing method without wall atom tethering [C. Gattinoni et al., Phys. Rev. E 90, 043302 (2014)]. The focus is on thick films in which the nonequilibrium phases formed in the confined region impact on the traction properties. The nonequilibrium phase and tribological diagrams are mapped out in detail as a function of load, wall sliding speed, and atomic scale surface roughness, which is shown can have a significant effect. The transition between these phases is typically not sharp as the external conditions are varied. The magnitude of the friction coefficient depends strongly on the nonequilibrium phase adopted by the confined region of molecules, and in general does not follow the classical friction relations between macroscopic bodies, e.g., the frictional force can decrease with increasing load in the Plug-Slip (PS) region of the phase diagram owing to structural changes induced in the confined film. The friction coefficient can be extremely low (∼0.01) in the PS region as a result of incommensurate alignment between a (100) face-centered cubic wall plane and reconstructed (111) layers of the confined region near the wall. It is possible to exploit hysteresis to retain low friction PS states well into the central localization high wall speed region of the phase diagram. Stick-slip behavior due to periodic in-plane melting of layers in the confined region and subsequent annealing is observed at low wall speeds and moderate external loads. At intermediate wall speeds and pressure values (at least) the friction coefficient decreases with increasing well depth of the LJ potential

  6. Prediction of Thermodynamic Equilibrium Temperature of Cu-Based Shape-Memory Smart Materials

    NASA Astrophysics Data System (ADS)

    Eskİl, Murat; Aldaş, Kemal; Özkul, İskender

    2015-01-01

    The thermodynamic equilibrium temperature ( T 0) is an important factor in the austenite and martensitic phases. In this study, the effects of alloying elements and heat treatments on T 0 temperature were investigated using Genetic Programming (GP) which has become one of the tools used in the study of condensed matter. Due to the changes in T 0, it is possible to analyze the changes in the entropy of the phase transitions. The data patterns of the GP formulation are based on well-established experimental results from the literature. The results of the GP-based formulation were compared with experimental results and found to be reliable with a very high correlation ( R 2 = 0.965 for training and R 2 = 0.952 for testing).

  7. 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.

  8. Phases, periphases, and interphases equilibrium by molecular modeling. I. Mass equilibrium by the semianalytical stochastic perturbations method and application to a solution between (120) gypsum faces

    NASA Astrophysics Data System (ADS)

    Pedesseau, Laurent; Jouanna, Paul

    2004-12-01

    The SASP (semianalytical stochastic perturbations) method is an original mixed macro-nano-approach dedicated to the mass equilibrium of multispecies phases, periphases, and interphases. This general method, applied here to the reflexive relation Ck⇔μk between the concentrations Ck and the chemical potentials μk of k species within a fluid in equilibrium, leads to the distribution of the particles at the atomic scale. The macroaspects of the method, based on analytical Taylor's developments of chemical potentials, are intimately mixed with the nanoaspects of molecular mechanics computations on stochastically perturbed states. This numerical approach, directly linked to definitions, is universal by comparison with current approaches, DLVO Derjaguin-Landau-Verwey-Overbeek, grand canonical Monte Carlo, etc., without any restriction on the number of species, concentrations, or boundary conditions. The determination of the relation Ck⇔μk implies in fact two problems: a direct problem Ck⇒μk and an inverse problem μk⇒Ck. Validation of the method is demonstrated in case studies A and B which treat, respectively, a direct problem and an inverse problem within a free saturated gypsum solution. The flexibility of the method is illustrated in case study C dealing with an inverse problem within a solution interphase, confined between two (120) gypsum faces, remaining in connection with a reference solution. This last inverse problem leads to the mass equilibrium of ions and water molecules within a 3 Å thick gypsum interface. The major unexpected observation is the repulsion of SO42- ions towards the reference solution and the attraction of Ca2+ ions from the reference solution, the concentration being 50 times higher within the interphase as compared to the free solution. The SASP method is today the unique approach able to tackle the simulation of the number and distribution of ions plus water molecules in such extreme confined conditions. This result is of prime

  9. Universal Off-Equilibrium Scaling of Critical Cumulants in the QCD Phase Diagram

    DOE PAGES

    Mukherjee, Swagato; Venugopalan, Raju; Yin, Yi

    2016-11-23

    Exploiting the universality between the QCD critical point and the three-dimensional Ising model, closed form expressions derived for nonequilibrium critical cumulants on the crossover side of the critical point reveal that they can differ in both magnitude and sign from equilibrium expectations. Here, we demonstrate here that key elements of the Kibble-Zurek framework of nonequilibrium phase transitions can be employed to describe the dynamics of these critical cumulants. Lastly, our results suggest that observables sensitive to critical dynamics in heavy-ion collisions should be expressible as universal scaling functions, thereby providing powerful model-independent guidance in searches for the QCD critical point.

  10. 3D equilibrium reconstruction with islands

    DOE PAGES

    Cianciosa, M.; Hirshman, S. P.; Seal, S. K.; ...

    2018-02-15

    This study presents the development of a 3D equilibrium reconstruction tool and the results of the first-ever reconstruction of an island equilibrium. The SIESTA non-nested equilibrium solver has been coupled to the V3FIT 3D equilibrium reconstruction code. Computed from a coupled VMEC and SIESTA model, synthetic signals are matched to measured signals by finding an optimal set of equilibrium parameters. By using the normalized pressure in place of normalized flux, non-equilibrium quantities needed by diagnostic signals can be efficiently mapped to the equilibrium. The effectiveness of this tool is demonstrated by reconstructing an island equilibrium of a DIII-D inner wallmore » limited L-mode case with an n = 1 error field applied. Finally, flat spots in Thomson and ECE temperature diagnostics show the reconstructed islands have the correct size and phase.« less

  11. 3D equilibrium reconstruction with islands

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

    Cianciosa, M.; Hirshman, S. P.; Seal, S. K.

    This study presents the development of a 3D equilibrium reconstruction tool and the results of the first-ever reconstruction of an island equilibrium. The SIESTA non-nested equilibrium solver has been coupled to the V3FIT 3D equilibrium reconstruction code. Computed from a coupled VMEC and SIESTA model, synthetic signals are matched to measured signals by finding an optimal set of equilibrium parameters. By using the normalized pressure in place of normalized flux, non-equilibrium quantities needed by diagnostic signals can be efficiently mapped to the equilibrium. The effectiveness of this tool is demonstrated by reconstructing an island equilibrium of a DIII-D inner wallmore » limited L-mode case with an n = 1 error field applied. Finally, flat spots in Thomson and ECE temperature diagnostics show the reconstructed islands have the correct size and phase.« less

  12. 3D equilibrium reconstruction with islands

    NASA Astrophysics Data System (ADS)

    Cianciosa, M.; Hirshman, S. P.; Seal, S. K.; Shafer, M. W.

    2018-04-01

    This paper presents the development of a 3D equilibrium reconstruction tool and the results of the first-ever reconstruction of an island equilibrium. The SIESTA non-nested equilibrium solver has been coupled to the V3FIT 3D equilibrium reconstruction code. Computed from a coupled VMEC and SIESTA model, synthetic signals are matched to measured signals by finding an optimal set of equilibrium parameters. By using the normalized pressure in place of normalized flux, non-equilibrium quantities needed by diagnostic signals can be efficiently mapped to the equilibrium. The effectiveness of this tool is demonstrated by reconstructing an island equilibrium of a DIII-D inner wall limited L-mode case with an n = 1 error field applied. Flat spots in Thomson and ECE temperature diagnostics show the reconstructed islands have the correct size and phase. ).

  13. Quantifying the equilibrium partitioning of substituted polycyclic aromatic hydrocarbons in aerosols and clouds using COSMOtherm.

    PubMed

    Awonaike, Boluwatife; Wang, Chen; Goss, Kai-Uwe; Wania, Frank

    2017-03-22

    Functional groups attached to polycyclic aromatic hydrocarbons (PAHs) can significantly modify the environmental fate of the parent compound. Equilibrium partition coefficients, which are essential for describing the environmental phase distribution of a compound, are largely unavailable for substituted PAHs (SPAHs). Here, COSMOtherm, a software based on quantum-chemical calculations is used to estimate the atmospherically relevant partition coefficients between the gas phase, the aqueous bulk phase, the water surface and the water insoluble organic matter phase, as well as the salting-out coefficients, for naphthalene, anthracene, phenanthrene, benz(a)anthracene, benzo(a)pyrene and dibenz(a,h)anthracene and 62 of their substituted counterparts. They serve as input parameters for the calculation of equilibrium phase distribution of these compounds in aerosols and clouds. Our results, which were compared with available experimental data, show that the effect of salts, the adsorption to the water surface and the dissolution in a bulk aqueous phase can be safely neglected when estimating the gas-particle partitioning of SPAHs in aerosols. However, for small PAHs with more than one polar functional group the aqueous phase can be the dominant reservoir in a cloud.

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

    NASA Astrophysics Data System (ADS)

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

    2018-03-01

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

  15. Entropic description of gas hydrate ice/liquid equilibrium via enhanced sampling of coexisting phases

    DOE PAGES

    Malolepsza, Edyta; Kim, Jaegil; Keyes, Tom

    2015-04-28

    Metastable β ice holds small guest molecules in stable gas hydrates, so its solid/liquid equilibrium is of interest. However, aqueous crystal/liquid transitions are very difficult to simulate. A new MD algorithm generates trajectories in a generalized NPT ensemble and equilibrates states of coexisting phases with a selectable enthalpy. Furthermore, with replicas spanning the range between β ice and liquid water we find the statistical temperature from the enthalpy histograms and characterize the transition by the entropy, introducing a general computational procedure for first-order transitions.

  16. Experimental Phasing: Substructure Solution and Density Modification as Implemented in SHELX.

    PubMed

    Thorn, Andrea

    2017-01-01

    This chapter describes experimental phasing methods as implemented in SHELX. After introducing fundamental concepts underlying all experimental phasing approaches, the methods used by SHELXC/D/E are described in greater detail, such as dual-space direct methods, Patterson seeding and density modification with the sphere of influence algorithm. Intensity differences from data for experimental phasing can also be used for the generation and usage of difference maps with ANODE for validation and phasing purposes. A short section describes how molecular replacement can be combined with experimental phasing methods. The second half covers practical challenges, such as prerequisites for successful experimental phasing, evaluation of potential solutions, and what to do if substructure search or density modification fails. It is also shown how auto-tracing in SHELXE can improve automation and how it ties in with automatic model building after phasing.

  17. In-cloud multiphase behaviour of acetone in the troposphere: gas uptake, Henry's law equilibrium and aqueous phase photooxidation.

    PubMed

    Poulain, Laurent; Katrib, Yasmine; Isikli, Estelle; Liu, Yao; Wortham, Henri; Mirabel, Philippe; Le Calvé, Stéphane; Monod, Anne

    2010-09-01

    Acetone is ubiquitous in the troposphere. Several papers have focused in the past on its gas phase reactivity and its impact on tropospheric chemistry. However, acetone is also present in atmospheric water droplets where its behaviour is still relatively unknown. In this work, we present its gas/aqueous phase transfer and its aqueous phase photooxidation. The uptake coefficient of acetone on water droplets was measured between 268 and 281K (γ=0.7 x 10(-2)-1.4 x 10(-2)), using the droplet train technique coupled to a mass spectrometer. The mass accommodation coefficient α (derived from γ) was found in the range (1.0-3.0±0.25) x 10(-2). Henry's law constant of acetone was directly measured between 283 and 298K using a dynamic equilibrium system (H((298K))=(29±5)Matm(-1)), with the Van't Hoff expression lnH(T)=(5100±1100)/T-(13.4±3.9). A recommended value of H was suggested according to comparison with literature. The OH-oxidation of acetone in the aqueous phase was carried out at 298K, under two different pH conditions: at pH=2, and under unbuffered conditions. In both cases, the formation of methylglyoxal, formaldehyde, hydroxyacetone, acetic acid/acetate and formic acid/formate was observed. The formation of small amounts of four hydroperoxides was also detected, and one of them was identified as peroxyacetic acid. A drastic effect of pH was observed on the yields of formaldehyde, one hydroperoxide, and, (to a lesser extent) acetic acid/acetate. Based on the experimental observations, a chemical mechanism of OH-oxidation of acetone in the aqueous phase was proposed and discussed. Atmospheric implications of these findings were finally discussed. Copyright © 2010 Elsevier Ltd. All rights reserved.

  18. Student Understanding of Liquid-Vapor Phase Equilibrium

    ERIC Educational Resources Information Center

    Boudreaux, Andrew; Campbell, Craig

    2012-01-01

    Student understanding of the equilibrium coexistence of a liquid and its vapor was the subject of an extended investigation. Written assessment questions were administered to undergraduates enrolled in introductory physics and chemistry courses. Responses have been analyzed to document conceptual and reasoning difficulties in sufficient detail to…

  19. Equilibrium high entropy alloy phase stability from experiments and thermodynamic modeling

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

    Saal, James E.; Berglund, Ida S.; Sebastian, Jason T.

    Long-term stability of high entropy alloys (HEAs) is a critical consideration for the design and practical application of HEAs. It has long been assumed that many HEAs are a kinetically-stabilized metastable structure, and recent experiments have confirmed this hypothesis by observing HEA ecomposition after long-termequilibration. In the presentwork,we demonstrate the use of the CALculation of PHAse Diagrams (CALPHAD) approach to predict HEA stability and processing parameters, comparing experimental long-term annealing observations to CALPHAD phase diagrams from a commercially-available HEA database. As a result, we find good agreement between single- and multi-phase predictions and experiments.

  20. Equilibrium high entropy alloy phase stability from experiments and thermodynamic modeling

    DOE PAGES

    Saal, James E.; Berglund, Ida S.; Sebastian, Jason T.; ...

    2017-10-29

    Long-term stability of high entropy alloys (HEAs) is a critical consideration for the design and practical application of HEAs. It has long been assumed that many HEAs are a kinetically-stabilized metastable structure, and recent experiments have confirmed this hypothesis by observing HEA ecomposition after long-termequilibration. In the presentwork,we demonstrate the use of the CALculation of PHAse Diagrams (CALPHAD) approach to predict HEA stability and processing parameters, comparing experimental long-term annealing observations to CALPHAD phase diagrams from a commercially-available HEA database. As a result, we find good agreement between single- and multi-phase predictions and experiments.

  1. Toward a Multi-scale Phase Transition Kinetics Methodology: From Non-Equilibrium Statistical Mechanics to Hydrodynamics

    NASA Astrophysics Data System (ADS)

    Belof, Jonathan; Orlikowski, Daniel; Wu, Christine; McLaughlin, Keith

    2013-06-01

    Shock and ramp compression experiments are allowing us to probe condensed matter under extreme conditions where phase transitions and other non-equilibrium aspects can now be directly observed, but first principles simulation of kinetics remains a challenge. A multi-scale approach is presented here, with non-equilibrium statistical mechanical quantities calculated by molecular dynamics (MD) and then leveraged to inform a classical nucleation and growth kinetics model at the hydrodynamic scale. Of central interest is the free energy barrier for the formation of a critical nucleus, with direct NEMD presenting the challenge of relatively long timescales necessary to resolve nucleation. Rather than attempt to resolve the time-dependent nucleation sequence directly, the methodology derived here is built upon the non-equilibrium work theorem in order to bias the formation of a critical nucleus and thus construct the nucleation and growth rates. Having determined these kinetic terms from MD, a hydrodynamics implementation of Kolmogorov-Johnson-Mehl-Avrami (KJMA) kinetics and metastabilty is applied to the dynamic compressive freezing of water and compared with recent ramp compression experiments [Dolan et al., Nature (2007)] Lawrence Livermore National Laboratory is operated by Lawrence Livermore National Security, LLC, for the U.S. Department of Energy, National Nuclear Security Administration under Contract DE-AC52-07NA27344.

  2. The temporal evolution of magnesium isotope fractionation during hydromagnesite dissolution, precipitation, and at equilibrium

    NASA Astrophysics Data System (ADS)

    Oelkers, Eric H.; Berninger, Ulf-Niklas; Pérez-Fernàndez, Andrea; Chmeleff, Jérôme; Mavromatis, Vasileios

    2018-04-01

    This study provides experimental evidence of the resetting of the magnesium (Mg) isotope signatures of hydromagnesite in the presence of an aqueous fluid during its congruent dissolution, precipitation, and at equilibrium at ambient temperatures over month-long timescales. All experiments were performed in batch reactors in aqueous sodium carbonate buffer solutions having a pH from 7.8 to 9.2. The fluid phase in all experiments attained bulk chemical equilibrium within analytical uncertainty with hydromagnesite within several days, but the experiments were allowed to continue for up to 575 days. During congruent hydromagnesite dissolution, the fluid first became enriched in isotopically light Mg compared to the dissolving hydromagnesite, but this Mg isotope composition became heavier after the fluid attained chemical equilibrium with the mineral. The δ26Mg composition of the fluid was up to ∼0.35‰ heavier than the initial dissolving hydromagnesite at the end of the dissolution experiments. Hydromagnesite precipitation was provoked during one experiment by increasing the reaction temperature from 4 to 50 °C. The δ26Mg composition of the fluid increased as hydromagnesite precipitated and continued to increase after the fluid attained bulk equilibrium with this phase. These observations are consistent with the hypothesis that mineral-fluid equilibrium is dynamic (i.e. dissolution and precipitation occur at equal, non-zero rates at equilibrium). Moreover the results presented in this study confirm (1) that the transfer of material from the solid to the fluid phase may not be conservative during stoichiometric dissolution, and (2) that the isotopic compositions of carbonate minerals can evolve even when the mineral is in bulk chemical equilibrium with its coexisting fluid. This latter observation suggests that the preservation of isotopic signatures of carbonate minerals in the geological record may require a combination of the isolation of fluid-mineral system

  3. Experimental Determination of Dynamical Lee-Yang Zeros

    NASA Astrophysics Data System (ADS)

    Brandner, Kay; Maisi, Ville F.; Pekola, Jukka P.; Garrahan, Juan P.; Flindt, Christian

    2017-05-01

    Statistical physics provides the concepts and methods to explain the phase behavior of interacting many-body systems. Investigations of Lee-Yang zeros—complex singularities of the free energy in systems of finite size—have led to a unified understanding of equilibrium phase transitions. The ideas of Lee and Yang, however, are not restricted to equilibrium phenomena. Recently, Lee-Yang zeros have been used to characterize nonequilibrium processes such as dynamical phase transitions in quantum systems after a quench or dynamic order-disorder transitions in glasses. Here, we experimentally realize a scheme for determining Lee-Yang zeros in such nonequilibrium settings. We extract the dynamical Lee-Yang zeros of a stochastic process involving Andreev tunneling between a normal-state island and two superconducting leads from measurements of the dynamical activity along a trajectory. From the short-time behavior of the Lee-Yang zeros, we predict the large-deviation statistics of the activity which is typically difficult to measure. Our method paves the way for further experiments on the statistical mechanics of many-body systems out of equilibrium.

  4. Physical principles of intracellular organization via active and passive phase transitions

    NASA Astrophysics Data System (ADS)

    Berry, Joel; Brangwynne, Clifford P.; Haataja, Mikko

    2018-04-01

    Exciting recent developments suggest that phase transitions represent an important and ubiquitous mechanism underlying intracellular organization. We describe key experimental findings in this area of study, as well as the application of classical theoretical approaches for quantitatively understanding these data. We also discuss the way in which equilibrium thermodynamic driving forces may interface with the fundamentally out-of-equilibrium nature of living cells. In particular, time and/or space-dependent concentration profiles may modulate the phase behavior of biomolecules in living cells. We suggest future directions for both theoretical and experimental work that will shed light on the way in which biological activity modulates the assembly, properties, and function of viscoelastic states of living matter.

  5. Physical principles of intracellular organization via active and passive phase transitions.

    PubMed

    Berry, Joel; Brangwynne, Clifford P; Haataja, Mikko

    2018-04-01

    Exciting recent developments suggest that phase transitions represent an important and ubiquitous mechanism underlying intracellular organization. We describe key experimental findings in this area of study, as well as the application of classical theoretical approaches for quantitatively understanding these data. We also discuss the way in which equilibrium thermodynamic driving forces may interface with the fundamentally out-of-equilibrium nature of living cells. In particular, time and/or space-dependent concentration profiles may modulate the phase behavior of biomolecules in living cells. We suggest future directions for both theoretical and experimental work that will shed light on the way in which biological activity modulates the assembly, properties, and function of viscoelastic states of living matter.

  6. Experimental demonstration of cheap and accurate phase estimation

    NASA Astrophysics Data System (ADS)

    Rudinger, Kenneth; Kimmel, Shelby; Lobser, Daniel; Maunz, Peter

    We demonstrate experimental implementation of robust phase estimation (RPE) to learn the phases of X and Y rotations on a trapped Yb+ ion qubit.. Unlike many other phase estimation protocols, RPE does not require ancillae nor near-perfect state preparation and measurement operations. Additionally, its computational requirements are minimal. Via RPE, using only 352 experimental samples per phase, we estimate phases of implemented gates with errors as small as 10-4 radians, as validated using gate set tomography. We also demonstrate that these estimates exhibit Heisenberg scaling in accuracy. Sandia National Laboratories is a multi-program laboratory managed and operated by Sandia Corporation, a wholly owned subsidiary of Lockheed Martin Corporation, for the U.S. Department of Energy's National Nuclear Security Administration under contract DE-AC04-94AL85000.

  7. Entropic Description of Gas Hydrate Ice-Liquid Equilibrium via Enhanced Sampling of Coexisting Phases

    NASA Astrophysics Data System (ADS)

    Małolepsza, Edyta; Kim, Jaegil; Keyes, Tom

    2015-05-01

    Metastable β ice holds small guest molecules in stable gas hydrates, so its solid-liquid equilibrium is of interest. However, aqueous crystal-liquid transitions are very difficult to simulate. A new molecular dynamics algorithm generates trajectories in a generalized N P T ensemble and equilibrates states of coexisting phases with a selectable enthalpy. With replicas spanning the range between β ice and liquid water, we find the statistical temperature from the enthalpy histograms and characterize the transition by the entropy, introducing a general computational procedure for first-order transitions.

  8. Equilibrium and out-of-equilibrium mechanics of living mammalian cytoplasm

    NASA Astrophysics Data System (ADS)

    Gupta, Satish Kumar; Guo, Ming

    2017-10-01

    Living cells are intrinsically non-equilibrium systems. They are driven out of equilibrium by the activity of the molecular motors and other enzymatic processes. This activity along with the ever present thermal agitation results in intracellular fluctuations inside the cytoplasm. In analogy to Brownian motion, the material property of the cytoplasm also influences the characteristics of these fluctuations. In this paper, through a combination of experimentation and theoretical analysis, we show that intracellular fluctuations are indeed due to non-thermal forces at relatively long time-scales, however, are dominated solely by thermal forces at relatively short time-scales. Thus, the cytoplasm of living mammalian cells behaves as an equilibrium material at short time-scales. The mean square displacement of these intracellular fluctuations scales inversely with the cytoplasmic shear modulus in this short time-scale equilibrium regime, and is inversely proportional to the square of the cytoplasmic shear modulus in the long time-scale out-of-equilibrium regime. Furthermore, we deploy passive microrheology based on these fluctuations to extract the mechanical property of the cytoplasm at the high-frequency regime. We show that the cytoplasm of living mammalian cells is a weak elastic gel in this regime; this is in an excellent agreement with an independent micromechanical measurement using optical tweezers.

  9. Non-equilibrium dynamics of artificial quantum matter

    NASA Astrophysics Data System (ADS)

    Babadi, Mehrtash

    The rapid progress of the field of ultracold atoms during the past two decades has set new milestones in our control over matter. By cooling dilute atomic gases and molecules to nano-Kelvin temperatures, novel quantum mechanical states of matter can be realized and studied on a table-top experimental setup while bulk matter can be tailored to faithfully simulate abstract theoretical models. Two of such models which have witnessed significant experimental and theoretical attention are (1) the two-component Fermi gas with resonant s-wave interactions, and (2) the single-component Fermi gas with dipole-dipole interactions. This thesis is devoted to studying the non-equilibrium collective dynamics of these systems using the general framework of quantum kinetic theory. We present a concise review of the utilized mathematical methods in the first two chapters, including the Schwinger-Keldysh formalism of non-equilibrium quantum fields, two-particle irreducible (2PI) effective actions and the framework of quantum kinetic theory. We study the collective dynamics of the dipolar Fermi gas in a quasi-two-dimensional optical trap in chapter 3 and provide a detailed account of its dynamical crossover from the collisionless to the hydrodynamical regime. Chapter 4 is devoted to studying the dynamics of the attractive Fermi gas in the normal phase. Starting from the self-consistent T-matrix (pairing fluctuation) approximation, we systematically derive a set of quantum kinetic equations and show that they provide a globally valid description of the dynamics of the attractive Fermi gas, ranging from the weak-coupling Fermi liquid phase to the intermediate non-Fermi liquid pairing pseudogap regime and finally the strong-coupling Bose liquid phase. The shortcomings of the self-consistent T-matrix approximation in two spatial dimensions are discussed along with a proposal to overcome its unphysical behaviors. The developed kinetic formalism is finally utilized to reproduce and

  10. Intermittent Fermi-Pasta-Ulam Dynamics at Equilibrium

    NASA Astrophysics Data System (ADS)

    Campbell, David; Danieli, Carlo; Flach, Sergej

    The equilibrium value of an observable defines a manifold in the phase space of an ergodic and equipartitioned many-body syste. A typical trajectory pierces that manifold infinitely often as time goes to infinity. We use these piercings to measure both the relaxation time of the lowest frequency eigenmode of the Fermi-Pasta-Ulam chain, as well as the fluctuations of the subsequent dynamics in equilibrium. We show that previously obtained scaling laws for equipartition times are modified at low energy density due to an unexpected slowing down of the relaxation. The dynamics in equilibrium is characterized by a power-law distribution of excursion times far off equilibrium, with diverging variance. The long excursions arise from sticky dynamics close to regular orbits in the phase space. Our method is generalizable to large classes of many-body systems. The authors acknowledge financial support from IBS (Project Code IBS-R024-D1).

  11. Non-equilibrium diffusion combustion of a fuel droplet

    NASA Astrophysics Data System (ADS)

    Tyurenkova, Veronika V.

    2012-06-01

    A mathematical model for the non-equilibrium combustion of droplets in rocket engines is developed. This model allows to determine the divergence of combustion rate for the equilibrium and non-equilibrium model. Criterion for droplet combustion deviation from equilibrium is introduced. It grows decreasing droplet radius, accommodation coefficient, temperature and decreases on decreasing diffusion coefficient. Also divergence from equilibrium increases on reduction of droplet radius. Droplet burning time essentially increases under non-equilibrium conditions. Comparison of theoretical and experimental data shows that to have adequate solution for small droplets it is necessary to use the non-equilibrium model.

  12. Dynamical quantum phase transitions: a review

    NASA Astrophysics Data System (ADS)

    Heyl, Markus

    2018-05-01

    Quantum theory provides an extensive framework for the description of the equilibrium properties of quantum matter. Yet experiments in quantum simulators have now opened up a route towards the generation of quantum states beyond this equilibrium paradigm. While these states promise to show properties not constrained by equilibrium principles, such as the equal a priori probability of the microcanonical ensemble, identifying the general properties of nonequilibrium quantum dynamics remains a major challenge, especially in view of the lack of conventional concepts such as free energies. The theory of dynamical quantum phase transitions attempts to identify such general principles by lifting the concept of phase transitions to coherent quantum real-time evolution. This review provides a pedagogical introduction to this field. Starting from the general setting of nonequilibrium dynamics in closed quantum many-body systems, we give the definition of dynamical quantum phase transitions as phase transitions in time with physical quantities becoming nonanalytic at critical times. We summarize the achieved theoretical advances as well as the first experimental observations, and furthermore provide an outlook to major open questions as well as future directions of research.

  13. Dynamical quantum phase transitions: a review.

    PubMed

    Heyl, Markus

    2018-05-01

    Quantum theory provides an extensive framework for the description of the equilibrium properties of quantum matter. Yet experiments in quantum simulators have now opened up a route towards the generation of quantum states beyond this equilibrium paradigm. While these states promise to show properties not constrained by equilibrium principles, such as the equal a priori probability of the microcanonical ensemble, identifying the general properties of nonequilibrium quantum dynamics remains a major challenge, especially in view of the lack of conventional concepts such as free energies. The theory of dynamical quantum phase transitions attempts to identify such general principles by lifting the concept of phase transitions to coherent quantum real-time evolution. This review provides a pedagogical introduction to this field. Starting from the general setting of nonequilibrium dynamics in closed quantum many-body systems, we give the definition of dynamical quantum phase transitions as phase transitions in time with physical quantities becoming nonanalytic at critical times. We summarize the achieved theoretical advances as well as the first experimental observations, and furthermore provide an outlook to major open questions as well as future directions of research.

  14. Experimental Demonstration of a Cheap and Accurate Phase Estimation

    DOE PAGES

    Rudinger, Kenneth; Kimmel, Shelby; Lobser, Daniel; ...

    2017-05-11

    We demonstrate an experimental implementation of robust phase estimation (RPE) to learn the phase of a single-qubit rotation on a trapped Yb + ion qubit. Here, we show this phase can be estimated with an uncertainty below 4 × 10 -4 rad using as few as 176 total experimental samples, and our estimates exhibit Heisenberg scaling. Unlike standard phase estimation protocols, RPE neither assumes perfect state preparation and measurement, nor requires access to ancillae. We crossvalidate the results of RPE with the more resource-intensive protocol of gate set tomography.

  15. Equation of state and phase diagram of carbon

    NASA Astrophysics Data System (ADS)

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

    1996-05-01

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

  16. Equilibrium expert: an add-in to Microsoft Excel for multiple binding equilibrium simulations and parameter estimations.

    PubMed

    Raguin, Olivier; Gruaz-Guyon, Anne; Barbet, Jacques

    2002-11-01

    An add-in to Microsoft Excel was developed to simulate multiple binding equilibriums. A partition function, readily written even when the equilibrium is complex, describes the experimental system. It involves the concentrations of the different free molecular species and of the different complexes present in the experiment. As a result, the software is not restricted to a series of predefined experimental setups but can handle a large variety of problems involving up to nine independent molecular species. Binding parameters are estimated by nonlinear least-square fitting of experimental measurements as supplied by the user. The fitting process allows user-defined weighting of the experimental data. The flexibility of the software and the way it may be used to describe common experimental situations and to deal with usual problems such as tracer reactivity or nonspecific binding is demonstrated by a few examples. The software is available free of charge upon request.

  17. Effects of Al2O3 and CaO/SiO2 Ratio on Phase Equilbria in the ZnO-"FeO"-Al2O3-CaO-SiO2 System in Equilibrium with Metallic Iron

    NASA Astrophysics Data System (ADS)

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

    2011-02-01

    The phase equilibria and liquidus temperatures in the ZnO-"FeO"-Al2O3-CaO-SiO2 system in equilibrium with metallic iron have been determined experimentally in the temperature range 1383 K to 1573 K (1150 °C to 1300 °C). The experimental conditions were selected to characterize lead blast furnace and imperial smelting furnace slags. The results are presented in a form of pseudoternary sections ZnO-"FeO"-(Al2O3 + CaO + SiO2) with fixed CaO/SiO2 and (CaO + SiO2)/Al2O3 ratios. It was found that wustite and spinel are the major primary phases in the composition range investigated. Effects of Al2O3 concentration as well as the CaO/SiO2 ratio on the primary phase field, the liquidus temperature, and the partitioning of ZnO between liquid and solid phases have been discussed for zinc-containing slags.

  18. Floquet Symmetry-Protected Topological Phases in Cold-Atom Systems

    NASA Astrophysics Data System (ADS)

    Potirniche, I.-D.; Potter, A. C.; Schleier-Smith, M.; Vishwanath, A.; Yao, N. Y.

    2017-09-01

    We propose and analyze two distinct routes toward realizing interacting symmetry-protected topological (SPT) phases via periodic driving. First, we demonstrate that a driven transverse-field Ising model can be used to engineer complex interactions which enable the emulation of an equilibrium SPT phase. This phase remains stable only within a parametric time scale controlled by the driving frequency, beyond which its topological features break down. To overcome this issue, we consider an alternate route based upon realizing an intrinsically Floquet SPT phase that does not have any equilibrium analog. In both cases, we show that disorder, leading to many-body localization, prevents runaway heating and enables the observation of coherent quantum dynamics at high energy densities. Furthermore, we clarify the distinction between the equilibrium and Floquet SPT phases by identifying a unique micromotion-based entanglement spectrum signature of the latter. Finally, we propose a unifying implementation in a one-dimensional chain of Rydberg-dressed atoms and show that protected edge modes are observable on realistic experimental time scales.

  19. Multiphase, multicomponent phase behavior prediction

    NASA Astrophysics Data System (ADS)

    Dadmohammadi, Younas

    Accurate prediction of phase behavior of fluid mixtures in the chemical industry is essential for designing and operating a multitude of processes. Reliable generalized predictions of phase equilibrium properties, such as pressure, temperature, and phase compositions offer an attractive alternative to costly and time consuming experimental measurements. The main purpose of this work was to assess the efficacy of recently generalized activity coefficient models based on binary experimental data to (a) predict binary and ternary vapor-liquid equilibrium systems, and (b) characterize liquid-liquid equilibrium systems. These studies were completed using a diverse binary VLE database consisting of 916 binary and 86 ternary systems involving 140 compounds belonging to 31 chemical classes. Specifically the following tasks were undertaken: First, a comprehensive assessment of the two common approaches (gamma-phi (gamma-ϕ) and phi-phi (ϕ-ϕ)) used for determining the phase behavior of vapor-liquid equilibrium systems is presented. Both the representation and predictive capabilities of these two approaches were examined, as delineated form internal and external consistency tests of 916 binary systems. For the purpose, the universal quasi-chemical (UNIQUAC) model and the Peng-Robinson (PR) equation of state (EOS) were used in this assessment. Second, the efficacy of recently developed generalized UNIQUAC and the nonrandom two-liquid (NRTL) for predicting multicomponent VLE systems were investigated. Third, the abilities of recently modified NRTL model (mNRTL2 and mNRTL1) to characterize liquid-liquid equilibria (LLE) phase conditions and attributes, including phase stability, miscibility, and consolute point coordinates, were assessed. The results of this work indicate that the ϕ-ϕ approach represents the binary VLE systems considered within three times the error of the gamma-ϕ approach. A similar trend was observed for the for the generalized model predictions using

  20. Modelling of phase transformations occurring in low activation martensitic steels

    NASA Astrophysics Data System (ADS)

    Brachet, J.-C.; Gavard, L.; Boussidan, C.; Lepoittevin, C.; Denis, S.; Servant, C.

    1998-10-01

    The main objective of this paper is to summarize modelling of on-heating and on-cooling phase transformations occurring in Low Activation Martensitic (LAM) steels. Calculations of thermodynamic equilibrium phase fractions and kinetic aspects of phase transformations have been performed by using different approaches from experimental data (CCT and TTT diagrams obtained by dilatometry). All the calculated data have been compared to an important and systematic set of experimental data obtained on different LAM steels of the 7.5-11% CrWVT a type.

  1. Investigation of island formation due to RMPs in DIII-D plasmas with the SIESTA resistive MHD equilibrium code

    NASA Astrophysics Data System (ADS)

    Hirshman, S. P.; Shafer, M. W.; Seal, S. K.; Canik, J. M.

    2016-04-01

    > The SIESTA magnetohydrodynamic (MHD) equilibrium code has been used to compute a sequence of ideally stable equilibria resulting from numerical variation of the helical resonant magnetic perturbation (RMP) applied to an axisymmetric DIII-D plasma equilibrium. Increasing the perturbation strength at the dominant , resonant surface leads to lower MHD energies and increases in the equilibrium island widths at the (and sidebands) surfaces, in agreement with theoretical expectations. Island overlap at large perturbation strengths leads to stochastic magnetic fields which correlate well with the experimentally inferred field structure. The magnitude and spatial phase (around the dominant rational surfaces) of the resonant (shielding) component of the parallel current are shown to change qualitatively with the magnetic island topology.

  2. A "User-Friendly" Program for Vapor-Liquid Equilibrium.

    ERIC Educational Resources Information Center

    Da Silva, Francisco A.; And Others

    1991-01-01

    Described is a computer software package suitable for teaching and research in the area of multicomponent vapor-liquid equilibrium. This program, which has a complete database, can accomplish phase-equilibrium calculations using various models and graph the results. (KR)

  3. Use of the augmented Young-Laplace equation to model equilibrium and evaporating extended menisci

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

    DasGupta, S.; Schonberg, J.A.; Kim, I.Y.

    1993-05-01

    The generic importance of fluid flow and change-of-phase heat transfer in the contact line region of an extended meniscus has led to theoretical and experimental research on the details of these transport processes. Numerical solutions of equilibrium and nonequilibrium models based on the augmented Young-Laplace equation were successfully used to evaluate experimental data for an extended meniscus. The data for the equilibrium and nonequilibrium meniscus profiles were obtained optically using ellipsometry and image processing interferometry. A Taylor series expansion of the fourth-order nonlinear transport model was used to obtain the extremely sensitive initial conditions at the interline. The solid-liquid-vapor Hamakermore » constants for the systems were obtained from the experimental data. The consistency of the data was demonstrated by using the combining rules to calculate the unknown value of the Hamaker constant for the experimental substrate. The sensitivity of the meniscus profile to small changes in the environment was demonstrated. Both temperature and intermolecular forces need to be included in modeling transport processes in the contact line region because the chemical potential is a function of both temperature and pressure.« less

  4. Thermodynamics and Kinetics of Chemical Equilibrium in Solution.

    ERIC Educational Resources Information Center

    Leenson, I. A.

    1986-01-01

    Discusses theory of thermodynamics of the equilibrium in solution and dissociation-dimerization kinetics. Describes experimental procedure including determination of molar absorptivity and equilibrium constant, reaction enthalpy, and kinetics of the dissociation-dimerization reaction. (JM)

  5. Experimental Investigation of the Cd-Pr Phase Diagram

    PubMed Central

    Reichmann, Thomas L.; Effenberger, Herta S.; Ipser, Herbert

    2014-01-01

    The complete Cd-Pr equilibrium phase diagram was investigated with a combination of powder-XRD, SEM and DTA. All intermetallic compounds within this system, already reported in literature, could be confirmed: CdPr, Cd2Pr, Cd3Pr, Cd45Pr11, Cd58Pr13, Cd6Pr and Cd11Pr. The corresponding phase boundaries were determined at distinct temperatures. The homogeneity range of the high-temperature allotropic modification of Pr could be determined precisely and a limited solubility of 22.1 at.% Cd was derived. Additionally, single-crystal X-ray diffraction was employed to investigate structural details of Cd2Pr; it is isotypic to the AlB2-type structure with a z value of the Cd site of 0.5. DTA results of alloys located in the adjacent two-phase fields of Cd2Pr suggested a phase transformation between 893 and 930°C. For the phase Cd3Pr it was found that the lattice parameter a changes linearly with increasing Cd content, following Vegard’s rule. The corresponding defect mechanism could be evaluated from structural data collected with single-crystal XRD. Introduction of a significant amount of vacancies on the Pr site and the reduction in symmetry of one Cd position (8c to 32f) resulted in a noticeable decrease of all R-values. PMID:24718502

  6. Dynamical Quasicondensation of Hard-Core Bosons at Finite Momenta: A Non-equilibrium Condensation Effect

    NASA Astrophysics Data System (ADS)

    Heidrich-Meisner, Fabian; Vidmar, L.; Ronzheimer, J. P.; Hodgman, S.; Schreiber, M.; Braun, S.; Langer, S.; Bloch, I.; Schneider, U.

    2016-05-01

    Long-range order in quantum many-body systems is usually associated with equilibrium situations. Here, we experimentally investigate the quasicondensation of strongly interacting bosons at finite momenta in a far-from-equilibrium case. We prepare an inhomogeneous initial state consisting of one-dimensional Mott insulators in the center of otherwise empty one-dimensional chains in an optical lattice with a lattice constant d. After suddenly quenching the trapping potential to zero, we observe the onset of coherence in spontaneously forming quasicondensates in the lattice. Remarkably, the emerging phase order differs from the ground-state order and is characterized by peaks at finite momenta +/-(π / 2)(ℏ / d) in the momentum distribution function. Supported by the DFG via FOR 801.

  7. Phase transformation pathways of Ln2O3 irradiated by ultrafast laser

    NASA Astrophysics Data System (ADS)

    Rittman, Dylan; Solomon, Jonathan; Chen, Curtis; Tracy, Cameron; Yalisove, Steven; Asta, Mark; Mao, Wendy; Ewing, Rodney

    Ultrafast laser irradiation induces highly non-equilibrium conditions in materials through intense electronic excitation over very short timescales. Here, we show that ultrafast laser irradiation drives an irreversible cubic-to-monoclinic phase transformation in Ln2O3 (Ln = Er-Lu). A combination of grazing incidence X-ray diffraction and transmission electron microscopy is used to characterize the amount and depth-dependence of the phase transformation. Results indicate that-although all materials experience the same transformation-it is achieved through different damage mechanisms (pressure vs. thermal), and the short timescales associated with damage provides non-equilibrium routes of material modification. Ab initio molecular dynamics are used to isolate the effects of electronic excitations, and results are shown to be consistent with the trend in radiation resistance observed experimentally. Overall, this study provides a path to gain insight into the relationship between a material's equilibrium phase diagram and its behavior under highly non-equilibrium conditions. DOE/BES.

  8. Linear free-energy relationships between a single gas-phase ab initio equilibrium bond length and experimental pKa values in aqueous solution.

    PubMed

    Alkorta, Ibon; Popelier, Paul L A

    2015-02-02

    Remarkably simple yet effective linear free energy relationships were discovered between a single ab initio computed bond length in the gas phase and experimental pKa values in aqueous solution. The formation of these relationships is driven by chemical features such as functional groups, meta/para substitution and tautomerism. The high structural content of the ab initio bond length makes a given data set essentially divide itself into high correlation subsets (HCSs). Surprisingly, all molecules in a given high correlation subset share the same conformation in the gas phase. Here we show that accurate pKa values can be predicted from such HCSs. This is achieved within an accuracy of 0.2 pKa units for 5 drug molecules. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. A two-phase restricted equilibrium model for combustion of metalized solid propellants

    NASA Technical Reports Server (NTRS)

    Sabnis, J. S.; Dejong, F. J.; Gibeling, H. J.

    1992-01-01

    An Eulerian-Lagrangian two-phase approach was adopted to model the multi-phase reacting internal flow in a solid rocket with a metalized propellant. An Eulerian description was used to analyze the motion of the continuous phase which includes the gas as well as the small (micron-sized) particulates, while a Lagrangian description is used for the analysis of the discrete phase which consists of the larger particulates in the motor chamber. The particulates consist of Al and Al2O3 such that the particulate composition is 100 percent Al at injection from the propellant surface with Al2O3 fraction increasing due to combustion along the particle trajectory. An empirical model is used to compute the combustion rate for agglomerates while the continuous phase chemistry is treated using chemical equilibrium. The computer code was used to simulate the reacting flow in a solid rocket motor with an AP/HTPB/Al propellant. The computed results show the existence of an extended combustion zone in the chamber rather than a thin reaction region. The presence of the extended combustion zone results in the chamber flow field and chemical being far from isothermal (as would be predicted by a surface combustion assumption). The temperature in the chamber increases from about 2600 K at the propellant surface to about 3350 K in the core. Similarly the chemical composition and the density of the propellant gas also show spatially non-uniform distribution in the chamber. The analysis developed under the present effort provides a more sophisticated tool for solid rocket internal flow predictions than is presently available, and can be useful in studying apparent anomalies and improving the simple correlations currently in use. The code can be used in the analysis of combustion efficiency, thermal load in the internal insulation, plume radiation, etc.

  10. Non-equilibrium flow and sediment transport distribution over mobile river dunes

    NASA Astrophysics Data System (ADS)

    Hoitink, T.; Naqshband, S.; McElroy, B. J.

    2017-12-01

    Flow and sediment transport are key processes in the morphodynamics of river dunes. During floods in several rivers (e.g., the Elkhorn, Missouri, Niobrara, and Rio Grande), dunes are observed to grow rapidly as flow strength increases, undergoing an unstable transition regime, after which they are washed out in what is called upper stage plane bed. This morphological evolution of dunes to upper stage plane bed is the strongest bed-form adjustment during non-equilibrium flows and is associated with a significant change in hydraulic roughness and water levels. Detailed experimental investigations, however, have mostly focused on fixed dunes limited to equilibrium flow and bed conditions that are rare in natural channels. Our understanding of the underlying sedimentary processes that result into the washing out of dunes is therefore very limited. In the present study, using the Acoustic Concentration and Velocity Profiler (ACVP), we were able to quantify flow structure and sediment transport distribution over mobile non-equilibrium dunes. Under these non-equilibrium flow conditions average dune heights were decreasing while dune lengths were increasing. Preliminary results suggest that this morphological behaviour is due to a positive phase lag between sediment transport maximum and topographic maximum leading to a larger erosion on the dune stoss side compared to deposition on dune lee side.

  11. Experimental evidence for an absorbing phase transition underlying yielding of a soft glass

    NASA Astrophysics Data System (ADS)

    Nagamanasa, K. Hima; Gokhale, Shreyas; Sood, A. K.; Ganapathy, Rajesh

    2014-03-01

    A characteristic feature of solids ranging from foams to atomic crystals is the existence of a yield point, which marks the threshold stress beyond which a material undergoes plastic deformation. In hard materials, it is well-known that local yield events occur collectively in the form of intermittent avalanches. The avalanche size distributions exhibit power-law scaling indicating the presence of self-organized criticality. These observations led to predictions of a non-equilibrium phase transition at the yield point. By contrast, for soft solids like gels and dense suspensions, no such predictions exist. In the present work, by combining particle scale imaging with bulk rheology, we provide a direct evidence for a non-equilibrium phase transition governing yielding of an archetypal soft solid - a colloidal glass. The order parameter and the relaxation time exponents revealed that yielding is an absorbing phase transition that belongs to the conserved directed percolation universality class. We also identified a growing length scale associated with clusters of particles with high Debye-Waller factor. Our findings highlight the importance of correlations between local yield events and may well stimulate the development of a unified description of yielding of soft solids.

  12. Experimental study of phase separation in dividing two phase flow

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

    Qian Yong; Yang Zhilin; Xu Jijun

    1996-12-31

    Experimental study of phase separation of air-water two phase bubbly, slug flow in the horizontal T-junction is carried out. The influences of the inlet mass quality X1, mass extraction rate G3/G1, and fraction of extracted liquid QL3/QL1 on phase separation characteristics are analyzed. For the first time, the authors have found and defined pulsating run effect by the visual experiments, which show that under certain conditions, the down stream flow of the T-junction has strangely affected the phase redistribution of the junction, and firstly point out that the downstream geometric condition is very important to the study of phase separationmore » phenomenon of two-phase flow in a T-junction. This kind of phenomenon has many applications in the field of energy, power, petroleum and chemical industries, such as the loss of coolant accident (LOCA) caused by a small break in a horizontal coolant pipe in nuclear reactor, and the flip-flop effect in the natural gas transportation pipeline system, etc.« less

  13. Phase equilibrium and preparation, crystallization and viscous sintering of glass in the alumina-silica-lanthanum phosphate system

    NASA Astrophysics Data System (ADS)

    He, Feng

    The phase equilibrium, viscosity of melt-quenched glasses, and processing of sol-gel glasses of the alumina-silica-lanthanum phosphate system were studied. These investigations were directed towards serving the objective of synthesizing nano-structured ceramic-matrix-composites via controlled crystallization of glass precursors. The thermal stability, phase equilibrium, and liquidus temperatures of the alumina- and mullite-lanthanum phosphate systems are determined. An iridium wire heater was constructed to anneal samples up to 2200°C. Phosphorus evaporation losses were significant at high temperatures, especially over 1800°C. The tentative phase diagrams of the two quasi-binary systems were presented. The viscosity of the melt-quenched mullite-lanthanum phosphate glasses was measured by three different methods, including viscous sintering of glass powder compacts, neck formation between two Frenkel glass beads, and thermal analysis of the glass transition. Improved methodologies were developed for applying the interpretative mathematical models to the results of the sintered powder and thermal analytical experiments. Good agreement was found between all three methods for both absolute values and temperature dependence. A sol-gel process was developed as a low temperature route to producing glasses. A unique, single phase mullite gel capable of low temperature (575°C) mullitization was made from tetraethoxysilane and aluminum isopropoxide at room temperature in three days. Low temperature crystallization was attributed to the avoidance of phase segregation during gel formation and annealing. This was greatly enhanced by a combination of low temperature preheating in the amorphous state, a high heating rate during crystallization and low water content. The Al2O3 content in mullite (61-68 mol%) depended on the highest annealing temperature. Two mullite-lanthanum phosphate gels were made based upon modifying the chemical procedures used for the homogeneous single

  14. Experimental implementation of phase locking in a nonlinear interferometer

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

    Wang, Hailong; Jing, Jietai, E-mail: jtjing@phy.ecnu.edu.cn; Marino, A. M.

    2015-09-21

    Based upon two cascade four-wave mixing processes in two identical hot rubidium vapor cells, a nonlinear interferometer has been experimentally realized [Jing et al., Appl. Phys. Lett. 99, 011110 (2011); Hudelist et al., Nat. Commun. 5, 3049 (2014)]. It has a higher degree of phase sensitivity than a traditional linear interferometer and has many potential applications in quantum metrology. Phase locking of the nonlinear interferometer is needed before it can find its way into applications. In this letter, we investigate the experimental implementation of phase locking of the relative phase between the three beams at different frequencies involved in suchmore » a nonlinear interferometer. We have utilized two different methods, namely, beat note locking and coherent modulation locking. We find that coherent modulation locking can achieve much better phase stability than beat note locking in our system. Our results pave the way for real applications of a nonlinear interferometer in precision measurement and quantum manipulation, for example, phase control in phase-sensitive N-wave mixing process, N-port nonlinear interferometer and quantum-enhanced real-time phase tracking.« less

  15. Equilibrium gas-oil ratio measurements using a microfluidic technique.

    PubMed

    Fisher, Robert; Shah, Mohammad Khalid; Eskin, Dmitry; Schmidt, Kurt; Singh, Anil; Molla, Shahnawaz; Mostowfi, Farshid

    2013-07-07

    A method for measuring the equilibrium GOR (gas-oil ratio) of reservoir fluids using microfluidic technology is developed. Live crude oils (crude oil with dissolved gas) are injected into a long serpentine microchannel at reservoir pressure. The fluid forms a segmented flow as it travels through the channel. Gas and liquid phases are produced from the exit port of the channel that is maintained at atmospheric conditions. The process is analogous to the production of crude oil from a formation. By using compositional analysis and thermodynamic principles of hydrocarbon fluids, we show excellent equilibrium between the produced gas and liquid phases is achieved. The GOR of a reservoir fluid is a key parameter in determining the equation of state of a crude oil. Equations of state that are commonly used in petroleum engineering and reservoir simulations describe the phase behaviour of a fluid at equilibrium state. Therefore, to accurately determine the coefficients of an equation of state, the produced gas and liquid phases have to be as close to the thermodynamic equilibrium as possible. In the examples presented here, the GORs measured with the microfluidic technique agreed with GOR values obtained from conventional methods. Furthermore, when compared to conventional methods, the microfluidic technique was simpler to perform, required less equipment, and yielded better repeatability.

  16. Equilibrium and non-equilibrium dynamics simultaneously operate in the Galápagos islands.

    PubMed

    Valente, Luis M; Phillimore, Albert B; Etienne, Rampal S

    2015-08-01

    Island biotas emerge from the interplay between colonisation, speciation and extinction and are often the scene of spectacular adaptive radiations. A common assumption is that insular diversity is at a dynamic equilibrium, but for remote islands, such as Hawaii or Galápagos, this idea remains untested. Here, we reconstruct the temporal accumulation of terrestrial bird species of the Galápagos using a novel phylogenetic method that estimates rates of biota assembly for an entire community. We show that species richness on the archipelago is in an ascending phase and does not tend towards equilibrium. The majority of the avifauna diversifies at a slow rate, without detectable ecological limits. However, Darwin's finches form an exception: they rapidly reach a carrying capacity and subsequently follow a coalescent-like diversification process. Together, these results suggest that avian diversity of remote islands is rising, and challenge the mutual exclusivity of the non-equilibrium and equilibrium ecological paradigms. © 2015 The Authors Ecology Letters published by John Wiley & Sons Ltd and CNRS.

  17. How should we understand non-equilibrium many-body steady states?

    NASA Astrophysics Data System (ADS)

    Maghrebi, Mohammad; Gorshkov, Alexey

    : Many-body systems with both coherent dynamics and dissipation constitute a rich class of models which are nevertheless much less explored than their dissipationless counterparts. The advent of numerous experimental platforms that simulate such dynamics poses an immediate challenge to systematically understand and classify these models. In particular, nontrivial many-body states emerge as steady states under non-equilibrium dynamics. In this talk, I use a field-theoretic approach based on the Keldysh formalism to study nonequilibrium phases and phase transitions in such models. I show that an effective temperature generically emerges as a result of dissipation, and the universal behavior including the dynamics near the steady state is described by a thermodynamic universality class. In the end, I will also discuss possibilities that go beyond the paradigm of an effective thermodynamic behavior.

  18. Intermittent many-body dynamics at equilibrium

    NASA Astrophysics Data System (ADS)

    Danieli, C.; Campbell, D. K.; Flach, S.

    2017-06-01

    The equilibrium value of an observable defines a manifold in the phase space of an ergodic and equipartitioned many-body system. A typical trajectory pierces that manifold infinitely often as time goes to infinity. We use these piercings to measure both the relaxation time of the lowest frequency eigenmode of the Fermi-Pasta-Ulam chain, as well as the fluctuations of the subsequent dynamics in equilibrium. The dynamics in equilibrium is characterized by a power-law distribution of excursion times far off equilibrium, with diverging variance. Long excursions arise from sticky dynamics close to q -breathers localized in normal mode space. Measuring the exponent allows one to predict the transition into nonergodic dynamics. We generalize our method to Klein-Gordon lattices where the sticky dynamics is due to discrete breathers localized in real space.

  19. Interfaces at equilibrium: A guide to fundamentals.

    PubMed

    Marmur, Abraham

    2017-06-01

    The fundamentals of the thermodynamics of interfaces are reviewed and concisely presented. The discussion starts with a short review of the elements of bulk thermodynamics that are also relevant to interfaces. It continues with the interfacial thermodynamics of two-phase systems, including the definition of interfacial tension and adsorption. Finally, the interfacial thermodynamics of three-phase (wetting) systems is discussed, including the topic of non-wettable surfaces. A clear distinction is made between equilibrium conditions, in terms of minimizing energies (internal, Gibbs or Helmholtz), and equilibrium indicators, in terms of measurable, intrinsic properties (temperature, chemical potential, pressure). It is emphasized that the equilibrium indicators are the same whatever energy is minimized, if the boundary conditions are properly chosen. Also, to avoid a common confusion, a distinction is made between systems of constant volume and systems with drops of constant volume. Copyright © 2016 Elsevier B.V. All rights reserved.

  20. Absolute Equilibrium Entropy

    NASA Technical Reports Server (NTRS)

    Shebalin, John V.

    1997-01-01

    The entropy associated with absolute equilibrium ensemble theories of ideal, homogeneous, fluid and magneto-fluid turbulence is discussed and the three-dimensional fluid case is examined in detail. A sigma-function is defined, whose minimum value with respect to global parameters is the entropy. A comparison is made between the use of global functions sigma and phase functions H (associated with the development of various H-theorems of ideal turbulence). It is shown that the two approaches are complimentary though conceptually different: H-theorems show that an isolated system tends to equilibrium while sigma-functions allow the demonstration that entropy never decreases when two previously isolated systems are combined. This provides a more complete picture of entropy in the statistical mechanics of ideal fluids.

  1. Equilibrium polymerization models of re-entrant self-assembly

    NASA Astrophysics Data System (ADS)

    Dudowicz, Jacek; Douglas, Jack F.; Freed, Karl F.

    2009-04-01

    As is well known, liquid-liquid phase separation can occur either upon heating or cooling, corresponding to lower and upper critical solution phase boundaries, respectively. Likewise, self-assembly transitions from a monomeric state to an organized polymeric state can proceed either upon increasing or decreasing temperature, and the concentration dependent ordering temperature is correspondingly called the "floor" or "ceiling" temperature. Motivated by the fact that some phase separating systems exhibit closed loop phase boundaries with two critical points, the present paper analyzes self-assembly analogs of re-entrant phase separation, i.e., re-entrant self-assembly. In particular, re-entrant self-assembly transitions are demonstrated to arise in thermally activated equilibrium self-assembling systems, when thermal activation is more favorable than chain propagation, and in equilibrium self-assembly near an adsorbing boundary where strong competition exists between adsorption and self-assembly. Apparently, the competition between interactions or equilibria generally underlies re-entrant behavior in both liquid-liquid phase separation and self-assembly transitions.

  2. Investigation of island formation due to RMPs in DIII-D plasmas with the SIESTA resistive MHD equilibrium code

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

    Hirshman, S. P.; Shafer, M. W.; Seal, S. K.

    The SIESTA magnetohydrodynamic (MHD) equilibrium code has been used to compute a sequence of ideally stable equilibria resulting from numerical variation of the helical resonant magnetic perturbation (RMP) applied to an axisymmetric DIII-D plasma equilibrium. Increasing the perturbation strength at the dominant m=2, n=-1 , resonant surface leads to lower MHD energies and increases in the equilibrium island widths at the m=2 (and sidebands) surfaces, in agreement with theoretical expectations. Island overlap at large perturbation strengths leads to stochastic magnetic fields which correlate well with the experimentally inferred field structure. The magnitude and spatial phase (around the dominant rational surfaces)more » of the resonant (shielding) component of the parallel current are shown to change qualitatively with the magnetic island topology.« less

  3. Investigation of island formation due to RMPs in DIII-D plasmas with the SIESTA resistive MHD equilibrium code

    DOE PAGES

    Hirshman, S. P.; Shafer, M. W.; Seal, S. K.; ...

    2016-03-03

    The SIESTA magnetohydrodynamic (MHD) equilibrium code has been used to compute a sequence of ideally stable equilibria resulting from numerical variation of the helical resonant magnetic perturbation (RMP) applied to an axisymmetric DIII-D plasma equilibrium. Increasing the perturbation strength at the dominant m=2, n=-1 , resonant surface leads to lower MHD energies and increases in the equilibrium island widths at the m=2 (and sidebands) surfaces, in agreement with theoretical expectations. Island overlap at large perturbation strengths leads to stochastic magnetic fields which correlate well with the experimentally inferred field structure. The magnitude and spatial phase (around the dominant rational surfaces)more » of the resonant (shielding) component of the parallel current are shown to change qualitatively with the magnetic island topology.« less

  4. Equilibrium econophysics: A unified formalism for neoclassical economics and equilibrium thermodynamics

    NASA Astrophysics Data System (ADS)

    Sousa, Tânia; Domingos, Tiago

    2006-11-01

    We develop a unified conceptual and mathematical structure for equilibrium econophysics, i.e., the use of concepts and tools of equilibrium thermodynamics in neoclassical microeconomics and vice versa. Within this conceptual structure the results obtained in microeconomic theory are: (1) the definition of irreversibility in economic behavior; (2) the clarification that the Engel curve and the offer curve are not descriptions of real processes dictated by the maximization of utility at constant endowment; (3) the derivation of a relation between elasticities proving that economic elasticities are not all independent; (4) the proof that Giffen goods do not exist in a stable equilibrium; (5) the derivation that ‘economic integrability’ is equivalent to the generalized Le Chatelier principle and (6) the definition of a first order phase transition, i.e., a transition between separate points in the utility function. In thermodynamics the results obtained are: (1) a relation between the non-dimensional isothermal and adiabatic compressibilities and the increase or decrease in the thermodynamic potentials; (2) the distinction between mathematical integrability and optimization behavior and (3) the generalization of the Clapeyron equation.

  5. Accelerating Multiagent Reinforcement Learning by Equilibrium Transfer.

    PubMed

    Hu, Yujing; Gao, Yang; An, Bo

    2015-07-01

    An important approach in multiagent reinforcement learning (MARL) is equilibrium-based MARL, which adopts equilibrium solution concepts in game theory and requires agents to play equilibrium strategies at each state. However, most existing equilibrium-based MARL algorithms cannot scale due to a large number of computationally expensive equilibrium computations (e.g., computing Nash equilibria is PPAD-hard) during learning. For the first time, this paper finds that during the learning process of equilibrium-based MARL, the one-shot games corresponding to each state's successive visits often have the same or similar equilibria (for some states more than 90% of games corresponding to successive visits have similar equilibria). Inspired by this observation, this paper proposes to use equilibrium transfer to accelerate equilibrium-based MARL. The key idea of equilibrium transfer is to reuse previously computed equilibria when each agent has a small incentive to deviate. By introducing transfer loss and transfer condition, a novel framework called equilibrium transfer-based MARL is proposed. We prove that although equilibrium transfer brings transfer loss, equilibrium-based MARL algorithms can still converge to an equilibrium policy under certain assumptions. Experimental results in widely used benchmarks (e.g., grid world game, soccer game, and wall game) show that the proposed framework: 1) not only significantly accelerates equilibrium-based MARL (up to 96.7% reduction in learning time), but also achieves higher average rewards than algorithms without equilibrium transfer and 2) scales significantly better than algorithms without equilibrium transfer when the state/action space grows and the number of agents increases.

  6. Two-phase vesicles: a study on evolutionary and stationary models.

    PubMed

    Sahebifard, MohammadMahdi; Shahidi, Alireza; Ziaei-Rad, Saeed

    2017-05-01

    In the current article, the dynamic evolution of two-phase vesicles is presented as an extension to a previous stationary model and based on an equilibrium of local forces. In the simplified model, ignoring the effects of membrane inertia, a dynamic equilibrium between the membrane bending potential and local fluid friction is considered in each phase. The equilibrium equations at the domain borders are completed by extended introduction of membrane section reactions. We show that in some cases, the results of stationary and evolutionary models are in agreement with each other and also with experimental observations, while in others the two models differ markedly. The value of our approach is that we can account for unresponsive points of uncertainty using our equations with the local velocity of the lipid membranes and calculating the intermediate states (shapes) in the consequent evolutionary, or response, path.

  7. Influence of arc current and pressure on non-chemical equilibrium air arc behavior

    NASA Astrophysics Data System (ADS)

    Yi, WU; Yufei, CUI; Jiawei, DUAN; Hao, SUN; Chunlin, WANG; Chunping, NIU

    2018-01-01

    The influence of arc current and pressure on the non-chemical equilibrium (non-CE) air arc behavior of a nozzle structure was investigated based on the self-consistent non-chemical equilibrium model. The arc behavior during both the arc burning and arc decay phases were discussed at different currents and different pressures. We also devised the concept of a non-equilibrium parameter for a better understanding of non-CE effects. During the arc burning phase, the increasing current leads to a decrease of the non-equilibrium parameter of the particles in the arc core, while the increasing pressure leads to an increase of the non-equilibrium parameter of the particles in the arc core. During the arc decay phase, the non-CE effect will decrease by increasing the arc burning current and the nozzle pressure. Three factors together—convection, diffusion and chemical reactions—influence non-CE behavior.

  8. Information-theoretic equilibrium and observable thermalization

    NASA Astrophysics Data System (ADS)

    Anzà, F.; Vedral, V.

    2017-03-01

    A crucial point in statistical mechanics is the definition of the notion of thermal equilibrium, which can be given as the state that maximises the von Neumann entropy, under the validity of some constraints. Arguing that such a notion can never be experimentally probed, in this paper we propose a new notion of thermal equilibrium, focused on observables rather than on the full state of the quantum system. We characterise such notion of thermal equilibrium for an arbitrary observable via the maximisation of its Shannon entropy and we bring to light the thermal properties that it heralds. The relation with Gibbs ensembles is studied and understood. We apply such a notion of equilibrium to a closed quantum system and show that there is always a class of observables which exhibits thermal equilibrium properties and we give a recipe to explicitly construct them. Eventually, an intimate connection with the Eigenstate Thermalisation Hypothesis is brought to light.

  9. Information-theoretic equilibrium and observable thermalization

    PubMed Central

    Anzà, F.; Vedral, V.

    2017-01-01

    A crucial point in statistical mechanics is the definition of the notion of thermal equilibrium, which can be given as the state that maximises the von Neumann entropy, under the validity of some constraints. Arguing that such a notion can never be experimentally probed, in this paper we propose a new notion of thermal equilibrium, focused on observables rather than on the full state of the quantum system. We characterise such notion of thermal equilibrium for an arbitrary observable via the maximisation of its Shannon entropy and we bring to light the thermal properties that it heralds. The relation with Gibbs ensembles is studied and understood. We apply such a notion of equilibrium to a closed quantum system and show that there is always a class of observables which exhibits thermal equilibrium properties and we give a recipe to explicitly construct them. Eventually, an intimate connection with the Eigenstate Thermalisation Hypothesis is brought to light. PMID:28266646

  10. Information-theoretic equilibrium and observable thermalization.

    PubMed

    Anzà, F; Vedral, V

    2017-03-07

    A crucial point in statistical mechanics is the definition of the notion of thermal equilibrium, which can be given as the state that maximises the von Neumann entropy, under the validity of some constraints. Arguing that such a notion can never be experimentally probed, in this paper we propose a new notion of thermal equilibrium, focused on observables rather than on the full state of the quantum system. We characterise such notion of thermal equilibrium for an arbitrary observable via the maximisation of its Shannon entropy and we bring to light the thermal properties that it heralds. The relation with Gibbs ensembles is studied and understood. We apply such a notion of equilibrium to a closed quantum system and show that there is always a class of observables which exhibits thermal equilibrium properties and we give a recipe to explicitly construct them. Eventually, an intimate connection with the Eigenstate Thermalisation Hypothesis is brought to light.

  11. New lipid family that forms inverted cubic phases in equilibrium with excess water: molecular structure-aqueous phase structure relationship for lipids with 5,9,13,17-tetramethyloctadecyl and 5,9,13,17-tetramethyloctadecanoyl chains.

    PubMed

    Yamashita, Jun; Shiono, Manzo; Hato, Masakatsu

    2008-10-02

    With a view to discovering a new family of lipids that form inverted cubic phases, the aqueous phase behavior of a series of lipids with isoprenoid-type hydrophobic chains has been examined over a temperature range from -40 to 65 degrees C by using optical microscopy, DSC (differential scanning calorimetry), and SAXS (small-angle X-ray scattering) techniques. The lipids examined are those with 5,9,13,17-tetramethyloctadecyl and 5,9,13,17-tetramethyloctadecanoyl chains linked to a series of headgroups, that is, erythritol, pentaerythritol, xylose, and glucose. All of the lipid/water systems displayed a "water + liquid crystalline phase" two-phase coexistence state when sufficiently diluted. The aqueous phase structures of the most diluted liquid crystalline phases in equilibrium with excess water depend both on the lipid molecular structure and on the temperature. Given an isoprenoid chain, the preferred phase consistently follows a phase sequence of an H II (an inverted hexagonal phase) to a Q II (an inverted bicontinuous cubic phase) to an L alpha (a lamellar phase) as A* (cross-section area of the headgroup) increases. For a given lipid/water system, the phase sequence observed as the temperature increases is L alpha to Q II to H II. The present study allowed us to find four cubic phase-forming lipid species, PEOC 18+4 [mono- O-(5,9,13,17-tetramethyloctadecyl)pentaerythritol], beta-XylOC 18+4 [1- O-(5,9,13,17-tetramethyloctadecyl)-beta- d-xylopyranoside], EROCOC 17+4 [1- O-(5,9,13,17-tetramethyloctadecanoyl)erythritol], and PEOCOC 17+4 [mono- O-(5,9,13,17-tetramethyloctadecanoyl)pentaerythritol]. The values of T K (hydrated solid-liquid crystalline phase transition temperature) of the cubic phase-forming lipids are all below 0 degrees C. Quantitative analyses of the lipid molecular structure-aqueous phase structure relationship in terms of the experimentally evaluated "surfactant parameter" allow us to rationally select an optimum combination of hydrophilic

  12. On structural transitions, thermodynamic equilibrium, and the phase diagram of DNA and RNA duplexes under torque and tension.

    PubMed

    Wereszczynski, Jeff; Andricioaei, Ioan

    2006-10-31

    A precise understanding of the flexibility of double stranded nucleic acids and the nature of their deformed conformations induced by external forces is important for a wide range of biological processes including transcriptional regulation, supercoil and catenane removal, and site-specific recombination. We present, at atomic resolution, a simulation of the dynamics involved in the transitions from B-DNA and A-RNA to Pauling (P) forms and to denatured states driven by application of external torque and tension. We then calculate the free energy profile along a B- to P-transition coordinate and from it, compute a reversible pathway, i.e., an isotherm of tension and torque pairs required to maintain P-DNA in equilibrium. The reversible isotherm maps correctly onto a phase diagram derived from single molecule experiments, and yields values of elongation, twist, and twist-stretch coupling in agreement with measured values. We also show that configurational entropy compensates significantly for the large electrostatic energy increase due to closer-packed P backbones. A similar set of simulations applied to RNA are used to predict a novel structure, P-RNA, with its associated free energy, equilibrium tension, torque and structural parameters, and to assign the location, on the phase-diagram, of a putative force-torque-dependent RNA "triple point."

  13. Simulations for Teaching Chemical Equilibrium

    NASA Astrophysics Data System (ADS)

    Huddle, Penelope A.; White, Margaret Dawn; Rogers, Fiona

    2000-07-01

    This paper outlines a systematic approach to teaching chemical equilibrium using simulation experiments that address most known alternate conceptions in the topic. Graphs drawn using the data from the simulations are identical to those obtained using real experimental data for reactions that go to equilibrium. This allows easy mapping of the analogy to the target. The requirements for the simulations are simple and inexpensive, making them accessible to even the poorest schools. The simulations can be adapted for all levels, from pupils who are first encountering equilibrium through students in tertiary education to qualified teachers who have experienced difficulty in teaching the topic. The simulations were piloted on four very different audiences. Minor modifications were then made before the Equilibrium Games as reported in this paper were tested on three groups of subjects: a Grade 12 class, college students, and university Chemistry I students. Marked improvements in understanding of the concept were shown in two of the three sets of subjects.

  14. Equilibrium sampling by reweighting nonequilibrium simulation trajectories

    NASA Astrophysics Data System (ADS)

    Yang, Cheng; Wan, Biao; Xu, Shun; Wang, Yanting; Zhou, Xin

    2016-03-01

    Based on equilibrium molecular simulations, it is usually difficult to efficiently visit the whole conformational space of complex systems, which are separated into some metastable regions by high free energy barriers. Nonequilibrium simulations could enhance transitions among these metastable regions and then be applied to sample equilibrium distributions in complex systems, since the associated nonequilibrium effects can be removed by employing the Jarzynski equality (JE). Here we present such a systematical method, named reweighted nonequilibrium ensemble dynamics (RNED), to efficiently sample equilibrium conformations. The RNED is a combination of the JE and our previous reweighted ensemble dynamics (RED) method. The original JE reproduces equilibrium from lots of nonequilibrium trajectories but requires that the initial distribution of these trajectories is equilibrium. The RED reweights many equilibrium trajectories from an arbitrary initial distribution to get the equilibrium distribution, whereas the RNED has both advantages of the two methods, reproducing equilibrium from lots of nonequilibrium simulation trajectories with an arbitrary initial conformational distribution. We illustrated the application of the RNED in a toy model and in a Lennard-Jones fluid to detect its liquid-solid phase coexistence. The results indicate that the RNED sufficiently extends the application of both the original JE and the RED in equilibrium sampling of complex systems.

  15. Equilibrium sampling by reweighting nonequilibrium simulation trajectories.

    PubMed

    Yang, Cheng; Wan, Biao; Xu, Shun; Wang, Yanting; Zhou, Xin

    2016-03-01

    Based on equilibrium molecular simulations, it is usually difficult to efficiently visit the whole conformational space of complex systems, which are separated into some metastable regions by high free energy barriers. Nonequilibrium simulations could enhance transitions among these metastable regions and then be applied to sample equilibrium distributions in complex systems, since the associated nonequilibrium effects can be removed by employing the Jarzynski equality (JE). Here we present such a systematical method, named reweighted nonequilibrium ensemble dynamics (RNED), to efficiently sample equilibrium conformations. The RNED is a combination of the JE and our previous reweighted ensemble dynamics (RED) method. The original JE reproduces equilibrium from lots of nonequilibrium trajectories but requires that the initial distribution of these trajectories is equilibrium. The RED reweights many equilibrium trajectories from an arbitrary initial distribution to get the equilibrium distribution, whereas the RNED has both advantages of the two methods, reproducing equilibrium from lots of nonequilibrium simulation trajectories with an arbitrary initial conformational distribution. We illustrated the application of the RNED in a toy model and in a Lennard-Jones fluid to detect its liquid-solid phase coexistence. The results indicate that the RNED sufficiently extends the application of both the original JE and the RED in equilibrium sampling of complex systems.

  16. Quasi-Particle Relaxation and Quantum Femtosecond Magnetism in Non-Equilibrium Phases of Insulating Manganites

    NASA Astrophysics Data System (ADS)

    Perakis, Ilias; Kapetanakis, Myron; Lingos, Panagiotis; Barmparis, George; Patz, A.; Li, T.; Wang, Jigang

    We study the role of spin quantum fluctuations driven by photoelectrons during 100fs photo-excitation of colossal magneto-resistive manganites in anti-ferromagnetic (AFM) charge-ordered insulating states with Jahn-Teller distortions. Our mean-field calculation of composite fermion excitations demonstrates that spin fluctuations reduce the energy gap by quasi-instantaneously deforming the AFM background, thus opening a conductive electronic pathway via FM correlation. We obtain two quasi-particle bands with distinct spin-charge dynamics and dependence on lattice distortions. To connect with fs-resolved spectroscopy experiments, we note the emergence of fs magnetization in the low-temperature magneto-optical signal, with threshold dependence on laser intensity characteristic of a photo-induced phase transition. Simultaneously, the differential reflectivity shows bi-exponential relaxation, with fs component, small at low intensity, exceeding ps component above threshold for fs AFM-to-FM switching. This suggests the emergence of a non-equilibrium metallic FM phase prior to establishment of a new lattice structure, linked with quantum magnetism via spin/charge/lattice couplings for weak magnetic fields.

  17. An experimental and thermodynamic equilibrium investigation of the Pb, Zn, Cr, Cu, Mn and Ni partitioning during sewage sludge incineration.

    PubMed

    Liu, Jingyong; Fu, Jiewen; Ning, Xun'an; Sun, Shuiyu; Wang, Yujie; Xie, Wuming; Huang, Shaosong; Zhong, Sheng

    2015-09-01

    The effects of different chlorides and operational conditions on the distribution and speciation of six heavy metals (Pb, Zn, Cr, Cu, Mn and Ni) during sludge incineration were investigated using a simulated laboratory tubular-furnace reactor. A thermodynamic equilibrium investigation using the FactSage software was performed to compare the experimental results. The results indicate that the volatility of the target metals was enhanced as the chlorine concentration increased. Inorganic-Cl influenced the volatilization of heavy metals in the order of Pb>Zn>Cr>Cu>Mn>Ni. However, the effects of organic-Cl on the volatility of Mn, Pb and Cu were greater than the effects on Zn, Cr and Ni. With increasing combustion temperature, the presence of organic-Cl (PVC) and inorganic-Cl (NaCl) improved the transfer of Pb and Zn from bottom ash to fly ash or fuse gas. However, the presence of chloride had no obvious influence on Mn, Cu and Ni. Increased retention time could increase the volatilization rate of heavy metals; however, this effect was insignificant. During the incineration process, Pb readily formed PbSiO4 and remained in the bottom ash. Different Pb compounds, primarily the volatile PbCl2, were found in the gas phase after the addition of NaCl; the dominant Pb compounds in the gas phase after the addition of PVC were PbCl2, Pb(ClO4)2 and PbCl2O4. Copyright © 2015. Published by Elsevier B.V.

  18. Unsteady Computational Tests of a Non-Equilibrium

    NASA Astrophysics Data System (ADS)

    Jirasek, Adam; Hamlington, Peter; Lofthouse, Andrew; Usafa Collaboration; Cu Boulder Collaboration

    2017-11-01

    A non-equilibrium turbulence model is assessed on simulations of three practically-relevant unsteady test cases; oscillating channel flow, transonic flow around an oscillating airfoil, and transonic flow around the Benchmark Super-Critical Wing. The first case is related to piston-driven flows while the remaining cases are relevant to unsteady aerodynamics at high angles of attack and transonic speeds. Non-equilibrium turbulence effects arise in each of these cases in the form of a lag between the mean strain rate and Reynolds stresses, resulting in reduced kinetic energy production compared to classical equilibrium turbulence models that are based on the gradient transport (or Boussinesq) hypothesis. As a result of the improved representation of unsteady flow effects, the non-equilibrium model provides substantially better agreement with available experimental data than do classical equilibrium turbulence models. This suggests that the non-equilibrium model may be ideally suited for simulations of modern high-speed, high angle of attack aerodynamics problems.

  19. Numerical modeling of an alloy droplet deposition with non-equilibrium solidification

    NASA Astrophysics Data System (ADS)

    Ramanuj, Vimal

    Droplet deposition is a process of extensive relevance to the microfabrication industry. Various bonding and film deposition methods utilize single or multiple droplet impingements on a substrate with subsequent splat formation through simultaneous spreading and solidification. Splat morphology and solidification characteristics play vital roles in determining the final outcome. Experimental methods have limited reach in studying such phenomena owing to the extremely small time and length scales involved. Fundamental understanding of the governing principles of fluid flow, heat transfer and phase change provide effective means of studying such processes through computational techniques. The present study aims at numerically modeling and analyzing the phenomenon of splat formation and phase change in an alloy droplet deposition process. Phase change in alloys occurs non-isothermally and its formulation poses mathematical challenges. A highly non-linear flow field in conjunction with multiple interfaces and convection-diffusion governed phase transition are some of the highlighting features involved in the numerical formulation. Moreover, the non-equilibrium solidification behavior in eutectic systems is of prime concern. The peculiar phenomenon requires special treatments in terms of modeling solid phase species diffusion, liquid phase enrichment during solute partitioning and isothermal eutectic transformation. The flow field is solved using a two-step projection algorithm coupled with enhanced interface modeling schemes. The free surface tracking and reconstruction is achieved through two approaches: VOF-PLIC and CLSVOF to achieve optimum interface accuracy with minimal computational resources. The energy equation is written in terms of enthalpy with an additional source term to account for the phase change. The solidification phenomenon is modeled using a coupled temperature-solute scheme that reflects the microscopic effects arising due to dendritic growth

  20. Development of an automated experimental setup for the study of ionic-exchange kinetics. Application to the ionic adsorption, equilibrium attainment and dissolution of apatite compounds.

    PubMed

    Thomann, J M; Gasser, P; Bres, E F; Voegel, J C; Gramain, P

    1990-02-01

    An ion-selective electrode and microcomputer-based experimental setup for the study of ionic-exchange kinetics between a powdered solid and the solution is described. The equipment is composed of easily available commercial devices and a data acquisition and regularization computer program is presented. The system, especially developed to investigate the ionic adsorption, equilibrium attainment and dissolution of hard mineralized tissues, provides good reliable results by taking into account the volume changes of the reacting solution and the electrode behaviour under different experimental conditions, and by avoiding carbonation of the solution. A second computer program, using the regularized data and the experimental parameters, calculates the quantities of protons consumed and calcium released in the case of equilibrium attainment and dissolution of apatite-like compounds. Finally, typical examples of ion-exchange and dissolution kinetics under constant pH of enamel and synthetic hydroxyapatite are examined.

  1. Diffusion relaxation times of nonequilibrium isolated small bodies and their solid phase ensembles to equilibrium states

    NASA Astrophysics Data System (ADS)

    Tovbin, Yu. K.

    2017-08-01

    The possibility of obtaining analytical estimates in a diffusion approximation of the times needed by nonequilibrium small bodies to relax to their equilibrium states based on knowledge of the mass transfer coefficient is considered. This coefficient is expressed as the product of the self-diffusion coefficient and the thermodynamic factor. A set of equations for the diffusion transport of mixture components is formulated, characteristic scales of the size of microheterogeneous phases are identified, and effective mass transfer coefficients are constructed for them. Allowing for the developed interface of coexisting and immiscible phases along with the porosity of solid phases is discussed. This approach can be applied to the diffusion equalization of concentrations of solid mixture components in many physicochemical systems: the mutual diffusion of components in multicomponent systems (alloys, semiconductors, solid mixtures of inert gases) and the mass transfer of an absorbed mobile component in the voids of a matrix consisting of slow components or a mixed composition of mobile and slow components (e.g., hydrogen in metals, oxygen in oxides, and the transfer of molecules through membranes of different natures, including polymeric).

  2. Quasi-equilibrium size distribution of subcritical nuclei in amorphous phase change AgIn-Sb2Te

    NASA Astrophysics Data System (ADS)

    Darmawikarta, Kristof; Lee, Bong-Sub; Shelby, Robert M.; Raoux, Simone; Bishop, Stephen G.; Abelson, John R.

    2013-07-01

    We investigate the effect of low temperature annealing or of extended storage at room temperature on the subsequent nucleation behavior of amorphous AgIn-incorporated Sb2Te (AIST), a material for phase change memories. Time-resolved reflectivity measurements during pulsed laser crystallization reveal the rates of solid-phase transformation, while fluctuation transmission electron microscopy detects the nanoscale order in the amorphous phase prior to crystallization. The nanoscale order is postulated to consist of subcritical nuclei that coarsen upon annealing at temperatures ranging from 25 °C (for months) or 100 °C (for hours). Samples that have been annealed remain fully amorphous as evaluated by conventional diffraction experiments. Shorter nucleation times are consistently associated with the observation of increased nanoscale order. The effect of annealing is observed to saturate: there is no further reduction in nucleation time or increase in nanoscale order for annealing at 100 °C beyond three hours. This result supports the general prediction of classical nucleation theory that the size distribution of subcritical nuclei increases from the as-deposited state to a quasi-equilibrium.

  3. Equilibrium, kinetic, and reactive transport models for plutonium

    NASA Astrophysics Data System (ADS)

    Schwantes, Jon Michael

    Equilibrium, kinetic, and reactive transport models for plutonium (Pu) have been developed to help meet environmental concerns posed by past war-related and present and future peacetime nuclear technologies. A thorough review of the literature identified several hurdles that needed to be overcome in order to develop capable predictive tools for Pu. These hurdles include: (1) missing or ill-defined chemical equilibrium and kinetic constants for environmentally important Pu species; (2) no adequate conceptual model describing the formation of Pu oxy/hydroxide colloids and solids; and (3) an inability of two-phase reactive transport models to adequately simulate Pu behavior in the presence of colloids. A computer program called INVRS K was developed that integrates the geochemical modeling software of PHREEQC with a nonlinear regression routine. This program provides a tool for estimating equilibrium and kinetic constants from experimental data. INVRS K was used to regress on binding constants for Pu sorbing onto various mineral and humic surfaces. These constants enhance the thermodynamic database for Pu and improve the capability of current predictive tools. Time and temperature studies of the Pu intrinsic colloid were also conducted and results of these studies were presented here. Formation constants for the fresh and aged Pu intrinsic colloid were regressed upon using INVRS K. From these results, it was possible to develop a cohesive diagenetic model that describes the formation of Pu oxy/hydroxide colloids and solids. This model provides for the first time a means of deciphering historically unexplained observations with respect to the Pu intrinsic colloid, as well as a basis for simulating the behavior within systems containing these solids. Discussion of the development and application of reactive transport models is also presented and includes: (1) the general application of a 1-D in flow, three-phase (i.e., dissolved, solid, and colloidal), reactive

  4. Dynamic relaxation of a levitated nanoparticle from a non-equilibrium steady state.

    PubMed

    Gieseler, Jan; Quidant, Romain; Dellago, Christoph; Novotny, Lukas

    2014-05-01

    Fluctuation theorems are a generalization of thermodynamics on small scales and provide the tools to characterize the fluctuations of thermodynamic quantities in non-equilibrium nanoscale systems. They are particularly important for understanding irreversibility and the second law in fundamental chemical and biological processes that are actively driven, thus operating far from thermal equilibrium. Here, we apply the framework of fluctuation theorems to investigate the important case of a system relaxing from a non-equilibrium state towards equilibrium. Using a vacuum-trapped nanoparticle, we demonstrate experimentally the validity of a fluctuation theorem for the relative entropy change occurring during relaxation from a non-equilibrium steady state. The platform established here allows non-equilibrium fluctuation theorems to be studied experimentally for arbitrary steady states and can be extended to investigate quantum fluctuation theorems as well as systems that do not obey detailed balance.

  5. Self-Organization of Blood Pressure Regulation: Experimental Evidence

    PubMed Central

    Fortrat, Jacques-Olivier; Levrard, Thibaud; Courcinous, Sandrine; Victor, Jacques

    2016-01-01

    Blood pressure regulation is a prime example of homeostatic regulation. However, some characteristics of the cardiovascular system better match a non-linear self-organized system than a homeostatic one. To determine whether blood pressure regulation is self-organized, we repeated the seminal demonstration of self-organized control of movement, but applied it to the cardiovascular system. We looked for two distinctive features peculiar to self-organization: non-equilibrium phase transitions and hysteresis in their occurrence when the system is challenged. We challenged the cardiovascular system by means of slow, 20-min Tilt-Up and Tilt-Down tilt table tests in random order. We continuously determined the phase between oscillations at the breathing frequency of Total Peripheral Resistances and Heart Rate Variability by means of cross-spectral analysis. We looked for a significant phase drift during these procedures, which signed a non-equilibrium phase transition. We determined at which head-up tilt angle it occurred. We checked that this angle was significantly different between Tilt-Up and Tilt-Down to demonstrate hysteresis. We observed a significant non-equilibrium phase transition in nine healthy volunteers out of 11 with significant hysteresis (48.1 ± 7.5° and 21.8 ± 3.9° during Tilt-Up and Tilt-Down, respectively, p < 0.05). Our study shows experimental evidence of self-organized short-term blood pressure regulation. It provides new insights into blood pressure regulation and its related disorders. PMID:27065880

  6. The nature of the continuous non-equilibrium phase transition of Axelrod's model

    NASA Astrophysics Data System (ADS)

    Peres, Lucas R.; Fontanari, José F.

    2015-09-01

    Axelrod's model in the square lattice with nearest-neighbors interactions exhibits culturally homogeneous as well as culturally fragmented absorbing configurations. In the case in which the agents are characterized by F = 2 cultural features and each feature assumes k states drawn from a Poisson distribution of parameter q, these regimes are separated by a continuous transition at qc = 3.10 +/- 0.02 . Using Monte Carlo simulations and finite-size scaling we show that the mean density of cultural domains μ is an order parameter of the model that vanishes as μ ∼ (q - q_c)^β with β = 0.67 +/- 0.01 at the critical point. In addition, for the correlation length critical exponent we find ν = 1.63 +/- 0.04 and for Fisher's exponent, τ = 1.76 +/- 0.01 . This set of critical exponents places the continuous phase transition of Axelrod's model apart from the known universality classes of non-equilibrium lattice models.

  7. Quantum quench in a p+ip superfluid: Winding numbers and topological states far from equilibrium

    NASA Astrophysics Data System (ADS)

    Foster, Matthew S.; Dzero, Maxim; Gurarie, Victor; Yuzbashyan, Emil A.

    2013-09-01

    We study the nonadiabatic dynamics of a two-dimensional p+ip superfluid following an instantaneous quantum quench of the BCS coupling constant. The model describes a topological superconductor with a nontrivial BCS (trivial BEC) phase appearing at weak- (strong-) coupling strengths. We extract the exact long-time asymptotics of the order parameter Δ(t) by exploiting the integrability of the classical p-wave Hamiltonian, which we establish via a Lax construction. Three different types of asymptotic behavior can occur depending upon the strength and direction of the interaction quench. We refer to these as the nonequilibrium phases {I, II, III}, characterized as follows. In phase I, the order parameter asymptotes to zero due to dephasing. In phase II, Δ→Δ∞, a nonzero constant. Phase III is characterized by persistent oscillations of Δ(t). For quenches within phases I and II, we determine the topological character of the asymptotic states. We show that two different formulations of the bulk topological winding number, although equivalent in the BCS or BEC ground states, must be regarded as independent out of equilibrium. The first winding number Q characterizes the Anderson pseudospin texture of the initial state; we show that Q is generically conserved. For Q≠0, this leads to the prediction of a “gapless topological” state when Δ asymptotes to zero. The presence or absence of Majorana edge modes in a sample with a boundary is encoded in the second winding number W, which is formulated in terms of the retarded Green's function. We establish that W can change following a quench across the quantum critical point. When the order parameter asymptotes to a nonzero constant, the final value of W is well defined and quantized. We discuss the implications for the (dis)appearance of Majorana edge modes. Finally, we show that the parity of zeros in the bulk out-of-equilibrium Cooper-pair distribution function constitutes a Z2-valued quantum number, which is

  8. Thermodynamic modelling of phase equilibrium in system Ti-B-Si-C, synthesis and phases composition of borides and carbides layers on titanic alloyVT-1 at electron beam treatment in vacuum

    NASA Astrophysics Data System (ADS)

    Smirnyagina, N. N.; Khaltanova, V. M.; Lapina, A. E.; Dasheev, D. E.

    2017-01-01

    Composite layers on the basis of carbides and borides the titan and silicon on titanic alloy VT-1 are generated at diffused saturation in vacuum. Formation in a composite of MAX phase Ti3SiC2 is shown. Thermodynamic research of phase equilibrium in systems Ti-Si-C and Ti-B-C in the conditions of high vacuum is executed. The thermodynamics, formation mechanisms of superfirm layers borides and carbides of the titan and silicon are investigated.

  9. Experimental Investigation of two-phase nitrogen Cryo transfer line

    NASA Astrophysics Data System (ADS)

    Singh, G. K.; Nimavat, H.; Panchal, R.; Garg, A.; Srikanth, GLN; Patel, K.; Shah, P.; Tanna, V. L.; Pradhan, S.

    2017-02-01

    A 6-m long liquid nitrogen based cryo transfer line has been designed, developed and tested at IPR. The test objectives include the thermo-hydraulic characteristics of Cryo transfer line under single phase as well as two phase flow conditions. It is always easy in experimentation to investigate the thermo-hydraulic parameters in case of single phase flow of cryogen but it is real challenge when one deals with the two phase flow of cryogen due to availibity of mass flow measurements (direct) under two phase flow conditions. Established models have been reported in the literature where one of the well-known model of Lockhart-Martenelli relationship has been used to determine the value of quality at the outlet of Cryo transfer line. Under homogenous flow conditions, by taking the ratio of the single-phase pressure drop and the two-phase pressure drop, we estimated the quality at the outlet. Based on these equations, vapor quality at the outlet of the transfer line was predicted at different heat loads. Experimental rresults shown that from inlet to outlet, there is a considerable increment in the pressure drop and vapour quality of the outlet depending upon heat load and mass flow rate of nitrogen flowing through the line.

  10. Dynamics and circuit of a chaotic system with a curve of equilibrium points

    NASA Astrophysics Data System (ADS)

    Pham, Viet-Thanh; Volos, Christos; Kapitaniak, Tomasz; Jafari, Sajad; Wang, Xiong

    2018-03-01

    Although chaotic systems have been intensively studied since the 1960s, new systems with mysterious features are still of interest. A novel chaotic system including hyperbolic functions is proposed in this work. Especially, the system has an infinite number of equilibrium points. Dynamics of the system are investigated by using non-linear tools such as phase portrait, bifurcation diagram, and Lyapunov exponent. It is interesting that the system can display coexisting chaotic attractors. An electronic circuit for realising the chaotic system has been implemented. Experimental results show a good agreement with theoretical ones.

  11. 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

  12. An experimental and theoretical evaluation of increased thermal diffusivity phase change devices

    NASA Technical Reports Server (NTRS)

    White, S. P.; Golden, J. O.; Stermole, F. J.

    1972-01-01

    This study was to experimentally evaluate and mathematically model the performance of phase change thermal control devices containing high thermal conductivity metal matrices. Three aluminum honeycomb filters were evaluated at five different heat flux levels using n-oct-adecane as the test material. The system was mathematically modeled by approximating the partial differential equations with a three-dimensional implicit alternating direction technique. The mathematical model predicts the system quite well. All of the phase change times are predicted. The heating of solid phase is predicted exactly while there is some variation between theoretical and experimental results in the liquid phase. This variation in the liquid phase could be accounted for by the fact that there are some heat losses in the cell and there could be some convection in the experimental system.

  13. Time, space and equilibrium means of continuous vector functions on the phase space of a dynamical system

    NASA Astrophysics Data System (ADS)

    Gurevich, Boris M.; Tempel'man, Arcady A.

    2010-05-01

    For a dynamical system \\tau with 'time' \\mathbb Z^d and compact phase space X, we introduce three subsets of the space \\mathbb R^m related to a continuous function f\\colon X\\to\\mathbb R^m: the set of time means of f and two sets of space means of f, namely those corresponding to all \\tau-invariant probability measures and those corresponding to some equilibrium measures on X. The main results concern topological properties of these sets of means and their mutual position. Bibliography: 18 titles.

  14. Reversible shear-induced crystallization above equilibrium freezing temperature in a lyotropic surfactant system

    PubMed Central

    Rathee, Vikram; Krishnaswamy, Rema; Pal, Antara; Raghunathan, V. A.; Impéror-Clerc, Marianne; Pansu, Brigitte; Sood, A. K.

    2013-01-01

    We demonstrate a unique shear-induced crystallization phenomenon above the equilibrium freezing temperature in weakly swollen isotropic and lamellar mesophases with bilayers formed in a cationic-anionic mixed surfactant system. Synchrotron rheological X-ray diffraction study reveals the crystallization transition to be reversible under shear (i.e., on stopping the shear, the nonequilibrium crystalline phase melts back to the equilibrium mesophase). This is different from the shear-driven crystallization below , which is irreversible. Rheological optical observations show that the growth of the crystalline phase occurs through a preordering of the phase to an phase induced by shear flow, before the nucleation of the phase. Shear diagram of the phase constructed in the parameter space of shear rate vs. temperature exhibits and transitions above the equilibrium crystallization temperature , in addition to the irreversible shear-driven nucleation of in the phase below . In addition to revealing a unique class of nonequilibrium phase transition, the present study urges a unique approach toward understanding shear-induced phenomena in concentrated mesophases of mixed amphiphilic systems. PMID:23986497

  15. Profiles of equilibrium constants for self-association of aromatic molecules

    NASA Astrophysics Data System (ADS)

    Beshnova, Daria A.; Lantushenko, Anastasia O.; Davies, David B.; Evstigneev, Maxim P.

    2009-04-01

    Analysis of the noncovalent, noncooperative self-association of identical aromatic molecules assumes that the equilibrium self-association constants are either independent of the number of molecules (the EK-model) or change progressively with increasing aggregation (the AK-model). The dependence of the self-association constant on the number of molecules in the aggregate (i.e., the profile of the equilibrium constant) was empirically derived in the AK-model but, in order to provide some physical understanding of the profile, it is proposed that the sources for attenuation of the equilibrium constant are the loss of translational and rotational degrees of freedom, the ordering of molecules in the aggregates and the electrostatic contribution (for charged units). Expressions are derived for the profiles of the equilibrium constants for both neutral and charged molecules. Although the EK-model has been widely used in the analysis of experimental data, it is shown in this work that the derived equilibrium constant, KEK, depends on the concentration range used and hence, on the experimental method employed. The relationship has also been demonstrated between the equilibrium constant KEK and the real dimerization constant, KD, which shows that the value of KEK is always lower than KD.

  16. Modeling of equilibrium hollow objects stabilized by electrostatics.

    PubMed

    Mani, Ethayaraja; Groenewold, Jan; Kegel, Willem K

    2011-05-18

    The equilibrium size of two largely different kinds of hollow objects behave qualitatively differently with respect to certain experimental conditions. Yet, we show that they can be described within the same theoretical framework. The objects we consider are 'minivesicles' of ionic and nonionic surfactant mixtures, and shells of Keplerate-type polyoxometalates. The finite-size of the objects in both systems is manifested by electrostatic interactions. We emphasize the importance of constant charge and constant potential boundary conditions. Taking these conditions into account, indeed, leads to the experimentally observed qualitatively different behavior of the equilibrium size of the objects.

  17. Dynamics of Charged Particles in an Adiabatic Thermal Beam Equilibrium

    NASA Astrophysics Data System (ADS)

    Chen, Chiping; Wei, Haofei

    2010-11-01

    Charged-particle motion is studied in the self-electric and self-magnetic fields of a well-matched, intense charged-particle beam and an applied periodic solenoidal magnetic focusing field. The beam is assumed to be in a state of adiabatic thermal equilibrium. The phase space is analyzed and compared with that of the well-known Kapchinskij-Vladimirskij (KV)-type beam equilibrium. It is found that the widths of nonlinear resonances in the adiabatic thermal beam equilibrium are narrower than those in the KV-type beam equilibrium. Numerical evidence is presented, indicating almost complete elimination of chaotic particle motion in the adiabatic thermal beam equilibrium.

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

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

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

    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. D 61, 899–902], the impact of identifying optimized phases for a small numbermore » 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.« less

  19. 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. D 61, 899–902], the impact of identifying optimized phases for a small numbermore » 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.« less

  20. Impact of higher order diagrams on phase equilibrium calculations for small molecules using lattice cluster theory

    NASA Astrophysics Data System (ADS)

    Zimmermann, Patrick; Walowski, Christoph; Enders, Sabine

    2018-03-01

    The Lattice Cluster Theory (LCT) provides a powerful tool to predict thermodynamic properties of large molecules (e.g., polymers) of different molecular architectures. When the pure-component parameters of a certain compound have been derived by adjustment to experimental data and the number of atoms is held constant within the molecule so that only the architecture is changed, the LCT is capable of predicting the properties of isomers without further parameter adjustment just based on the incorporation of molecular architecture. Trying to predict the thermodynamic properties of smaller molecules, one might face some challenges, which are addressed in this contribution. After factoring out the mean field term of the partition function, the LCT poses an expression that involves corrections to the mean field depending on molecular architecture, resulting in the free energy formally being expressed as a double series expansion in lattice coordination number z and interaction energy ɛ ˜ . In the process of deriving all contributing sub-structures within a molecule, some parts have been neglected to this point due to the double series expansion being truncated after the order ɛ˜ 2z-2. We consider the neglected parts that are of the order z-3 and reformulate the expression for the free energy within the LCT to achieve a higher predictive capability of the theory when it comes to small isomers and compressible systems. The modified version was successfully applied for phase equilibrium calculations of binary mixtures composed of linear and branched alkanes.

  1. Dependence of growth of the phases of multiphase binary systems on the diffusion parameters

    NASA Astrophysics Data System (ADS)

    Molokhina, L. A.; Rogalin, V. E.; Filin, S. A.; Kaplunov, I. A.

    2017-12-01

    A mathematical model of the diffusion interaction of a binary system with several phases on the equilibrium phase diagram is presented. The theoretical and calculated dependences of the layer thickness of each phase in the multiphase diffusion zone on the isothermal annealing time and the ratio of the diffusion parameters in the neighboring phases with an unlimited supply of both components were constructed. The phase formation and growth in the diffusion zone during "reactive" diffusion corresponds to the equilibrium state diagram for two components, and the order of their appearance in the diffusion zone depends only on the ratio of the diffusion parameters in the phases themselves and on the duration of the incubation periods. The dependence of phase appearance on the incubation periods, annealing time, and difference in the movement rates of the components across the interface boundaries was obtained. An example of the application of the model for processing the experimental data on phase growth in a two-component three-phase system was given.

  2. Crystalline liquids: the blue phases

    NASA Astrophysics Data System (ADS)

    Wright, David C.; Mermin, N. David

    1989-04-01

    The blue phases of cholesteric liquid crystals are liquids that exhibit orientational order characterized by crystallographic space-group symmetries. We present here a pedagogical introduction to the current understanding of the equilibrium structure of these phases accompanied by a general overview of major experimental results. Using the Ginzburg-Landau free energy appropriate to the system, we first discuss in detail the character and stability of the usual helical phase of cholesterics, showing that for certain parameter ranges the helical phase is unstable to the appearance of one or more blue phases. The two principal models for the blue phases are two limiting cases of the Ginzburg-Landau theory. We explore each limit and conclude with some general considerations of defects in both models and an exact minimization of the free energy in a curved three-dimensional space.

  3. Experimental phase synchronization detection in non-phase coherent chaotic systems by using the discrete complex wavelet approach

    NASA Astrophysics Data System (ADS)

    Ferreira, Maria Teodora; Follmann, Rosangela; Domingues, Margarete O.; Macau, Elbert E. N.; Kiss, István Z.

    2017-08-01

    Phase synchronization may emerge from mutually interacting non-linear oscillators, even under weak coupling, when phase differences are bounded, while amplitudes remain uncorrelated. However, the detection of this phenomenon can be a challenging problem to tackle. In this work, we apply the Discrete Complex Wavelet Approach (DCWA) for phase assignment, considering signals from coupled chaotic systems and experimental data. The DCWA is based on the Dual-Tree Complex Wavelet Transform (DT-CWT), which is a discrete transformation. Due to its multi-scale properties in the context of phase characterization, it is possible to obtain very good results from scalar time series, even with non-phase-coherent chaotic systems without state space reconstruction or pre-processing. The method correctly predicts the phase synchronization for a chemical experiment with three locally coupled, non-phase-coherent chaotic processes. The impact of different time-scales is demonstrated on the synchronization process that outlines the advantages of DCWA for analysis of experimental data.

  4. The keto-enol equilibrium and thermal conversion kinetics of 2- and 4-hydroxyacetophenone in the gas phase: a DFT study

    NASA Astrophysics Data System (ADS)

    Monascal, Yeljair; Gallardo, Eliana; Cartaya, Loriett; Maldonado, Alexis; Bentarcurt, Yenner; Chuchani, Gabriel

    2018-01-01

    Keto-enol tautomeric equilibrium and the mechanism of thermal conversion of 2- and 4-hydroxyacetophenone in gas phase have been studied by means of electronic structure calculations using density functional theory (DFT). A topological analysis of electron density evidence that the structure of keto and enol forms of 2-hydroxyacetophenone are stabilised by a relatively strong intramolecular hydrogen bond. 2- and 4-hydroxyacetophenone undergo deacetylation reactions yielding phenol and ketene. Two possible mechanisms are considered for these eliminations: the process takes place from the keto form (mechanism A), or occurs from the enolic form of the substrate (mechanism B). Quantum chemical calculations support the mechanism B, being found a good agreement with the experimental activation parameters. These results suggest that the rate-limiting step is the reaction of the enol through a concerted, non-synchronous, semi-polar, four-membered cyclic transition state (TS). The most advanced reaction coordinate in the TS is the rupture of O1...H1 bond, with an evolution in the order of 79.7%-80.9%. Theoretical results also suggest a three-step mechanism for the phenyl acetate formation from 2-hydroxyacetophenone.

  5. Enhanced Night Visibility Series, Volume XII : Overview of Phase II and Development of Phase III Experimental Plan

    DOT National Transportation Integrated Search

    2005-12-01

    This volume provides an overview of the six studies that compose Phase II of the Enhanced Night Visibility project and the experimental plan for its third and final portion, Phase III. The Phase II studies evaluated up to 12 vision enhancement system...

  6. Demonstrating Phase Changes.

    ERIC Educational Resources Information Center

    Rohr, Walter

    1995-01-01

    Presents two experiments that demonstrate phase changes. The first experiment explores phase changes of carbon dioxide using powdered dry ice sealed in a piece of clear plastic tubing. The second experiment demonstrates an equilibrium process in which a crystal grows in equilibrium with its saturated solution. (PVD)

  7. Effects of resident water and non-equilibrium adsorption on the primary and enhanced coalbed methane gas recovery

    NASA Astrophysics Data System (ADS)

    Jahediesfanjani, Hossein

    The major part of the gas in coalbed methane and shale gas reservoirs is stored as the adsorbed gas in the coal and organic materials of the black shale internal surfaces. The sorption sites in both reservoirs are composed of several macropores that contain very small pore sizes. Therefore, the adsorption/desorption is very slow process and follows a non-equilibrium trend. The time-dependency of the sorption process is further affected by the reservoir resident water. Water can diffuse into the matrix and adsorption sites, plug the pores and affect the reservoir gas production. This study presents an experimental and theoretical procedure to investigate the effects of the resident water and time-dependency of the sorption process on coalbed and shale gas primary and enhanced recovery by simultaneous CO 2/N2 injection. Series of the experiments are conducted to construct both equilibrium and non-equilibrium single and multi-component isotherms with the presence of water. A novel and rapid data interpretation technique is developed based on the nonequilibrium adsorption/desorption thermodynamics, mass conservation law, and volume filling adsorption theory. The developed technique is implemented to construct both equilibrium and non-equilibrium multi-component multi-phase isotherms from the early time experimental measurements. The non-equilibrium isotherms are incorporated in the coalbed methane/shale gas reservoir simulations to account for the time-dependency of the sorption process. The experimental results indicate that the presence of water in the sorption system reduces both carbon dioxide and nitrogen adsorption rates. Reduction in the adsorption rate for carbon dioxide is more than nitrogen. The results also indicate that the resident water reduces the adsorption ability of low rank coals more than high rank ones. The results of the multi-component sorption tests indicate that increasing the initial mole fraction of the nitrogen gas in the injected CO2/N2

  8. Determination of methane concentrations in water in equilibrium with sI methane hydrate in the absence of a vapor phase by in situ Raman spectroscopy

    USGS Publications Warehouse

    Lu, W.; Chou, I.-Ming; Burruss, R.C.

    2008-01-01

    Most submarine gas hydrates are located within the two-phase equilibrium region of hydrate and interstitial water with pressures (P) ranging from 8 to 60 MPa and temperatures (T) from 275 to 293 K. However, current measurements of solubilities of methane in equilibrium with hydrate in the absence of a vapor phase are limited below 20 MPa and 283.15 K, and the differences among these data are up to 30%. When these data were extrapolated to other P-T conditions, it leads to large and poorly known uncertainties. In this study, in situ Raman spectroscopy was used to measure methane concentrations in pure water in equilibrium with sI (structure one) methane hydrate, in the absence of a vapor phase, at temperatures from 276.6 to 294.6 (??0.3) K and pressures at 10, 20, 30 and 40 (??0.4%) MPa. The relationship among concentration of methane in water in equilibrium with hydrate, in mole fraction [X(CH4)], the temperature in K, and pressure in MPa was derived as: X(CH4) = exp [11.0464 + 0.023267 P - (4886.0 + 8.0158 P)/T]. Both the standard enthalpy and entropy of hydrate dissolution at the studied T-P conditions increase slightly with increasing pressure, ranging from 41.29 to 43.29 kJ/mol and from 0.1272 to 0.1330 kJ/K ?? mol, respectively. When compared with traditional sampling and analytical methods, the advantages of our method include: (1) the use of in situ Raman signals for methane concentration measurements eliminates possible uncertainty caused by sampling and ex situ analysis, (2) it is simple and efficient, and (3) high-pressure data can be obtained safely. ?? 2007 Elsevier Ltd. All rights reserved.

  9. A procedure to find thermodynamic equilibrium constants for CO2 and CH4 adsorption on activated carbon.

    PubMed

    Trinh, T T; van Erp, T S; Bedeaux, D; Kjelstrup, S; Grande, C A

    2015-03-28

    Thermodynamic equilibrium for adsorption means that the chemical potential of gas and adsorbed phase are equal. A precise knowledge of the chemical potential is, however, often lacking, because the activity coefficient of the adsorbate is not known. Adsorption isotherms are therefore commonly fitted to ideal models such as the Langmuir, Sips or Henry models. We propose here a new procedure to find the activity coefficient and the equilibrium constant for adsorption which uses the thermodynamic factor. Instead of fitting the data to a model, we calculate the thermodynamic factor and use this to find first the activity coefficient. We show, using published molecular simulation data, how this procedure gives the thermodynamic equilibrium constant and enthalpies of adsorption for CO2(g) on graphite. We also use published experimental data to find similar thermodynamic properties of CO2(g) and of CH4(g) adsorbed on activated carbon. The procedure gives a higher accuracy in the determination of enthalpies of adsorption than ideal models do.

  10. Analyzing slowly exchanging protein conformations by ion mobility mass spectrometry: study of the dynamic equilibrium of prolyl oligopeptidase.

    PubMed

    López, Abraham; Vilaseca, Marta; Madurga, Sergio; Varese, Monica; Tarragó, Teresa; Giralt, Ernest

    2016-07-01

    Ion mobility mass spectrometry (IMMS) is a biophysical technique that allows the separation of isobaric species on the basis of their size and shape. The high separation capacity, sensitivity and relatively fast time scale measurements confer IMMS great potential for the study of proteins in slow (µs-ms) conformational equilibrium in solution. However, the use of this technique for examining dynamic proteins is still not generalized. One of the major limitations is the instability of protein ions in the gas phase, which raises the question as to what extent the structures detected reflect those in solution. Here, we addressed this issue by analyzing the conformational landscape of prolyl oligopeptidase (POP) - a model of a large dynamic enzyme in the µs-ms range - by native IMMS and compared the results obtained in the gas phase with those obtained in solution. In order to interpret the experimental results, we used theoretical simulations. In addition, the stability of POP gaseous ions was explored by charge reduction and collision-induced unfolding experiments. Our experiments disclosed two species of POP in the gas phase, which correlated well with the open and closed conformations in equilibrium in solution; moreover, a gas-phase collapsed form of POP was also detected. Therefore, our findings not only support the potential of IMMS for the study of multiple co-existing conformations of large proteins in slow dynamic equilibrium in solution but also stress the need for careful data analysis to avoid artifacts. Copyright © 2016 John Wiley & Sons, Ltd. Copyright © 2016 John Wiley & Sons, Ltd.

  11. Comparison of forcefields for molecular dynamics simulations of hydrocarbon phase diagrams

    NASA Astrophysics Data System (ADS)

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

    2018-01-01

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

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

    PubMed

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

    2015-06-25

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

  13. Experimental study and thermodynamic modeling of the Al–Co–Cr–Ni system

    DOE PAGES

    Gheno, Thomas; Liu, Xuan L.; Lindwall, Greta; ...

    2015-09-21

    In this study, a thermodynamic database for the Al–Co–Cr–Ni system is built via the Calphad method by extrapolating re-assessed ternary subsystems. A minimum number of quaternary parameters are included, which are optimized using experimental phase equilibrium data obtained by electron probe micro-analysis and x-ray diffraction analysis of NiCoCrAlY alloys spanning a wide compositional range, after annealing at 900 °C, 1100 °C and 1200 °C, and water quenching. These temperatures are relevant to oxidation and corrosion resistant MCrAlY coatings, where M corresponds to some combination of nickel and cobalt. Comparisons of calculated and measured phase compositions show excellent agreement for themore » β–γ equilibrium, and good agreement for three-phase β–γ–σ and β–γ–α equilibria. An extensive comparison with existing Ni-base databases (TCNI6, TTNI8, NIST) is presented in terms of phase compositions.« less

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

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

    Uervirojnangkoorn, Monarin; University of Lübeck, Ratzeburger Allee 160, 23538 Lübeck; Hilgenfeld, Rolf, E-mail: hilgenfeld@biochem.uni-luebeck.de

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

  15. Non-equilibrium theory of arrested spinodal decomposition

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

    Olais-Govea, José Manuel; López-Flores, Leticia; Medina-Noyola, Magdaleno

    The non-equilibrium self-consistent generalized Langevin equation theory of irreversible relaxation [P. E. Ramŕez-González and M. Medina-Noyola, Phys. Rev. E 82, 061503 (2010); 82, 061504 (2010)] is applied to the description of the non-equilibrium processes involved in the spinodal decomposition of suddenly and deeply quenched simple liquids. For model liquids with hard-sphere plus attractive (Yukawa or square well) pair potential, the theory predicts that the spinodal curve, besides being the threshold of the thermodynamic stability of homogeneous states, is also the borderline between the regions of ergodic and non-ergodic homogeneous states. It also predicts that the high-density liquid-glass transition line, whosemore » high-temperature limit corresponds to the well-known hard-sphere glass transition, at lower temperature intersects the spinodal curve and continues inside the spinodal region as a glass-glass transition line. Within the region bounded from below by this low-temperature glass-glass transition and from above by the spinodal dynamic arrest line, we can recognize two distinct domains with qualitatively different temperature dependence of various physical properties. We interpret these two domains as corresponding to full gas-liquid phase separation conditions and to the formation of physical gels by arrested spinodal decomposition. The resulting theoretical scenario is consistent with the corresponding experimental observations in a specific colloidal model system.« less

  16. Absolute determination of the gelling point of gelatin under quasi-thermodynamic equilibrium.

    PubMed

    Bellini, Franco; Alberini, Ivana; Ferreyra, María G; Rintoul, Ignacio

    2015-05-01

    Thermodynamic studies on phase transformation of biopolymers in solution are useful to understand their nature and to evaluate their technological potentials. Thermodynamic studies should be conducted avoiding time-related phenomena. This condition is not easily achieved in hydrophilic biopolymers. In this contribution, the simultaneous effects of pH, salt concentration, and cooling rate (Cr) on the folding from random coil to triple helical collagen-like structures of gelatin were systematically studied. The phase transformation temperature at the absolute invariant condition of Cr = 0 °C/min (T(T)Cr=0) ) is introduced as a conceptual parameter to study phase transformations in biopolymers under quasi-thermodynamic equilibrium and avoiding interferences coming from time-related phenomena. Experimental phase diagrams obtained at different Cr are presented. The T(T)(Cr=0) compared with pH and TT(Cr=0) compared with [NaCl] diagram allowed to explore the transformation process at Cr = 0 °C/min. The results were explained by electrostatic interactions between the biopolymers and its solvation milieu. © 2015 Institute of Food Technologists®

  17. Lindemann histograms as a new method to analyse nano-patterns and phases

    NASA Astrophysics Data System (ADS)

    Makey, Ghaith; Ilday, Serim; Tokel, Onur; Ibrahim, Muhamet; Yavuz, Ozgun; Pavlov, Ihor; Gulseren, Oguz; Ilday, Omer

    The detection, observation, and analysis of material phases and atomistic patterns are of great importance for understanding systems exhibiting both equilibrium and far-from-equilibrium dynamics. As such, there is intense research on phase transitions and pattern dynamics in soft matter, statistical and nonlinear physics, and polymer physics. In order to identify phases and nano-patterns, the pair correlation function is commonly used. However, this approach is limited in terms of recognizing competing patterns in dynamic systems, and lacks visualisation capabilities. In order to solve these limitations, we introduce Lindemann histogram quantification as an alternative method to analyse solid, liquid, and gas phases, along with hexagonal, square, and amorphous nano-pattern symmetries. We show that the proposed approach based on Lindemann parameter calculated per particle maps local number densities to material phase or particles pattern. We apply the Lindemann histogram method on dynamical colloidal self-assembly experimental data and identify competing patterns.

  18. Chemical potential in active systems: predicting phase equilibrium from bulk equations of state?

    NASA Astrophysics Data System (ADS)

    Paliwal, Siddharth; Rodenburg, Jeroen; van Roij, René; Dijkstra, Marjolein

    2018-01-01

    We derive a microscopic expression for a quantity μ that plays the role of chemical potential of active Brownian particles (ABPs) in a steady state in the absence of vortices. We show that μ consists of (i) an intrinsic chemical potential similar to passive systems, which depends on density and self-propulsion speed, but not on the external potential, (ii) the external potential, and (iii) a newly derived one-body swim potential due to the activity of the particles. Our simulations on ABPs show good agreement with our Fokker-Planck calculations, and confirm that μ (z) is spatially constant for several inhomogeneous active fluids in their steady states in a planar geometry. Finally, we show that phase coexistence of ABPs with a planar interface satisfies not only mechanical but also diffusive equilibrium. The coexistence can be well-described by equating the bulk chemical potential and bulk pressure obtained from bulk simulations for systems with low activity but requires explicit evaluation of the interfacial contributions at high activity.

  19. A Generalized Multi-Phase Framework for Modeling Cavitation in Cryogenic Fluids

    NASA Technical Reports Server (NTRS)

    Dorney, Dan (Technical Monitor); Hosangadi, Ashvin; Ahuja, Vineet

    2003-01-01

    A generalized multi-phase formulation for cavitation in fluids operating at temperatures elevated relative to their critical temperatures is presented. The thermal effects and the accompanying property variations due to phase change are modeled rigorously. Thermal equilibrium is assumed and fluid thermodynamic properties are specified along the saturation line using the NIST-12 databank. Fundamental changes in the physical characteristics of the cavity when thermal effects become pronounced are identified; the cavity becomes more porous, the interface less distinct, and has increased entrainment when temperature variations are present. Quantitative estimates of temperature and pressure depressions in both liquid nitrogen and liquid hydrogen were computed and compared with experimental data of Hord for hydrofoils. Excellent estimates of the leading edge temperature and pressure depression were obtained while the comparisons in the cavity closure region were reasonable. Liquid nitrogen cavities were consistently found to be in thermal equilibrium while liquid hydrogen cavities exhibited small, but distinct, non-equilibrium effects.

  20. Development of solid-gas equilibrium propulsion system for small spacecraft

    NASA Astrophysics Data System (ADS)

    Chujo, Toshihiro; Mori, Osamu; Kubo, Yuki

    2017-11-01

    A phase equilibrium propulsion system is a kind of cold-gas jet in which the phase equilibrium state of the fuel is maintained in a tank and its vapor is ejected when a valve is opened. One such example is a gas-liquid equilibrium propulsion system that uses liquefied gas as fuel. This system was mounted on the IKAROS solar sail and has been demonstrated in orbit. The system has a higher storage efficiency and a lighter configuration than a high-pressure cold-gas jet because the vapor pressure is lower, and is suitable for small spacecraft. However, the system requires a gas-liquid separation device in order to avoid leakage of the liquid, which makes the system complex. As another example of a phase equilibrium propulsion system, we introduce a solid-gas equilibrium propulsion system, which uses a sublimable substance as fuel and ejects its vapor. This system has an even lower vapor pressure and does not require such a separation device, instead requiring only a filter to keep the solid inside the tank. Moreover, the system is much simpler and lighter, making it more suitable for small spacecraft, especially CubeSat-class spacecraft, and the low thrust of the system allows spacecraft motion to be controlled precisely. In addition, the thrust level can be controlled by controlling the temperature of the fuel, which changes the vapor pressure. The present paper introduces the concept of the proposed system, and describes ejection experiments and its evaluation. The basic function of the proposed system is demonstrated in order to verify its usefulness.

  1. Experimental clean combustor program, phase 2

    NASA Technical Reports Server (NTRS)

    Gleason, C. C.; Rogers, D. W.; Bahr, D. W.

    1976-01-01

    The primary objectives of this three-phase program are to develop technology for the design of advanced combustors with significantly lower pollutant emission levels than those of current combustors, and to demonstrate these pollutant emission reductions in CF6-50C engine tests. The purpose of the Phase 2 Program was to further develop the two most promising concepts identified in the Phase 1 Program, the double annular combustor and the radial/axial staged combustor, and to design a combustor and breadboard fuel splitter control for CF6-50 engine demonstration testing in the Phase 3 Program. Noise measurement and alternate fuels addendums to the basic program were conducted to obtain additional experimental data. Twenty-one full annular and fifty-two sector combustor configurations were evaluated. Both combustor types demonstrated the capability for significantly reducing pollutant emission levels. The most promising results were obtained with the double annular combustor. Rig test results corrected to CF-50C engine conditions produced EPA emission parameters for CO, HC, and NOX of 3.4, 0.4, and 4.5 respectively. These levels represent CO, HC, and NOX reductions of 69, 90, and 42 percent respectively from current combustor emission levels. The combustor also met smoke emission level requirements and development engine performance and installation requirements.

  2. Dynamical behaviors of inter-out-of-equilibrium state intervals in Korean futures exchange markets

    NASA Astrophysics Data System (ADS)

    Lim, Gyuchang; Kim, SooYong; Kim, Kyungsik; Lee, Dong-In; Scalas, Enrico

    2008-05-01

    A recently discovered feature of financial markets, the two-phase phenomenon, is utilized to categorize a financial time series into two phases, namely equilibrium and out-of-equilibrium states. For out-of-equilibrium states, we analyze the time intervals at which the state is revisited. The power-law distribution of inter-out-of-equilibrium state intervals is shown and we present an analogy with discrete-time heat bath dynamics, similar to random Ising systems. In the mean-field approximation, this model reduces to a one-dimensional multiplicative process. By varying global and local model parameters, the relevance between volatilities in financial markets and the interaction strengths between agents in the Ising model are investigated and discussed.

  3. Cosmological QCD phase transition in steady non-equilibrium dissipative Hořava–Lifshitz early universe

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

    Khodadi, M., E-mail: M.Khodadi@sbu.ac.ir; Sepangi, H.R., E-mail: hr-sepangi@sbu.ac.ir

    We study the phase transition from quark–gluon plasma to hadrons in the early universe in the context of non-equilibrium thermodynamics. According to the standard model of cosmology, a phase transition associated with chiral symmetry breaking after the electro-weak transition has occurred when the universe was about 1–10 μs old. We focus attention on such a phase transition in the presence of a viscous relativistic cosmological background fluid in the framework of non-detailed balance Hořava–Lifshitz cosmology within an effective model of QCD. We consider a flat Friedmann–Robertson–Walker universe filled with a non-causal and a causal bulk viscous cosmological fluid respectively and investigatemore » the effects of the running coupling constants of Hořava–Lifshitz gravity, λ, on the evolution of the physical quantities relevant to a description of the early universe, namely, the temperature T, scale factor a, deceleration parameter q and dimensionless ratio of the bulk viscosity coefficient to entropy density (ξ)/s . We assume that the bulk viscosity cosmological background fluid obeys the evolution equation of the steady truncated (Eckart) and full version of the Israel–Stewart fluid, respectively. -- Highlights: •In this paper we have studied quark–hadron phase transition in the early universe in the context of the Hořava–Lifshitz model. •We use a flat FRW universe with the bulk viscosity cosmological background fluid obeying the evolution equation of the steady truncated (Eckart) and full version of the Israel–Stewart fluid, respectively.« less

  4. Anchoring the Gas-Phase Acidity Scale from Hydrogen Sulfide to Pyrrole. Experimental Bond Dissociation Energies of Nitromethane, Ethanethiol, and Cyclopentadiene.

    PubMed

    Ervin, Kent M; Nickel, Alex A; Lanorio, Jerry G; Ghale, Surja B

    2015-07-16

    A meta-analysis of experimental information from a variety of sources is combined with statistical thermodynamics calculations to refine the gas-phase acidity scale from hydrogen sulfide to pyrrole. The absolute acidities of hydrogen sulfide, methanethiol, and pyrrole are evaluated from literature R-H bond energies and radical electron affinities to anchor the scale. Relative acidities from proton-transfer equilibrium experiments are used in a local thermochemical network optimized by least-squares analysis to obtain absolute acidities of 14 additional acids in the region. Thermal enthalpy and entropy corrections are applied using molecular parameters from density functional theory, with explicit calculation of hindered rotor energy levels for torsional modes. The analysis reduces the uncertainties of the absolute acidities of the 14 acids to within ±1.2 to ±3.3 kJ/mol, expressed as estimates of the 95% confidence level. The experimental gas-phase acidities are compared with calculations, with generally good agreement. For nitromethane, ethanethiol, and cyclopentadiene, the refined acidities can be combined with electron affinities of the corresponding radicals from photoelectron spectroscopy to obtain improved values of the C-H or S-H bond dissociation energies, yielding D298(H-CH2NO2) = 423.5 ± 2.2 kJ mol(-1), D298(C2H5S-H) = 364.7 ± 2.2 kJ mol(-1), and D298(C5H5-H) = 347.4 ± 2.2 kJ mol(-1). These values represent the best-available experimental bond dissociation energies for these species.

  5. Quantum gambling based on Nash-equilibrium

    NASA Astrophysics Data System (ADS)

    Zhang, Pei; Zhou, Xiao-Qi; Wang, Yun-Long; Liu, Bi-Heng; Shadbolt, Pete; Zhang, Yong-Sheng; Gao, Hong; Li, Fu-Li; O'Brien, Jeremy L.

    2017-06-01

    The problem of establishing a fair bet between spatially separated gambler and casino can only be solved in the classical regime by relying on a trusted third party. By combining Nash-equilibrium theory with quantum game theory, we show that a secure, remote, two-party game can be played using a quantum gambling machine which has no classical counterpart. Specifically, by modifying the Nash-equilibrium point we can construct games with arbitrary amount of bias, including a game that is demonstrably fair to both parties. We also report a proof-of-principle experimental demonstration using linear optics.

  6. Near-equilibrium desorption of helium films

    NASA Astrophysics Data System (ADS)

    Weimer, M.; Housley, R. M.; Goodstein, D. L.

    1987-10-01

    The thermal desorption of helium films in the presence of their equilibrium vapor is studied experimentally for small but rapid departures from ambient temperature. The results are analyzed within the framework of a quasithermodynamic phenomenological model based on detailed balance. Under the usual experimental conditions, isothermal desorption at the temperature of the substrate is a general prediction of the model which seems to be substantiated. For realistic adsorption isotherms the time evolution of the net desorption flux nevertheless appears to be governed by a highly nonlinear equation. In such circumstances, a number of characteristic relaxation times may be identified. These time scales are distinct from, and in general unrelated to, the coverage-dependent mean lifetime of an atom on the surface. To characterize the overall nonlinear evolution towards steady state, a global time scale, defined in terms of both initial- and steady-state properties, is introduced to summarize the experimental data. Internal evidence suggests a criterion for judging when collisions among desorbed atoms are unimportant. When this condition is satisfied, data for near-equilibrium desorption agree well with the predictions of the model. Combining our results with earlier data at higher substrate temperatures and different ambient conditions, the overall picture is consistent with scaling properties implied by the theory. We show that the values of the parameters deduced from a Frenkel-Arrhenius parametrization of the global relaxation times, as well as a variety of other aspects of desorption kinetics, are actually consequences of the shape of the equilibrium adsorption isotherm.

  7. Using nonequilibrium capillary electrophoresis of equilibrium mixtures (NECEEM) for simultaneous determination of concentration and equilibrium constant.

    PubMed

    Kanoatov, Mirzo; Galievsky, Victor A; Krylova, Svetlana M; Cherney, Leonid T; Jankowski, Hanna K; Krylov, Sergey N

    2015-03-03

    Nonequilibrium capillary electrophoresis of equilibrium mixtures (NECEEM) is a versatile tool for studying affinity binding. Here we describe a NECEEM-based approach for simultaneous determination of both the equilibrium constant, K(d), and the unknown concentration of a binder that we call a target, T. In essence, NECEEM is used to measure the unbound equilibrium fraction, R, for the binder with a known concentration that we call a ligand, L. The first set of experiments is performed at varying concentrations of T, prepared by serial dilution of the stock solution, but at a constant concentration of L, which is as low as its reliable quantitation allows. The value of R is plotted as a function of the dilution coefficient, and dilution corresponding to R = 0.5 is determined. This dilution of T is used in the second set of experiments in which the concentration of T is fixed but the concentration of L is varied. The experimental dependence of R on the concentration of L is fitted with a function describing their theoretical dependence. Both K(d) and the concentration of T are used as fitting parameters, and their sought values are determined as the ones that generate the best fit. We have fully validated this approach in silico by using computer-simulated NECEEM electropherograms and then applied it to experimental determination of the unknown concentration of MutS protein and K(d) of its interactions with a DNA aptamer. The general approach described here is applicable not only to NECEEM but also to any other method that can determine a fraction of unbound molecules at equilibrium.

  8. Aerospace Applications of Non-Equilibrium Plasma

    NASA Technical Reports Server (NTRS)

    Blankson, Isaiah M.

    2016-01-01

    Nonequilibrium plasma/non-thermal plasma/cold plasmas are being used in a wide range of new applications in aeronautics, active flow control, heat transfer reduction, plasma-assisted ignition and combustion, noise suppression, and power generation. Industrial applications may be found in pollution control, materials surface treatment, and water purification. In order for these plasma processes to become practical, efficient means of ionization are necessary. A primary challenge for these applications is to create a desired non-equilibrium plasma in air by preventing the discharge from transitioning into an arc. Of particular interest is the impact on simulations and experimental data with and without detailed consideration of non-equilibrium effects, and the consequences of neglecting non-equilibrium. This presentation will provide an assessment of the presence and influence of non-equilibrium phenomena for various aerospace needs and applications. Specific examples to be considered will include the forward energy deposition of laser-induced non-equilibrium plasmoids for sonic boom mitigation, weakly ionized flows obtained from pulsed nanosecond discharges for an annular Hall type MHD generator duct for turbojet energy bypass, and fundamental mechanisms affecting the design and operation of novel plasma-assisted reactive systems in dielectric liquids (water purification, in-pipe modification of fuels, etc.).

  9. FastChem: An ultra-fast equilibrium chemistry

    NASA Astrophysics Data System (ADS)

    Kitzmann, Daniel; Stock, Joachim

    2018-04-01

    FastChem is an equilibrium chemistry code that calculates the chemical composition of the gas phase for given temperatures and pressures. Written in C++, it is based on a semi-analytic approach, and is optimized for extremely fast and accurate calculations.

  10. Analytical and experimental study of high phase order induction motors

    NASA Technical Reports Server (NTRS)

    Klingshirn, Eugene A.

    1989-01-01

    Induction motors having more than three phases were investigated to determine their suitability for electric vehicle applications. The objective was to have a motor with a current rating lower than that of a three-phase motor. The name chosen for these is high phase order (HPO) motors. Motors having six phases and nine phases were given the most attention. It was found that HPO motors are quite suitable for electric vehicles, and for many other applications as well. They have characteristics which are as good as or better than three-phase motors for practically all applications where polyphase induction motors are appropriate. Some of the analysis methods are presented, and several of the equivalent circuits which facilitate the determination of harmonic currents and losses, or currents with unbalanced sources, are included. The sometimes large stator currents due to harmonics in the source voltages are pointed out. Filters which can limit these currents were developed. An analysis and description of these filters is included. Experimental results which confirm and illustrate much of the theory are also included. These include locked rotor test results and full-load performance with an open phase. Also shown are oscillograms which display the reduction in harmonic currents when a filter is used with the experimental motor supplied by a non-sinusoidal source.

  11. Equilibrium Droplets on Deformable Substrates: Equilibrium Conditions.

    PubMed

    Koursari, Nektaria; Ahmed, Gulraiz; Starov, Victor M

    2018-05-15

    Equilibrium conditions of droplets on deformable substrates are investigated, and it is proven using Jacobi's sufficient condition that the obtained solutions really provide equilibrium profiles of both the droplet and the deformed support. At the equilibrium, the excess free energy of the system should have a minimum value, which means that both necessary and sufficient conditions of the minimum should be fulfilled. Only in this case, the obtained profiles provide the minimum of the excess free energy. The necessary condition of the equilibrium means that the first variation of the excess free energy should vanish, and the second variation should be positive. Unfortunately, the mentioned two conditions are not the proof that the obtained profiles correspond to the minimum of the excess free energy and they could not be. It is necessary to check whether the sufficient condition of the equilibrium (Jacobi's condition) is satisfied. To the best of our knowledge Jacobi's condition has never been verified for any already published equilibrium profiles of both the droplet and the deformable substrate. A simple model of the equilibrium droplet on the deformable substrate is considered, and it is shown that the deduced profiles of the equilibrium droplet and deformable substrate satisfy the Jacobi's condition, that is, really provide the minimum to the excess free energy of the system. To simplify calculations, a simplified linear disjoining/conjoining pressure isotherm is adopted for the calculations. It is shown that both necessary and sufficient conditions for equilibrium are satisfied. For the first time, validity of the Jacobi's condition is verified. The latter proves that the developed model really provides (i) the minimum of the excess free energy of the system droplet/deformable substrate and (ii) equilibrium profiles of both the droplet and the deformable substrate.

  12. Towards Non-Equilibrium Dynamics with Trapped Ions

    NASA Astrophysics Data System (ADS)

    Silbert, Ariel; Jubin, Sierra; Doret, Charlie

    2016-05-01

    Atomic systems are superbly suited to the study of non-equilibrium dynamics. These systems' exquisite isolation from environmental perturbations leads to long relaxation times that enable exploration of far-from-equilibrium phenomena. One example of particular relevance to experiments in trapped ion quantum information processing, metrology, and precision spectroscopy is the approach to thermal equilibrium of sympathetically cooled linear ion chains. Suitable manipulation of experimental parameters permits exploration of the quantum-to-classical crossover between ballistic transport and diffusive, Fourier's Law conduction, a topic of interest not only to the trapped ion community but also for the development of microelectronic devices and other nanoscale structures. We present progress towards trapping chains of multiple co-trapped calcium isotopes geared towards measuring thermal equilibration and discuss plans for future experiments in non-equilibrium statistical mechanics. This work is supported by Cottrell College Science Award from the Research Corporation for Science Advancement and by Williams College.

  13. Equilibrium & Nonequilibrium Fluctuation Effects in Biopolymer Networks

    NASA Astrophysics Data System (ADS)

    Kachan, Devin Michael

    Fluctuation-induced interactions are an important organizing principle in a variety of soft matter systems. In this dissertation, I explore the role of both thermal and active fluctuations within cross-linked polymer networks. The systems I study are in large part inspired by the amazing physics found within the cytoskeleton of eukaryotic cells. I first predict and verify the existence of a thermal Casimir force between cross-linkers bound to a semi-flexible polymer. The calculation is complicated by the appearance of second order derivatives in the bending Hamiltonian for such polymers, which requires a careful evaluation of the the path integral formulation of the partition function in order to arrive at the physically correct continuum limit and properly address ultraviolet divergences. I find that cross linkers interact along a filament with an attractive logarithmic potential proportional to thermal energy. The proportionality constant depends on whether and how the cross linkers constrain the relative angle between the two filaments to which they are bound. The interaction has important implications for the synthesis of biopolymer bundles within cells. I model the cross-linkers as existing in two phases: bound to the bundle and free in solution. When the cross-linkers are bound, they behave as a one-dimensional gas of particles interacting with the Casimir force, while the free phase is a simple ideal gas. Demanding equilibrium between the two phases, I find a discontinuous transition between a sparsely and a densely bound bundle. This discontinuous condensation transition induced by the long-ranged nature of the Casimir interaction allows for a similarly abrupt structural transition in semiflexible filament networks between a low cross linker density isotropic phase and a higher cross link density bundle network. This work is supported by the results of finite element Brownian dynamics simulations of semiflexible filaments and transient cross-linkers. I

  14. Spinel cataclasites in 15445 and 72435 - Petrology and criteria for equilibrium

    NASA Technical Reports Server (NTRS)

    Baker, M. B.; Herzberg, C. T.

    1980-01-01

    The problem of establishing the existence of equilibrium among the coexisting phases in the rock is addressed by presenting petrographic and mineral chemistry data on a new spinel cataclasite from 15445 (clast H) and data more extensive than those previously available on two clasts in 72435. Criteria useful in reconstructing the original petrology of these and other spinel cataclasites are analyzed by considering equilibrium among the different phases, that is, the mono- or polymict nature of these cataclasized samples. Finally, the role of impact processes in disturbing the equilibria is discussed.

  15. ASHEE: a compressible, Equilibrium-Eulerian model for volcanic ash plumes

    NASA Astrophysics Data System (ADS)

    Cerminara, M.; Esposti Ongaro, T.; Berselli, L. C.

    2015-10-01

    A new fluid-dynamic model is developed to numerically simulate the non-equilibrium dynamics of polydisperse gas-particle mixtures forming volcanic plumes. Starting from the three-dimensional N-phase Eulerian transport equations (Neri et al., 2003) for a mixture of gases and solid dispersed particles, we adopt an asymptotic expansion strategy to derive a compressible version of the first-order non-equilibrium model (Ferry and Balachandar, 2001), valid for low concentration regimes (particle volume fraction less than 10-3) and particles Stokes number (St, i.e., the ratio between their relaxation time and flow characteristic time) not exceeding about 0.2. The new model, which is called ASHEE (ASH Equilibrium Eulerian), is significantly faster than the N-phase Eulerian model while retaining the capability to describe gas-particle non-equilibrium effects. Direct numerical simulation accurately reproduce the dynamics of isotropic, compressible turbulence in subsonic regime. For gas-particle mixtures, it describes the main features of density fluctuations and the preferential concentration and clustering of particles by turbulence, thus verifying the model reliability and suitability for the numerical simulation of high-Reynolds number and high-temperature regimes in presence of a dispersed phase. On the other hand, Large-Eddy Numerical Simulations of forced plumes are able to reproduce their observed averaged and instantaneous flow properties. In particular, the self-similar Gaussian radial profile and the development of large-scale coherent structures are reproduced, including the rate of turbulent mixing and entrainment of atmospheric air. Application to the Large-Eddy Simulation of the injection of the eruptive mixture in a stratified atmosphere describes some of important features of turbulent volcanic plumes, including air entrainment, buoyancy reversal, and maximum plume height. For very fine particles (St → 0, when non-equilibrium effects are negligible) the

  16. "Non-equilibrium" block copolymer micelles with glassy cores: a predictive approach based on theory of equilibrium micelles.

    PubMed

    Nagarajan, Ramanathan

    2015-07-01

    Micelles generated in water from most amphiphilic block copolymers are widely recognized to be non-equilibrium structures. Typically, the micelles are prepared by a kinetic process, first allowing molecular scale dissolution of the block copolymer in a common solvent that likes both the blocks and then gradually replacing the common solvent by water to promote the hydrophobic blocks to aggregate and create the micelles. The non-equilibrium nature of the micelle originates from the fact that dynamic exchange between the block copolymer molecules in the micelle and the singly dispersed block copolymer molecules in water is suppressed, because of the glassy nature of the core forming polymer block and/or its very large hydrophobicity. Although most amphiphilic block copolymers generate such non-equilibrium micelles, no theoretical approach to a priori predict the micelle characteristics currently exists. In this work, we propose a predictive approach for non-equilibrium micelles with glassy cores by applying the equilibrium theory of micelles in two steps. In the first, we calculate the properties of micelles formed in the mixed solvent while true equilibrium prevails, until the micelle core becomes glassy. In the second step, we freeze the micelle aggregation number at this glassy state and calculate the corona dimension from the equilibrium theory of micelles. The condition when the micelle core becomes glassy is independently determined from a statistical thermodynamic treatment of diluent effect on polymer glass transition temperature. The predictions based on this "non-equilibrium" model compare reasonably well with experimental data for polystyrene-polyethylene oxide diblock copolymer, which is the most extensively studied system in the literature. In contrast, the application of the equilibrium model to describe such a system significantly overpredicts the micelle core and corona dimensions and the aggregation number. The non-equilibrium model suggests ways to

  17. Balance training of the equilibrium organ and its effect on flight strategy

    NASA Technical Reports Server (NTRS)

    Eikemeier, K. D.; Melzig, H. D.; Reicke, N.; Schmidt, W.

    1979-01-01

    An experimental program was conducted with the pendular platform of the Oto-Rhino-Laryngology Clinic, which was developed for the investigation of disturbances of the equilibrium. The equilibrium sense of the glider pilot was emphasized. Results are presented.

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

    NASA Astrophysics Data System (ADS)

    Limmer, David; Chandler, David

    2013-03-01

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

  19. Local thermodynamic equilibrium for globally disequilibrium open systems under stress

    NASA Astrophysics Data System (ADS)

    Podladchikov, Yury

    2016-04-01

    Predictive modeling of far and near equilibrium processes is essential for understanding of patterns formation and for quantifying of natural processes that are never in global equilibrium. Methods of both equilibrium and non-equilibrium thermodynamics are needed and have to be combined. For example, predicting temperature evolution due to heat conduction requires simultaneous use of equilibrium relationship between internal energy and temperature via heat capacity (the caloric equation of state) and disequilibrium relationship between heat flux and temperature gradient. Similarly, modeling of rocks deforming under stress, reactions in system open for the porous fluid flow, or kinetic overstepping of the equilibrium reaction boundary necessarily needs both equilibrium and disequilibrium material properties measured under fundamentally different laboratory conditions. Classical irreversible thermodynamics (CIT) is the well-developed discipline providing the working recipes for the combined application of mutually exclusive experimental data such as density and chemical potential at rest under constant pressure and temperature and viscosity of the flow under stress. Several examples will be presented.

  20. Protonation equilibrium and lipophilicity of olamufloxacin (HSR-903), a newly synthesized fluoroquinolone antibacterial.

    PubMed

    Sun, Jin; Sakai, Shigeko; Tauchi, Yoshihiko; Deguchi, Yoshiharu; Cheng, Gang; Chen, Jimin; Morimoto, Kazuhiro

    2003-09-01

    This study was performed to characterize the protonation equilibrium at the molecular level and pH-dependent lipophilicity of olamufloxacin. The deprotonation fraction of the carboxyl group as a function of pH was specifically calculated at the critical wavelength 294 nm, where UV pH-dependent absorbance of olamufloxacin was independent of the ionized state of the aminopyrrolidinyl amino group but heavily depended on that of the carboxyl moiety. Accordingly, micro-protonation equilibrium could be described using a nonlinear least-squares regression program MULTI. In contrast, macro-protonation equilibrium was depicted at most wavelengths where olamufloxacin absorbance was influenced by ionized states of both proton-binding groups, results coinciding with the former. Furthermore, distribution features of four microspecies in aqueous phase were assessed. The apparent partition coefficient versus pH profile of olamufloxacin showed a parabolic curve in n-octanol/buffer system which reached peak near pH 8, agreeing with the above determined isoelectric point (pI). Ion-pair effect was observed for olamufloxacin under an acidic condition, eliciting experimental values higher than those theoretically calculated, which was similar to ciprofloxacin but not levofloxacin due to amino group type. Moreover, olamufloxacin was moderately lipophilic in comparison with other quinolones, with an apparent partition coefficient of 1.95 at pH 7.4.

  1. Flat-roof phenomenon of dynamic equilibrium phase in the negative bias temperature instability effect on a power MOSFET

    NASA Astrophysics Data System (ADS)

    Zhang, Yue; Zhuo, Qing-Qing; Liu, Hong-Xia; Ma, Xiao-Hua; Hao, Yue

    2014-05-01

    The effect of the static negative bias temperature (NBT) stress on a p-channel power metal—oxide—semiconductor field-effect transistor (MOSFET) is investigated by experiment and simulation. The time evolution of the negative bias temperature instability (NBTI) degradation has the trend predicted by the reaction—diffusion (R—D) model but with an exaggerated time scale. The phenomena of the flat-roof section are observed under various stress conditions, which can be considered as the dynamic equilibrium phase in the R—D process. Based on the simulated results, the variation of the flat-roof section with the stress condition can be explained.

  2. Experimental Investigation of the 1073 K (800 °C) Isothermal Section of the Al-V-Zr Ternary System

    NASA Astrophysics Data System (ADS)

    Zhu, Yude; Ouyang, Xuemei; Yin, Fucheng; Zhao, Manxiu; Lou, Jia

    2018-03-01

    This work is focused on an experimental investigation of the phase equilibria of the Al-V-Zr system at 1073 K (800 °C). The phase equilibria were analyzed using scanning electron microscopy (SEM) coupled with energy-dispersive spectrometry and X-ray diffraction. The results confirmed the presence of twelve three-phase regions and one ternary compound, Τ, which contains 10.0 to 16.5 at. pct Zr, 52.8 to 55.2 at. pct Al, and 29.3 to 36.3 at. pct V. The T phase can be in equilibrium with Al8V5, Al3Zr, Al2Zr, and α-V. The T phase belongs to the tetragonal crystal system with confirmed lattice parameters of a = 0.658531 nm and c = 0.517334 nm. The Al2Zr phase region is extraordinarily large and can be in equilibrium with all the compounds in the Al-Zr and V-Zr systems, with the exception of the AlZr phase.

  3. Instability of quantum equilibrium in Bohm's dynamics

    PubMed Central

    Colin, Samuel; Valentini, Antony

    2014-01-01

    We consider Bohm's second-order dynamics for arbitrary initial conditions in phase space. In principle, Bohm's dynamics allows for ‘extended’ non-equilibrium, with initial momenta not equal to the gradient of phase of the wave function (as well as initial positions whose distribution departs from the Born rule). We show that extended non-equilibrium does not relax in general and is in fact unstable. This is in sharp contrast with de Broglie's first-order dynamics, for which non-standard momenta are not allowed and which shows an efficient relaxation to the Born rule for positions. On this basis, we argue that, while de Broglie's dynamics is a tenable physical theory, Bohm's dynamics is not. In a world governed by Bohm's dynamics, there would be no reason to expect to see an effective quantum theory today (even approximately), in contradiction with observation. PMID:25383020

  4. Equilibrium statistical-thermal models in high-energy physics

    NASA Astrophysics Data System (ADS)

    Tawfik, Abdel Nasser

    2014-05-01

    We review some recent highlights from the applications of statistical-thermal models to different experimental measurements and lattice QCD thermodynamics that have been made during the last decade. We start with a short review of the historical milestones on the path of constructing statistical-thermal models for heavy-ion physics. We discovered that Heinz Koppe formulated in 1948, an almost complete recipe for the statistical-thermal models. In 1950, Enrico Fermi generalized this statistical approach, in which he started with a general cross-section formula and inserted into it, the simplifying assumptions about the matrix element of the interaction process that likely reflects many features of the high-energy reactions dominated by density in the phase space of final states. In 1964, Hagedorn systematically analyzed the high-energy phenomena using all tools of statistical physics and introduced the concept of limiting temperature based on the statistical bootstrap model. It turns to be quite often that many-particle systems can be studied with the help of statistical-thermal methods. The analysis of yield multiplicities in high-energy collisions gives an overwhelming evidence for the chemical equilibrium in the final state. The strange particles might be an exception, as they are suppressed at lower beam energies. However, their relative yields fulfill statistical equilibrium, as well. We review the equilibrium statistical-thermal models for particle production, fluctuations and collective flow in heavy-ion experiments. We also review their reproduction of the lattice QCD thermodynamics at vanishing and finite chemical potential. During the last decade, five conditions have been suggested to describe the universal behavior of the chemical freeze-out parameters. The higher order moments of multiplicity have been discussed. They offer deep insights about particle production and to critical fluctuations. Therefore, we use them to describe the freeze-out parameters

  5. Efficiency of muscle contraction. The chemimechanic equilibrium

    NASA Astrophysics Data System (ADS)

    Becker, E. W.

    1991-10-01

    Although muscle contraction is one of the principal themes of biological research, the exact mechanism whereby the chemical free energy of ATP hydrolysis is converted into mechanical work remains elusive. The high thermodynamic efficiency of the process, above all, is difficult to explain on the basis of present theories. A model of the elementary effect in muscle contraction is proposed which aims at high thermodynamic efficiency based on an approximate equilibrium between chemical and mechanical forces throughout the transfer of free energy. The experimental results described in the literature support the assumption that chemimechanic equilibrium is approximated by a free energy transfer system based on the binding of divalent metal ions to the myosin light chains. Muscle contraction demonstrated without light chains is expected to proceed with a considerably lower efficiency. Free energy transfer systems based on the binding of ions to proteins seem to be widespread in the cell. By establishing an approximate chemimechanic equilibrium, they could facilitate biological reactions considerably and save large amounts of free energy. The concept of chemimechanic equilibrium is seen as a supplementation to the concept of chemiosmotic equilibrium introduced for the membrane transport by P. Mitchell.

  6. A novel multiphysic model for simulation of swelling equilibrium of ionized thermal-stimulus responsive hydrogels

    NASA Astrophysics Data System (ADS)

    Li, Hua; Wang, Xiaogui; Yan, Guoping; Lam, K. Y.; Cheng, Sixue; Zou, Tao; Zhuo, Renxi

    2005-03-01

    In this paper, a novel multiphysic mathematical model is developed for simulation of swelling equilibrium of ionized temperature sensitive hydrogels with the volume phase transition, and it is termed the multi-effect-coupling thermal-stimulus (MECtherm) model. This model consists of the steady-state Nernst-Planck equation, Poisson equation and swelling equilibrium governing equation based on the Flory's mean field theory, in which two types of polymer-solvent interaction parameters, as the functions of temperature and polymer-network volume fraction, are specified with or without consideration of the hydrogen bond interaction. In order to examine the MECtherm model consisting of nonlinear partial differential equations, a meshless Hermite-Cloud method is used for numerical solution of one-dimensional swelling equilibrium of thermal-stimulus responsive hydrogels immersed in a bathing solution. The computed results are in very good agreements with experimental data for the variation of volume swelling ratio with temperature. The influences of the salt concentration and initial fixed-charge density are discussed in detail on the variations of volume swelling ratio of hydrogels, mobile ion concentrations and electric potential of both interior hydrogels and exterior bathing solution.

  7. Reactive solute transport in streams: 1. Development of an equilibrium- based model

    USGS Publications Warehouse

    Runkel, Robert L.; Bencala, Kenneth E.; Broshears, Robert E.; Chapra, Steven C.

    1996-01-01

    An equilibrium-based solute transport model is developed for the simulation of trace metal fate and transport in streams. The model is formed by coupling a solute transport model with a chemical equilibrium submodel based on MINTEQ. The solute transport model considers the physical processes of advection, dispersion, lateral inflow, and transient storage, while the equilibrium submodel considers the speciation and complexation of aqueous species, precipitation/dissolution and sorption. Within the model, reactions in the water column may result in the formation of solid phases (precipitates and sorbed species) that are subject to downstream transport and settling processes. Solid phases on the streambed may also interact with the water column through dissolution and sorption/desorption reactions. Consideration of both mobile (water-borne) and immobile (streambed) solid phases requires a unique set of governing differential equations and solution techniques that are developed herein. The partial differential equations describing physical transport and the algebraic equations describing chemical equilibria are coupled using the sequential iteration approach.

  8. Coupled phase and aqueous species equilibrium of the H 2O-CO 2-NaCl-CaCO 3 system from 0 to 250 °C, 1 to 1000 bar with NaCl concentrations up to saturation of halite

    NASA Astrophysics Data System (ADS)

    Duan, Zhenhao; Li, Dedong

    2008-10-01

    A model is developed for the calculation of coupled phase and aqueous species equilibrium in the H 2O-CO 2-NaCl-CaCO 3 system from 0 to 250 °C, 1 to 1000 bar with NaCl concentrations up to saturation of halite. The vapor-liquid-solid (calcite, halite) equilibrium together with the chemical equilibrium of H +, Na +, Ca 2+, CaHCO3+, Ca(OH) +, OH -, Cl -, HCO3-, CO32-, CO 2(aq) and CaCO 3(aq) in the aqueous liquid phase as a function of temperature, pressure, NaCl concentrations, CO 2(aq) concentrations can be calculated, with accuracy close to those of experiments in the stated T- P- m range, hence calcite solubility, CO 2 gas solubility, alkalinity and pH values can be accurately calculated. The merit and advantage of this model is its predictability, the model was generally not constructed by fitting experimental data. One of the focuses of this study is to predict calcite solubility, with accuracy consistent with the works in previous experimental studies. The resulted model reproduces the following: (1) as temperature increases, the calcite solubility decreases. For example, when temperature increases from 273 to 373 K, calcite solubility decreases by about 50%; (2) with the increase of pressure, calcite solubility increases. For example, at 373 K changing pressure from 10 to 500 bar may increase calcite solubility by as much as 30%; (3) dissolved CO 2 can increase calcite solubility substantially; (4) increasing concentration of NaCl up to 2 m will increase calcite solubility, but further increasing NaCl solubility beyond 2 m will decrease its solubility. The functionality of pH value, alkalinity, CO 2 gas solubility, and the concentrations of many aqueous species with temperature, pressure and NaCl (aq) concentrations can be found from the application of this model. Online calculation is made available on www.geochem-model.org/models/h2o_co2_nacl_caco3/calc.php.

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

    USGS Publications Warehouse

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

    1990-01-01

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

  10. Experimental Investigation of Gas/Slag/Matte/Tridymite Equilibria in the Cu-Fe-O-S-Si System in Controlled Atmospheres: Development of Technique

    NASA Astrophysics Data System (ADS)

    Fallah-Mehrjardi, Ata; Hidayat, Taufiq; Hayes, Peter C.; Jak, Evgueni

    2017-12-01

    The majority of primary pyrometallurgical copper making processes involve the formation of two immiscible liquid phases, i.e., matte product and the slag phase. There are significant gaps and discrepancies in the phase equilibria data of the slag and the matte systems due to issues and difficulties in performing the experiments and phase analysis. The present study aims to develop an improved experimental methodology for accurate characterisation of gas/slag/matte/tridymite equilibria in the Cu-Fe-O-S-Si system under controlled atmospheres. The experiments involve high-temperature equilibration of synthetic mixtures on silica substrates in CO/CO2/SO2/Ar atmospheres, rapid quenching of samples into water, and direct composition measurement of the equilibrium phases using Electron Probe X-ray Microanalysis (EPMA). A four-point-test procedure was applied to ensure the achievement of equilibrium, which included the following: (i) investigation of equilibration as a function of time, (ii) assessment of phase homogeneity, (iii) confirmation of equilibrium by approaching from different starting conditions, and (iv) systematic analysis of the reactions specific to the system. An iterative improved experimental methodology was developed using this four-point-test approach to characterize the complex multi-component, multi-phase equilibria with high accuracy and precision. The present study is a part of a broader overall research program on the characterisation of the multi-component (Cu-Fe-O-S-Si-Al-Ca-Mg), multi-phase (gas/slag/matte/metal/solids) systems with minor elements (Pb, Zn, As, Bi, Sn, Sb, Ag, and Au).

  11. Phase transition kinetics in DIET of vanadium pentoxide. I. Experimental results

    NASA Astrophysics Data System (ADS)

    Ai, R.; Fan, H.-J.; Marks, L. D.

    1993-01-01

    Experimental results of the kinetics of phase transformation in vanadium pentoxide during surface loss of oxygen from electron irradiation are described. Phase transformations under three different regimes were examined: (a) low flux; (b) intermediate flux and (c) high flux. Different phase transformation routes were observed under different fluxes. In a companion paper, numerical calculations are presented demonstrating that these results are due to a mixed interface/diffusion controlled phase transition pumped by surface oxygen loss.

  12. Significance of vapor phase chemical reactions on CVD rates predicted by chemically frozen and local thermochemical equilibrium boundary layer theories

    NASA Technical Reports Server (NTRS)

    Gokoglu, Suleyman A.

    1988-01-01

    This paper investigates the role played by vapor-phase chemical reactions on CVD rates by comparing the results of two extreme theories developed to predict CVD mass transport rates in the absence of interfacial kinetic barrier: one based on chemically frozen boundary layer and the other based on local thermochemical equilibrium. Both theories consider laminar convective-diffusion boundary layers at high Reynolds numbers and include thermal (Soret) diffusion and variable property effects. As an example, Na2SO4 deposition was studied. It was found that gas phase reactions have no important role on Na2SO4 deposition rates and on the predictions of the theories. The implications of the predictions of the two theories to other CVD systems are discussed.

  13. Equilibrium and non-equilibrium controls on the abundances of clumped isotopologues of methane during thermogenic formation in laboratory experiments: Implications for the chemistry of pyrolysis and the origins of natural gases

    NASA Astrophysics Data System (ADS)

    Shuai, Yanhua; Douglas, Peter M. J.; Zhang, Shuichang; Stolper, Daniel A.; Ellis, Geoffrey S.; Lawson, Michael; Lewan, Michael D.; Formolo, Michael; Mi, Jingkui; He, Kun; Hu, Guoyi; Eiler, John M.

    2018-02-01

    Multiply isotopically substituted molecules ('clumped' isotopologues) can be used as geothermometers because their proportions at isotopic equilibrium relative to a random distribution of isotopes amongst all isotopologues are functions of temperature. This has allowed measurements of clumped-isotope abundances to be used to constrain formation temperatures of several natural materials. However, kinetic processes during generation, modification, or transport of natural materials can also affect their clumped-isotope compositions. Herein, we show that methane generated experimentally by closed-system hydrous pyrolysis of shale or nonhydrous pyrolysis of coal yields clumped-isotope compositions consistent with an equilibrium distribution of isotopologues under some experimental conditions (temperature-time conditions corresponding to 'low,' 'mature,' and 'over-mature' stages of catagenesis), but can have non-equilibrium (i.e., kinetically controlled) distributions under other experimental conditions ('high' to 'over-mature' stages), particularly for pyrolysis of coal. Non-equilibrium compositions, when present, lead the measured proportions of clumped species to be lower than expected for equilibrium at the experimental temperature, and in some cases to be lower than a random distribution of isotopes (i.e., negative Δ18 values). We propose that the consistency with equilibrium for methane formed by relatively low temperature pyrolysis reflects local reversibility of isotope exchange reactions involving a reactant or transition state species during demethylation of one or more components of kerogen. Non-equilibrium clumped-isotope compositions occur under conditions where 'secondary' cracking of retained oil in shale or wet gas hydrocarbons (C2-5, especially ethane) in coal is prominent. We suggest these non-equilibrium isotopic compositions are the result of the expression of kinetic isotope effects during the irreversible generation of methane from an alkyl

  14. Theoretical and Experimental Estimations of Volumetric Inductive Phase Shift in Breast Cancer Tissue

    NASA Astrophysics Data System (ADS)

    González, C. A.; Lozano, L. M.; Uscanga, M. C.; Silva, J. G.; Polo, S. M.

    2013-04-01

    Impedance measurements based on magnetic induction for breast cancer detection has been proposed in some studies. This study evaluates theoretical and experimentally the use of a non-invasive technique based on magnetic induction for detection of patho-physiological conditions in breast cancer tissue associated to its volumetric electrical conductivity changes through inductive phase shift measurements. An induction coils-breast 3D pixel model was designed and tested. The model involves two circular coils coaxially centered and a human breast volume centrally placed with respect to the coils. A time-harmonic numerical simulation study addressed the effects of frequency-dependent electrical properties of tumoral tissue on the volumetric inductive phase shift of the breast model measured with the circular coils as inductor and sensor elements. Experimentally; five female volunteer patients with infiltrating ductal carcinoma previously diagnosed by the radiology and oncology departments of the Specialty Clinic for Women of the Mexican Army were measured by an experimental inductive spectrometer and the use of an ergonomic inductor-sensor coil designed to estimate the volumetric inductive phase shift in human breast tissue. Theoretical and experimental inductive phase shift estimations were developed at four frequencies: 0.01, 0.1, 1 and 10 MHz. The theoretical estimations were qualitatively in agreement with the experimental findings. Important increments in volumetric inductive phase shift measurements were evident at 0.01MHz in theoretical and experimental observations. The results suggest that the tested technique has the potential to detect pathological conditions in breast tissue associated to cancer by non-invasive monitoring. Further complementary studies are warranted to confirm the observations.

  15. 2-Pyridinethiol/2-pyridinethione tautomeric equilibrium. A comparative experimental and computational study.

    PubMed

    Moran, Damian; Sukcharoenphon, Kengkaj; Puchta, Ralph; Schaefer, Henry F; Schleyer, Paul V R; Hoff, Carl D

    2002-12-13

    The gas phase and solvent dependent preference of the tautomerization between 2-pyridinethiol (2SH) and 2-pyridinethione (2S) has been assessed using variable temperature Fourier transform infrared (FTIR) experiments, as well as ab initio and density functional theory computations. No spectroscopic evidence (nu(S)(-)(H) stretch) for 2SH was observed in toluene, C(6)D(6), heptane, or methylene chloride solutions. Although, C(s)() 2SH is 2.61 kcal/mol more stable than C(s)() 2S (CCSD(T)/cc-pVTZ//B3LYP/6-311+G(3df,2p)+ZPE), cyclohexane solvent-field relative energies (IPCM-MP2/6-311+G(3df,2p)) favor 2S by 1.96 kcal/mol. This is in accord with the FTIR observations and in quantitative agreement with the -2.6 kcal/mol solution (toluene or C(6)D(6)) calorimetric enthalpy for the 2S/2SH tautomerization favoring the thione. As the intramolecular transition state for the 2S, 2SH tautomerization (2TS) lies 25 (CBS-Q) to 30 kcal/mol (CCSD/cc-pVTZ) higher in energy than either tautomer, tautomerization probably occurs in the hydrogen bonded dimer. The B3LYP/6-311+G(3df,2p) optimized C(2) 2SH dimer is 10.23 kcal/mol + ZPE higher in energy than the C(2)(h)() 2S dimer and is only 2.95 kcal/mol + ZPE lower in energy than the C(2) 2TS dimer transition state. Dimerization equilibrium measurements (FTIR, C(6)D(6)) over the temperature range 22-63 degrees C agree: K(eq)(298) = 165 +/- 40 M(-)(1), DeltaH = -7.0 +/- 0.7 kcal/mol, and DeltaS = -13.4 +/- 3.0 cal/(mol deg). The difference between experimental and B3LYP/6-311+G(3df,2p) [-34.62 cal/(mol deg)] entropy changes is due to solvent effects. The B3LYP/6-311+G(3df,2p) nucleus independent chemical shifts (NICS) are -8.8 and -3.5 ppm 1 A above the 2SH and 2S ring centers, respectively, and the thiol is aromatic. Although the thione is not aromatic, it is stabilized by the thioamide resonance. In solvent, the large 2S dipole, 2-3 times greater than 2SH, favors the thione tautomer and, in conclusion, 2S is thermodynamically more stable

  16. Spontaneous and Flow-Driven Interfacial Phase Change: Dynamics of Microemulsion Formation at the Pore Scale.

    PubMed

    Tagavifar, Mohsen; Xu, Ke; Jang, Sung Hyun; Balhoff, Matthew T; Pope, Gary A

    2017-11-14

    The dynamic behavior of microemulsion-forming water-oil-amphiphiles mixtures is investigated in a 2.5D micromodel. The equilibrium phase behavior of such mixtures is well-understood in terms of macroscopic phase transitions. However, what is less understood and where experimental data are lacking is the coupling between the phase change and the bulk flow. Herein, we study the flow of an aqueous surfactant solution-oil mixture in porous media and analyze the dependence of phase formation and spatial phase configurations on the bulk flow rate. We find that a microemulsion forms instantaneously as a boundary layer at the initial surface of contact between the surfactant solution and oil. The boundary layer is temporally continuous because of the imposed convection. In addition to the imposed flow, we observe spontaneous pulsed Marangoni flows that drag the microemulsion and surfactant solution into the oil stream, forming large (macro)emulsion droplets. The formation of the microemulsion phase at the interface distinguishes the situation from that of the more common Marangoni flow with only two phases present. Additionally, an emulsion forms via liquid-liquid nucleation or the Ouzo effect (i.e., spontaneous emulsification) at low flow rates and via mechanical mixing at high flow rates. With regard to multiphase flow, contrary to the common belief that the microemulsion is the wetting liquid, we observe that the minor oil phase wets the solid surface. We show that a layered flow pattern is formed because of the out-of-equilibrium phase behavior at high volumetric flow rates (order of 2 m/day) where advection is much faster than the diffusive interfacial mass transfer and transverse mixing, which promote equilibrium behavior. At lower flow rates (order of 30 cm/day), however, the dynamic and equilibrium phase behaviors are well-correlated. These results clearly show that the phase change influences the macroscale flow behavior.

  17. Probing equilibrium by nonequilibrium dynamics: Aging in Co/Cr superlattices

    NASA Astrophysics Data System (ADS)

    Binek, Christian

    2013-03-01

    Magnetic aging phenomena are investigated in a structurally ordered Co/Cr superlattice through measurements of magnetization relaxation, magnetic susceptibility, and hysteresis at various temperatures above and below the onset of collective magnetic order. We take advantage of the fact that controlled growth of magnetic multilayer thin films via molecular beam epitaxy allows tailoring the intra and inter-layer exchange interaction and thus enables tuning of magnetic properties including the spin-fluctuation spectra. Tailored nanoscale periodicity in Co/Cr multilayers creates mesoscopic spatial magnetic correlations with slow relaxation dynamics when quenching the system into a nonequilibrium state. Magnetization relaxation in weakly correlated spin systems depends on the microscopic spin-flip time of about 10 ns and is therefore a fast process. The spin correlations in our Co/Cr superlattice bring the magnetization dynamics to experimentally better accessible time scales of seconds or hours. In contrast to spin-glasses, where slow dynamics due to disorder and frustration is a well-known phenomenon, we tune and increase relaxation times in ordered structures. This is achieved by increasing spin-spin correlation between mesoscopically correlated regions rather than individual atomic spins, a concept with some similarity to block spin renormalization. Magnetization transients are measured after exposing the Co/Cr heterostructure to a magnetic set field for various waiting times. Scaling analysis reveals an asymptotic power-law behavior in accordance with a full aging scenario. The temperature dependence of the relaxation exponent shows pronounced anomalies at the equilibrium phase transitions of the antiferromagnetic superstructure and the ferromagnetic to paramagnetic transition of the Co layers. The latter leaves only weak fingerprints in the equilibrium magnetic behavior but gives rise to a prominent change in nonequilibrium properties. Our findings suggest that

  18. Tautomerism, molecular structure, intramolecular hydrogen bond, and enol-enol equilibrium of para halo substituted 4,4,4-trifluoro-1-phenyl-1,3-butanedione; Experimental and theoretical studies

    NASA Astrophysics Data System (ADS)

    Darugar, V. R.; Vakili, M.; Nekoei, A. R.; Tayyari, S. F.; Afzali, R.

    2017-12-01

    Para halo, X = F, Cl, and Br, substitution effect on tautomerism, keto-enol content, molecular structure, intramolecular hydrogen bonding, and enol-enol equilibrium constants of 4,4,4-trifluoro-1-phenyl-1,3-butanedione, known as trifluorobenzoylacetone (TFBA), have been investigated by means of density functional theory calculations and NMR, IR, and UV-Vis spectroscopic methods. Comparing the calculated and experimental results suggests coexisting of two stable cis-enol forms of titled molecules in comparable proportions in the sample. The theoretical and experimental results show that the equilibrium constants between both stable cis-enol forms of the studied molecules are similar, about 1.1-1.2. According to the AIM calculated results performed at the B3LYP/6-311++G∗∗ level, the target para halo molecules have a hydrogen bond strength of about 18.6 kcal/mol, as a medium hydrogen bond, similar to that of TFBA. The theoretical and experimental results indicate that there is no considerable difference between the hydrogen bond strength of the X-substituted titled molecules.

  19. BCS superconductors: The out-of-equilibrium response to a laser pulse

    NASA Astrophysics Data System (ADS)

    Avella, Adolfo

    2018-05-01

    The dynamics of a 2D d-wave BCS superconductor driven out-of-equilibrium by a perpendicularly-impinging polarized laser pulse is analyzed on varying the laser pulse characteristics. The observed effects include: oscillations both in the amplitude and in the phase of the superconducting order parameter, suppression of the superconductivity, but also its enhancement with a strong dependence on all varying parameters and, in particular, on the polarization in plane of the applied vector potential and on the value of its frequency. This study opens up the possibility to distinguish very clearly the behavior of the nodal and anti-nodal non-thermal excitations and to tackle some of the puzzling results of the current experimental scenario in the field.

  20. Sphingomyelinase-Induced Domain Shape Relaxation Driven by Out-of-Equilibrium Changes of Composition

    PubMed Central

    Fanani, Maria Laura; De Tullio, Luisina; Hartel, Steffen; Jara, Jorge; Maggio, Bruno

    2009-01-01

    Abstract Sphingomyelinase (SMase)-induced ceramide (Cer)-enriched domains in a lipid monolayer are shown to result from an out-of-equilibrium situation. This is induced by a change of composition caused by the enzymatic production of Cer in a sphingomyelin (SM) monolayer that leads to a fast SM/Cer demixing into a liquid-condensed (LC), Cer-enriched and a liquid-expanded, SM-enriched phases. The morphological evolution and kinetic dependence of Cer-enriched domains is studied under continuous observation by epifluorescence microscopy. Domain shape annealing is observed from branched to rounded shapes after SMase activity quenching by EDTA, with a decay halftime of ∼10 min. An out-of-equilibrium fast domain growth is not the determinant factor for domain morphology. Domain shape rearrangement in nearly equilibrium conditions result from the counteraction of intradomain dipolar repulsion and line tension, according to McConnell's shape transition theory. Phase separation causes a transient compositional overshoot within the LC phase that implies an increased out-of-equilibrium enrichment of Cer into the LC domains. As a consequence, higher intradomain repulsion leads to transient branched structures that relax to rounded shapes by lowering the proportion of Cer in the domain to equilibrium values. The fast action of SMase can be taken as a compositional perturbation that brings about important consequences for the surface organization. PMID:18849413

  1. Experimental investigation of condensation predictions for dust-enriched systems

    NASA Astrophysics Data System (ADS)

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

    2014-10-01

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

  2. Discovery of a meta-stable Al-Sm phase with unknown stoichiometry using a genetic algorithm

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

    Zhang, Feng; McBrearty, Ian; Ott, R. T.

    Unknown crystalline phases observed during the devitrification process of glassy metal alloys significantly limit our ability to understand and control phase selection in these systems driven far from equilibrium. Here, we report a new meta-stable Al 5Sm phase identified by simultaneously searching Al-rich compositions of the Al–Sm system, using an efficient genetic algorithm. The excellent match between calculated and experimental X-ray diffraction patterns confirms that this new phase appeared in the crystallization of melt-spun Al 90Sm 10 alloys.

  3. Criticality in a non-equilibrium, driven system: charged colloidal rods (fd-viruses) in electric fields.

    PubMed

    Kang, K; Dhont, J K G

    2009-11-01

    Experiments on suspensions of charged colloidal rods (fd-virus particles) in external electric fields are performed, which show that a non-equilibrium critical point can be identified. Several transition lines of field-induced phases and states meet at this point and it is shown that there is a length- and time-scale which diverge at the non-equilibrium critical point. The off-critical and critical behavior is characterized, with both power law and logarithmic divergencies. These experiments show that analogous features of the classical, critical divergence of correlation lengths and relaxation times in equilibrium systems are also exhibited by driven systems that are far out of equilibrium, related to phases/states that do not exist in the absence of the external field.

  4. Out-of-Equilibrium Dynamics of Colloidal Particles at Interfaces

    NASA Astrophysics Data System (ADS)

    Wang, Anna

    It is widely assumed that when colloidal particles adsorb to a fluid-fluid interface, they reach equilibrium rapidly. Recently, however, Kaz et al. [Nature Materials, 11, 138-142 (2012)] found that a variety of functionalised latex microspheres breaching an aqueous phase-oil interface relax logarithmically with time toward equilibrium. The relaxation is so slow that the time projected for the particles to reach the equilibrium contact angle of 110° is months--far longer than typical experimental timescales. In this thesis, we seek to understand the out-of-equilibrium behaviour of particles near interfaces. Because contact line pinning is likely an extra source of dissipation at interfaces, we start with experiments to elucidate the origins of contact-line pinning and find that polymer hairs on aqueous dispersed polymer particles strongly pin the contact-line. For particles without polymer hairs, nanoscale surface roughness can also pin the contact-line, though with a lower energy. We then extend our digital holography capabilities to track non-spherical particles. We demonstrate that we can track the centre-of-mass of a colloidal spherocylinder to a precision of 35 nm in all three dimensions and its orientation to a precision of 1.5°. Furthermore, the measured translational and rotational diffusion coefficients for the spherocylinders agree with hydrodynamic predictions to within 0.3%. This new functionality enables us to track colloidal ellipsoids and spherocylinders as they breach interfaces. By comparing the adsorption trajectories of the non-spherical particles to what is predicted from energy minimisation, we learn that contact-line pinning affects not just the timescales of breaching, but also the pathway to equilibrium. In fact, a particle's path to equilibrium can have complications even before the particle breaches the interface. Some particles are attracted to the interface, but stay within a few nanometers without ever breaching. We refer to this

  5. Equilibrium of particle nitrite with gas phase HONO: Tropospheric measurements in the high Arctic during polar sunrise

    NASA Astrophysics Data System (ADS)

    Li, Shao-Meng

    1994-12-01

    Gas phase HONO(g) and nitrite in particles of <5-μm size were measured in the troposphere during the Polar Sunrise Experiment at Alert, Northwest Territories, Canada, during January 19 to April 20, 1992, using denuder-filter pack sampling and IC-UV detection. The measurements indicated that HONO(g) existed at concentrations of up to 70 ppt before polar sunrise but gradually decreased to 5-10 ppt after sunrise. The calculated OH formation rate from HONO(g) photolysis was greater than from the photolysis of both O3 and CH2O by more than one order of magnitude during the sunlit period and led to moderately high levels of OH, e.g., 3×105 molecules cm-3 OH at noontime on April 5. Particle nitrite measurements showed a gradual increase in concentrations with increasing solar insolation, but the concentrations were generally less than 10 ppt. The pH and the sulfate molar concentrations of the particles and the water vapor mixing ratio indicate that the particles were highly acidic being approximately 70% (W/W) H2SO4 solution. In such highly concentrated H2SO4 solution, most particle nitrite should exist as hydrated nitrosonium ion H2ONO+. Taking this into consideration, the particle nitrite was in an approximate equilibrium with the measured HONO(g). This equilibrium, with HONO(g) rapidly photolyzed, was a good indication that the particles were effective sources of HONO(g) and implied rapid production of particle N(+III) during this period. Two possible pathways leading to the formation of particle N(+III) species are suggested, i.e., reduction of HNO3(aq) by SO2(g) and reduction of NO3-; (aq) by Br- (aq). However, N2O5 reaction with NaBr cannot be ruled out as the alternative HONO(g) formation mechanism which bypasses the equilibrium.

  6. Far-from-Equilibrium Route to Superthermal Light in Bimodal Nanolasers

    NASA Astrophysics Data System (ADS)

    Marconi, Mathias; Javaloyes, Julien; Hamel, Philippe; Raineri, Fabrice; Levenson, Ariel; Yacomotti, Alejandro M.

    2018-02-01

    Microscale and nanoscale lasers inherently exhibit rich photon statistics due to complex light-matter interaction in a strong spontaneous emission noise background. It is well known that they may display superthermal fluctuations—photon superbunching—in specific situations due to either gain competition, leading to mode-switching instabilities, or carrier-carrier coupling in superradiant microcavities. Here we show a generic route to superbunching in bimodal nanolasers by preparing the system far from equilibrium through a parameter quench. We demonstrate, both theoretically and experimentally, that transient dynamics after a short-pump-pulse-induced quench leads to heavy-tailed superthermal statistics when projected onto the weak mode. We implement a simple experimental technique to access the probability density functions that further enables quantifying the distance from thermal equilibrium via the thermodynamic entropy. The universality of this mechanism relies on the far-from-equilibrium dynamical scenario, which can be mapped to a fast cooling process of a suspension of Brownian particles in a liquid. Our results open up new avenues to mold photon statistics in multimode optical systems and may constitute a test bed to investigate out-of-equilibrium thermodynamics using micro or nanocavity arrays.

  7. Determination of the partition coefficient between dissolved organic carbon and seawater using differential equilibrium kinetics.

    PubMed

    Kim, Du Yung; Kwon, Jung-Hwan

    2018-05-04

    Because the freely dissolved fraction of highly hydrophobic organic chemicals is bioavailable, knowing the partition coefficient between dissolved organic carbon and water (K DOCw ) is crucial to estimate the freely dissolved fraction from the total concentration. A kinetic method was developed to obtain K DOCw that required a shorter experimental time than equilibrium methods. The equilibrium partition coefficients of four polychlorinated biphenyls (PCBs) (2,4,4'-trichlorobiphenyl (PCB 28), 2,2',3,5'-tetrachlorobiphenyl (PCB 44), 2,2',4,5,5'-pentachlorobiphenyl (PCB 101), and 2,2',4,4',5,5'-hexachlorobiphenyl (PCB 153)) between dissolved organic carbon and seawater (K DOCsw ) were determined using seawater samples from the Korean coast. The log K DOCsw values of PCB 28 were measured by equilibrating PCB 28, the least hydrophobic congener, with seawater samples, and the values ranged from 6.60 to 7.20. For the more hydrophobic PCBs (PCB 44, PCB 101, and PCB 153), kinetic experiments were conducted to determine the sorption rate constants (k 2 ) and their log K DOCsw values were obtained by comparing their k 2 with that of PCB 28. The calculated log K DOCsw values were 6.57-7.35 for PCB 44, 6.23-7.44 for PCB 101, and 6.35-7.73 for PCB 153. The validity of the proposed method was further confirmed using three less hydrophobic polycyclic aromatic hydrocarbons. This kinetic method shortened the experimental time to obtain the K DOCsw values of the more hydrophobic PCBs, which did not reach phase equilibrium. Copyright © 2018 Elsevier Ltd. All rights reserved.

  8. Experimental Investigation of Gas/Slag/Matte/Spinel Equilibria in the Cu-Fe-O-S-Si System at 1473 K (1200 °C) and P(SO2) = 0.25 atm

    NASA Astrophysics Data System (ADS)

    Hidayat, Taufiq; Fallah-Mehrjardi, Ata; Hayes, Peter C.; Jak, Evgueni

    2018-04-01

    New experimental data were obtained on the gas/slag/matte/spinel equilibria in the Cu-Fe-O-S-Si system at 1473 K (1200 °C) and P(SO2) = 0.25 atm covering Cu concentrations in matte between 42 and 78 wt pct Cu. Accurate measurements were obtained using high-temperature equilibration and the rapid quenching technique, followed by electron-probe X-ray microanalysis of equilibrium phase compositions. The use of spinel substrates made to support the samples ensures equilibrium with this primary phase solid, eliminates crucible contamination, and facilitates direct gas-condensed phase equilibrium and high quenching rates. Particular attention was given to the confirmation of the achievement of equilibrium. The results quantify the relationship between Cu in matte and oxygen partial pressure, sulfur in matte, oxygen in matte, Fe/SiO2 at slag liquidus, sulfur in slag, and dissolved copper in slag.

  9. Acid-base equilibrium dynamics in methanol and dimethyl sulfoxide probed by two-dimensional infrared spectroscopy.

    PubMed

    Lee, Chiho; Son, Hyewon; Park, Sungnam

    2015-07-21

    Two-dimensional infrared (2DIR) spectroscopy, which has been proven to be an excellent experimental method for studying thermally-driven chemical processes, was successfully used to investigate the acid dissociation equilibrium of HN3 in methanol (CH3OH) and dimethyl sulfoxide (DMSO) for the first time. Our 2DIR experimental results indicate that the acid-base equilibrium occurs on picosecond timescales in CH3OH but that it occurs on much longer timescales in DMSO. Our results imply that the different timescales of the acid-base equilibrium originate from different proton transfer mechanisms between the acidic (HN3) and basic (N3(-)) species in CH3OH and DMSO. In CH3OH, the acid-base equilibrium is assisted by the surrounding CH3OH molecules which can directly donate H(+) to N3(-) and accept H(+) from HN3 and the proton migrates through the hydrogen-bonded chain of CH3OH. On the other hand, the acid-base equilibrium in DMSO occurs through the mutual diffusion of HN3 and N3(-) or direct proton transfer. Our 2DIR experimental results corroborate different proton transfer mechanisms in the acid-base equilibrium in protic (CH3OH) and aprotic (DMSO) solvents.

  10. Experimental demonstration of a phased-array antenna optically controlled with phase and time delays.

    PubMed

    Dolfi, D; Joffre, P; Antoine, J; Huignard, J P; Philippet, D; Granger, P

    1996-09-10

    The experimental demonstration and the far-field pattern characterization of an optically controlled phased-array antenna are described. It operates between 2.5 and 3.5 GHz and is made of 16 radiating elements. The optical control uses a two-dimensional architecture based on free-space propagation and on polarization switching by N spatial light modulators of p × p pixels. It provides 2(N-1) time-delay values and an analog control of the 0 to 2π phase for each of the p × p signals feeding the antenna (N = 5, p = 4).

  11. Experimental study of the replacement of calcite by calcium sulphates

    NASA Astrophysics Data System (ADS)

    Ruiz-Agudo, E.; Putnis, C. V.; Hövelmann, J.; Álvarez-Lloret, P.; Ibáñez-Velasco, A.; Putnis, A.

    2015-05-01

    Among the most relevant mineral replacement reactions are those involving sulphates and carbonates, which have important geological and technological implications. Here it is shown experimentally that during the interaction of calcite (CaCO3) cleavage surfaces with sulphate-bearing acidic solutions, calcite is ultimately replaced by gypsum (CaSO4 2H2O) and anhydrite (CaSO4), depending on the reaction temperature. Observations suggest that this occurs most likely via an interface-coupled dissolution-precipitation reaction, in which the substrate is replaced pseudomorphically by the product. At 120 and 200 °C gypsum and/or bassanite (CaSO4·0.5H2O) form as precursor phases for the thermodynamically stable anhydrite. Salinity promotes the formation of less hydrated precursor phases during the replacement of calcite by anhydrite. The reaction stops before equilibrium with respect to calcite is reached and during the course of the reaction most of the bulk solutions are undersaturated with respect to the precipitating phase(s). A mechanism consisting of the dissolution of small amounts of solid in a thin layer of fluid at the mineral-fluid interface and the subsequent precipitation of the product phase from this layer is in agreement with these observations. PHREEQC simulations performed in the framework of this mechanism highlight the relevance of transport and surface reaction kinetics on the volume change associated with the CaCO3-CaSO4 replacement. Under our experimental conditions, this reaction occurs with a positive volume change, which ultimately results in passivation of the unreacted substrate before calcite attains equilibrium with respect to the bulk solution.

  12. Coherent and incoherent phase stabilities of thermoelectric rocksalt IV-VI semiconductor alloys

    NASA Astrophysics Data System (ADS)

    Doak, Jeff W.; Wolverton, C.

    2012-10-01

    Nanostructures formed by phase separation improve the thermoelectric figure of merit in lead chalcogenide semiconductor alloys, with coherent nanostructures giving larger improvements than incoherent nanostructures. However, large coherency strains in these alloys drastically alter the thermodynamics of phase stability. Incoherent phase stability can be easily inferred from an equilibrium phase diagram, but coherent phase stability is more difficult to assess experimentally. Therefore, we use density functional theory calculations to investigate the coherent and incoherent phase stability of the IV-VI rocksalt semiconductor alloy systems Pb(S,Te), Pb(Te,Se), Pb(Se,S), (Pb,Sn)Te, (Sn,Ge)Te, and (Ge,Pb)Te. Here we use the term coherent to indicate that there is a common and unbroken lattice between the phases under consideration, and we use the term incoherent to indicate that the lattices of coexisting phases are unconstrained and allowed to take on equilibrium volumes. We find that the thermodynamic ground state of all of the IV-VI pseudobinary systems studied is incoherent phase separation. We also find that the coherency strain energy, previously neglected in studies of these IV-VI alloys, is lowest along [111] (in contrast to most fcc metals) and is a large fraction of the thermodynamic driving force for incoherent phase separation in all systems. The driving force for coherent phase separation is significantly reduced, and we find that coherent nanostructures can only form at low temperatures where kinetics may prohibit their precipitation. Furthermore, by calculating the energies of ordered structures for these systems we find that the coherent phase stability of most IV-VI systems favors ordering over spinodal decomposition. Our results suggest that experimental reports of spinodal decomposition in the IV-VI rocksalt alloys should be re-examined.

  13. Discovery of a meta-stable Al–Sm phase with unknown stoichiometry using a genetic algorithm

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

    Zhang, Feng; McBrearty, Ian; Ott, R T

    Unknown crystalline phases observed during the devitrification process of glassy metal alloys significantly limit our ability to understand and control phase selection in these systems driven far from equilibrium. Here, we report a new meta-stable Al5Sm phase identified by simultaneously searching Al-rich compositions of the Al-Sm system, using an efficient genetic algorithm. The excellent match between calculated and experimental X-ray diffraction patterns confirms that this new phase appeared in the crystallization of melt-spun Al90Sm10 alloys. Published by Elsevier Ltd. on behalf of Acta Materialia Inc.

  14. Thermal Equilibrium of a Macroscopic Quantum System in a Pure State.

    PubMed

    Goldstein, Sheldon; Huse, David A; Lebowitz, Joel L; Tumulka, Roderich

    2015-09-04

    We consider the notion of thermal equilibrium for an individual closed macroscopic quantum system in a pure state, i.e., described by a wave function. The macroscopic properties in thermal equilibrium of such a system, determined by its wave function, must be the same as those obtained from thermodynamics, e.g., spatial uniformity of temperature and chemical potential. When this is true we say that the system is in macroscopic thermal equilibrium (MATE). Such a system may, however, not be in microscopic thermal equilibrium (MITE). The latter requires that the reduced density matrices of small subsystems be close to those obtained from the microcanonical, equivalently the canonical, ensemble for the whole system. The distinction between MITE and MATE is particularly relevant for systems with many-body localization for which the energy eigenfuctions fail to be in MITE while necessarily most of them, but not all, are in MATE. We note, however, that for generic macroscopic systems, including those with MBL, most wave functions in an energy shell are in both MATE and MITE. For a classical macroscopic system, MATE holds for most phase points on the energy surface, but MITE fails to hold for any phase point.

  15. Calculation of individual isotope equilibrium constants for implementation in geochemical models

    USGS Publications Warehouse

    Thorstenson, Donald C.; Parkhurst, David L.

    2002-01-01

    Theory is derived from the work of Urey to calculate equilibrium constants commonly used in geochemical equilibrium and reaction-transport models for reactions of individual isotopic species. Urey showed that equilibrium constants of isotope exchange reactions for molecules that contain two or more atoms of the same element in equivalent positions are related to isotope fractionation factors by , where is n the number of atoms exchanged. This relation is extended to include species containing multiple isotopes, for example and , and to include the effects of nonideality. The equilibrium constants of the isotope exchange reactions provide a basis for calculating the individual isotope equilibrium constants for the geochemical modeling reactions. The temperature dependence of the individual isotope equilibrium constants can be calculated from the temperature dependence of the fractionation factors. Equilibrium constants are calculated for all species that can be formed from and selected species containing , in the molecules and the ion pairs with where the subscripts g, aq, l, and s refer to gas, aqueous, liquid, and solid, respectively. These equilibrium constants are used in the geochemical model PHREEQC to produce an equilibrium and reaction-transport model that includes these isotopic species. Methods are presented for calculation of the individual isotope equilibrium constants for the asymmetric bicarbonate ion. An example calculates the equilibrium of multiple isotopes among multiple species and phases.

  16. Equilibrium aluminium hydroxo-oxalate phases during initial clay formation; H +-Al 3+-oxalic acid-Na + system

    NASA Astrophysics Data System (ADS)

    Bilinski, Halka; Horvath, Laszlo; Ingri, Nils; Sjöberg, Staffan

    1986-09-01

    The conditions necessary for initial clay formation have been studied in different model systems comprising different organic acids besides Si and Al. In the present paper the solid phases and the precipitation boundary characterizing the subsystem H +-Al 3+-oxalic acid (H 2L) are discussed. pH and tyndallometric measurements were performed in an ionic medium of 0.6 M Na(Cl) at 25 °C. The two phases Al 3(OH) 7(C 2O 4) · 3H 2O (phase I) and NaAl(OH) 2(C 2O 4) · 3H 2O (phase II) determine the precipitation boundary. The following formation constants for the two phases were deduced: lgβ1 = lg([ Al3+] -3[ H2C2O4] -1[ H+] 9 = -21.87 ± 0.08 and lgβ11 = lg([ Al3+] -1[ H2C2O4] -1[ H+] 4 = -5.61 ± 0.06. Phase I exists in the range [ Al] tot≥ 10 -4.4moldm-3,[ H2C2O4] tot ≥ 10 -4.9moldm-3 and at pH < 6.8, thus being a possible precipitate in oxalic-rich natural waters. The more soluble sodium phase is unlikely to exist in natural waters. The two phases are metastable relative to crystalline gibbsite and may be considered as the first precipitation step in the transition from aqueous Al oxalates down to stable Al hydroxide. Model calculations illustrating these competing hydrolysis-complexation reactions are discussed in terms of predominance and speciation diagrams. The solid phases have been characterized by X-ray analysis of powders, TGA and IR spectra, and tentative structures are proposed. Phase I seems to be an octahedral layer structure, in which 3/5 of the octahedral sites between two close packed oxygen sheets are occupied by Al 3+ and the oxalate ion acts as a bridge ligand between two aluminium atoms. Phase II forms a more open sheet structure and has ion exchange properties. Powder data for a phase crystallized from the studied solution after a year are also presented. This phase, Na 4Al 2(OH) 2(C 2O 4) 4 · 10H 2O, supports the results from the equilibrium analysis of recent solution data by SJöBERG and ÖHMAN (1985), who have found the dinuclear

  17. Equilibrium and non-equilibrium controls on the abundances of clumped isotopologues of methane during thermogenic formation in laboratory experiments: Implications for the chemistry of pyrolysis and the origins of natural gases

    USGS Publications Warehouse

    Shuai, Yanhua; Douglas, Peter M.J.; Zhang, Shuichang; Stolper, Daniel A.; Ellis, Geoffrey S.; Lawson, Michael; Lewan, Michael; Formolo, Michael; Mi, Jingkui; He, Kun; Hu, Guoyi; Eiler, John M.

    2018-01-01

    Multiply isotopically substituted molecules (‘clumped’ isotopologues) can be used as geothermometers because their proportions at isotopic equilibrium relative to a random distribution of isotopes amongst all isotopologues are functions of temperature. This has allowed measurements of clumped-isotope abundances to be used to constrain formation temperatures of several natural materials. However, kinetic processes during generation, modification, or transport of natural materials can also affect their clumped-isotope compositions. Herein, we show that methane generated experimentally by closed-system hydrous pyrolysis of shale or nonhydrous pyrolysis of coal yields clumped-isotope compositions consistent with an equilibrium distribution of isotopologues under some experimental conditions (temperature–time conditions corresponding to ‘low,’ ‘mature,’ and ‘over-mature’ stages of catagenesis), but can have non-equilibrium (i.e., kinetically controlled) distributions under other experimental conditions (‘high’ to ‘over-mature’ stages), particularly for pyrolysis of coal. Non-equilibrium compositions, when present, lead the measured proportions of clumped species to be lower than expected for equilibrium at the experimental temperature, and in some cases to be lower than a random distribution of isotopes (i.e., negative Δ18 values). We propose that the consistency with equilibrium for methane formed by relatively low temperature pyrolysis reflects local reversibility of isotope exchange reactions involving a reactant or transition state species during demethylation of one or more components of kerogen. Non-equilibrium clumped-isotope compositions occur under conditions where ‘secondary’ cracking of retained oil in shale or wet gas hydrocarbons (C2-5, especially ethane) in coal is prominent. We suggest these non-equilibrium isotopic compositions are the result of the expression of kinetic isotope effects during the irreversible generation

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

    USGS Publications Warehouse

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

    1996-01-01

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

  19. Evaluating equilibrium and non-equilibrium transport of bromide and isoproturon in disturbed and undisturbed soil columns.

    PubMed

    Dousset, S; Thevenot, M; Pot, V; Simunek, J; Andreux, F

    2007-12-07

    In this study, displacement experiments of isoproturon were conducted in disturbed and undisturbed columns of a silty clay loam soil under similar rainfall intensities. Solute transport occurred under saturated conditions in the undisturbed soil and under unsaturated conditions in the sieved soil because of a greater bulk density of the compacted undisturbed soil compared to the sieved soil. The objective of this work was to determine transport characteristics of isoproturon relative to bromide tracer. Triplicate column experiments were performed with sieved (structure partially destroyed to simulate conventional tillage) and undisturbed (structure preserved) soils. Bromide experimental breakthrough curves were analyzed using convective-dispersive and dual-permeability (DP) models (HYDRUS-1D). Isoproturon breakthrough curves (BTCs) were analyzed using the DP model that considered either chemical equilibrium or non-equilibrium transport. The DP model described the bromide elution curves of the sieved soil columns well, whereas it overestimated the tailing of the bromide BTCs of the undisturbed soil columns. A higher degree of physical non-equilibrium was found in the undisturbed soil, where 56% of total water was contained in the slow-flow matrix, compared to 26% in the sieved soil. Isoproturon BTCs were best described in both sieved and undisturbed soil columns using the DP model combined with the chemical non-equilibrium. Higher degradation rates were obtained in the transport experiments than in batch studies, for both soils. This was likely caused by hysteresis in sorption of isoproturon. However, it cannot be ruled out that higher degradation rates were due, at least in part, to the adopted first-order model. Results showed that for similar rainfall intensity, physical and chemical non-equilibrium were greater in the saturated undisturbed soil than in the unsaturated sieved soil. Results also suggested faster transport of isoproturon in the undisturbed soil due

  20. Evaluating equilibrium and non-equilibrium transport of bromide and isoproturon in disturbed and undisturbed soil columns

    NASA Astrophysics Data System (ADS)

    Dousset, S.; Thevenot, M.; Pot, V.; Šimunek, J.; Andreux, F.

    2007-12-01

    In this study, displacement experiments of isoproturon were conducted in disturbed and undisturbed columns of a silty clay loam soil under similar rainfall intensities. Solute transport occurred under saturated conditions in the undisturbed soil and under unsaturated conditions in the sieved soil because of a greater bulk density of the compacted undisturbed soil compared to the sieved soil. The objective of this work was to determine transport characteristics of isoproturon relative to bromide tracer. Triplicate column experiments were performed with sieved (structure partially destroyed to simulate conventional tillage) and undisturbed (structure preserved) soils. Bromide experimental breakthrough curves were analyzed using convective-dispersive and dual-permeability (DP) models (HYDRUS-1D). Isoproturon breakthrough curves (BTCs) were analyzed using the DP model that considered either chemical equilibrium or non-equilibrium transport. The DP model described the bromide elution curves of the sieved soil columns well, whereas it overestimated the tailing of the bromide BTCs of the undisturbed soil columns. A higher degree of physical non-equilibrium was found in the undisturbed soil, where 56% of total water was contained in the slow-flow matrix, compared to 26% in the sieved soil. Isoproturon BTCs were best described in both sieved and undisturbed soil columns using the DP model combined with the chemical non-equilibrium. Higher degradation rates were obtained in the transport experiments than in batch studies, for both soils. This was likely caused by hysteresis in sorption of isoproturon. However, it cannot be ruled out that higher degradation rates were due, at least in part, to the adopted first-order model. Results showed that for similar rainfall intensity, physical and chemical non-equilibrium were greater in the saturated undisturbed soil than in the unsaturated sieved soil. Results also suggested faster transport of isoproturon in the undisturbed soil due

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

    PubMed

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

    2005-05-12

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

  2. On the equilibrium charge density at tilt grain boundaries

    NASA Astrophysics Data System (ADS)

    Srikant, V.; Clarke, D. R.

    1998-05-01

    The equilibrium charge density and free energy of tilt grain boundaries as a function of their misorientation is computed using a Monte Carlo simulation that takes into account both the electrostatic and configurational energies associated with charges at the grain boundary. The computed equilibrium charge density increases with the grain-boundary angle and approaches a saturation value. The equilibrium charge density at large-angle grain boundaries compares well with experimental values for large-angle tilt boundaries in GaAs. The computed grain-boundary electrostatic energy is in agreement with the analytical solution to a one-dimensional Poisson equation at high donor densities but indicates that the analytical solution overestimates the electrostatic energy at lower donor densities.

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

    PubMed

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

    2005-03-01

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

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

    NASA Astrophysics Data System (ADS)

    Moortgat, Joachim; Firoozabadi, Abbas

    2013-10-01

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

  5. Experimental Bayesian Quantum Phase Estimation on a Silicon Photonic Chip.

    PubMed

    Paesani, S; Gentile, A A; Santagati, R; Wang, J; Wiebe, N; Tew, D P; O'Brien, J L; Thompson, M G

    2017-03-10

    Quantum phase estimation is a fundamental subroutine in many quantum algorithms, including Shor's factorization algorithm and quantum simulation. However, so far results have cast doubt on its practicability for near-term, nonfault tolerant, quantum devices. Here we report experimental results demonstrating that this intuition need not be true. We implement a recently proposed adaptive Bayesian approach to quantum phase estimation and use it to simulate molecular energies on a silicon quantum photonic device. The approach is verified to be well suited for prethreshold quantum processors by investigating its superior robustness to noise and decoherence compared to the iterative phase estimation algorithm. This shows a promising route to unlock the power of quantum phase estimation much sooner than previously believed.

  6. Studying non-equilibrium many-body dynamics using one-dimensional Bose gases

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

    Langen, Tim; Gring, Michael; Kuhnert, Maximilian

    2014-12-04

    Non-equilibrium dynamics of isolated quantum many-body systems play an important role in many areas of physics. However, a general answer to the question of how these systems relax is still lacking. We experimentally study the dynamics of ultracold one-dimensional (1D) Bose gases. This reveals the existence of a quasi-steady prethermalized state which differs significantly from the thermal equilibrium of the system. Our results demonstrate that the dynamics of non-equilibrium quantum many-body systems is a far richer process than has been assumed in the past.

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

    NASA Astrophysics Data System (ADS)

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

    2016-02-01

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

  8. Experimental formation enthalpies for intermetallic phases and other inorganic compounds

    PubMed Central

    Kim, George; Meschel, S. V.; Nash, Philip; Chen, Wei

    2017-01-01

    The standard enthalpy of formation of a compound is the energy associated with the reaction to form the compound from its component elements. The standard enthalpy of formation is a fundamental thermodynamic property that determines its phase stability, which can be coupled with other thermodynamic data to calculate phase diagrams. Calorimetry provides the only direct method by which the standard enthalpy of formation is experimentally measured. However, the measurement is often a time and energy intensive process. We present a dataset of enthalpies of formation measured by high-temperature calorimetry. The phases measured in this dataset include intermetallic compounds with transition metal and rare-earth elements, metal borides, metal carbides, and metallic silicides. These measurements were collected from over 50 years of calorimetric experiments. The dataset contains 1,276 entries on experimental enthalpy of formation values and structural information. Most of the entries are for binary compounds but ternary and quaternary compounds are being added as they become available. The dataset also contains predictions of enthalpy of formation from first-principles calculations for comparison. PMID:29064466

  9. Linear viscoelasticity and thermorheological simplicity of n-hexadecane fluids under oscillatory shear via non-equilibrium molecular dynamics simulations.

    PubMed

    Tseng, Huan-Chang; Wu, Jiann-Shing; Chang, Rong-Yeu

    2010-04-28

    A small amplitude oscillatory shear flows with the classic characteristic of a phase shift when using non-equilibrium molecular dynamics simulations for n-hexadecane fluids. In a suitable range of strain amplitude, the fluid possesses significant linear viscoelastic behavior. Non-linear viscoelastic behavior of strain thinning, which means the dynamic modulus monotonously decreased with increasing strain amplitudes, was found at extreme strain amplitudes. Under isobaric conditions, different temperatures strongly affected the range of linear viscoelasticity and the slope of strain thinning. The fluid's phase states, containing solid-, liquid-, and gel-like states, can be distinguished through a criterion of the viscoelastic spectrum. As a result, a particular condition for the viscoelastic behavior of n-hexadecane molecules approaching that of the Rouse chain was obtained. Besides, more importantly, evidence of thermorheologically simple materials was presented in which the relaxation modulus obeys the time-temperature superposition principle. Therefore, using shift factors from the time-temperature superposition principle, the estimated Arrhenius flow activation energy was in good agreement with related experimental values. Furthermore, one relaxation modulus master curve well exhibited both transition and terminal zones. Especially regarding non-equilibrium thermodynamic states, variations in the density, with respect to frequencies, were revealed.

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

    NASA Astrophysics Data System (ADS)

    Kenmoe, Stephane; Biedermann, P. Ulrich

    2018-02-01

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

  11. Variable-Field Analytical Ultracentrifugation: I. Time-Optimized Sedimentation Equilibrium

    PubMed Central

    Ma, Jia; Metrick, Michael; Ghirlando, Rodolfo; Zhao, Huaying; Schuck, Peter

    2015-01-01

    Sedimentation equilibrium (SE) analytical ultracentrifugation (AUC) is a gold standard for the rigorous determination of macromolecular buoyant molar masses and the thermodynamic study of reversible interactions in solution. A significant experimental drawback is the long time required to attain SE, which is usually on the order of days. We have developed a method for time-optimized SE (toSE) with defined time-varying centrifugal fields that allow SE to be attained in a significantly (up to 10-fold) shorter time than is usually required. To achieve this, numerical Lamm equation solutions for sedimentation in time-varying fields are computed based on initial estimates of macromolecular transport properties. A parameterized rotor-speed schedule is optimized with the goal of achieving a minimal time to equilibrium while limiting transient sample preconcentration at the base of the solution column. The resulting rotor-speed schedule may include multiple over- and underspeeding phases, balancing the formation of gradients from strong sedimentation fluxes with periods of high diffusional transport. The computation is carried out in a new software program called TOSE, which also facilitates convenient experimental implementation. Further, we extend AUC data analysis to sedimentation processes in such time-varying centrifugal fields. Due to the initially high centrifugal fields in toSE and the resulting strong migration, it is possible to extract sedimentation coefficient distributions from the early data. This can provide better estimates of the size of macromolecular complexes and report on sample homogeneity early on, which may be used to further refine the prediction of the rotor-speed schedule. In this manner, the toSE experiment can be adapted in real time to the system under study, maximizing both the information content and the time efficiency of SE experiments. PMID:26287634

  12. EAST kinetic equilibrium reconstruction combining with Polarimeter-Interferometer internal measurement constraints

    NASA Astrophysics Data System (ADS)

    Lian, H.; Liu, H. Q.; Li, K.; Zou, Z. Y.; Qian, J. P.; Wu, M. Q.; Li, G. Q.; Zeng, L.; Zang, Q.; Lv, B.; Jie, Y. X.; EAST Team

    2017-12-01

    Plasma equilibrium reconstruction plays an important role in the tokamak plasma research. With a high temporal and spatial resolution, the POlarimeter-INTerferometer (POINT) system on EAST has provided effective measurements for 102s H-mode operation. Based on internal Faraday rotation measurements provided by the POINT system, the equilibrium reconstruction with a more accurate core current profile constraint has been demonstrated successfully on EAST. Combining other experimental diagnostics and external magnetic fields measurement, the kinetic equilibrium has also been reconstructed on EAST. Take the pressure and edge current information from kinetic EFIT into the equilibrium reconstruction with Faraday rotation constraint, the new equilibrium reconstruction not only provides a more accurate internal current profile but also contains edge current and pressure information. One time slice result using new kinetic equilibrium reconstruction with POINT data constraints is demonstrated in this paper and the result shows there is a reversed shear of q profile and the pressure profile is also contained. The new improved equilibrium reconstruction is greatly helpful to the future theoretical analysis.

  13. An equilibrium-point model of electromyographic patterns during single-joint movements based on experimentally reconstructed control signals.

    PubMed

    Latash, M L; Goodman, S R

    1994-01-01

    The purpose of this work has been to develop a model of electromyographic (EMG) patterns during single-joint movements based on a version of the equilibrium-point hypothesis, a method for experimental reconstruction of the joint compliant characteristics, the dual-strategy hypothesis, and a kinematic model of movement trajectory. EMG patterns are considered emergent properties of hypothetical control patterns that are equally affected by the control signals and peripheral feedback reflecting actual movement trajectory. A computer model generated the EMG patterns based on simulated movement kinematics and hypothetical control signals derived from the reconstructed joint compliant characteristics. The model predictions have been compared to published recordings of movement kinematics and EMG patterns in a variety of movement conditions, including movements over different distances, at different speeds, against different-known inertial loads, and in conditions of possible unexpected decrease in the inertial load. Changes in task parameters within the model led to simulated EMG patterns qualitatively similar to the experimentally recorded EMG patterns. The model's predictive power compares it favourably to the existing models of the EMG patterns. Copyright © 1994. Published by Elsevier Ltd.

  14. Experimental Validation of Pulse Phase Tracking for X-Ray Pulsar Based

    NASA Technical Reports Server (NTRS)

    Anderson, Kevin

    2012-01-01

    Pulsars are a form of variable celestial source that have shown to be usable as aids for autonomous, deep space navigation. Particularly those sources emitting in the X-ray band are ideal for navigation due to smaller detector sizes. In this paper X-ray photons arriving from a pulsar are modeled as a non-homogeneous Poisson process. The method of pulse phase tracking is then investigated as a technique to measure the radial distance traveled by a spacecraft over an observation interval. A maximum-likelihood phase estimator (MLE) is used for the case where the observed frequency signal is constant. For the varying signal frequency case, an algorithm is used in which the observation window is broken up into smaller blocks over which an MLE is used. The outputs of this phase estimation process were then looped through a digital phase-locked loop (DPLL) in order to reduce the errors and produce estimates of the doppler frequency. These phase tracking algorithms were tested both in a computer simulation environment and using the NASA Goddard Space flight Center X-ray Navigation Laboratory Testbed (GXLT). This provided an experimental validation with photons being emitted by a modulated X-ray source and detected by a silicon-drift detector. Models of the Crab pulsar and the pulsar B1821-24 were used in order to generate test scenarios. Three different simulated detector trajectories were used to be tracked by the phase tracking algorithm: a stationary case, one with constant velocity, and one with constant acceleration. All three were performed in one-dimension along the line of sight to the pulsar. The first two had a constant signal frequency and the third had a time varying frequency. All of the constant frequency cases were processed using the MLE, and it was shown that they tracked the initial phase within 0.15% for the simulations and 2.5% in the experiments, based on an average of ten runs. The MLE-DPLL cascade version of the phase tracking algorithm was used in

  15. Phase and vacancy behaviour of hard "slanted" cubes

    NASA Astrophysics Data System (ADS)

    van Damme, R.; van der Meer, B.; van den Broeke, J. J.; Smallenburg, F.; Filion, L.

    2017-09-01

    We use computer simulations to study the phase behaviour for hard, right rhombic prisms as a function of the angle of their rhombic face (the "slant" angle). More specifically, using a combination of event-driven molecular dynamics simulations, Monte Carlo simulations, and free-energy calculations, we determine and characterize the equilibrium phases formed by these particles for various slant angles and densities. Surprisingly, we find that the equilibrium crystal structure for a large range of slant angles and densities is the simple cubic crystal—despite the fact that the particles do not have cubic symmetry. Moreover, we find that the equilibrium vacancy concentration in this simple cubic phase is extremely high and depends only on the packing fraction and not the particle shape. At higher densities, a rhombic crystal appears as the equilibrium phase. We summarize the phase behaviour of this system by drawing a phase diagram in the slant angle-packing fraction plane.

  16. The Oxygen Equilibrium of Mammalian Hemoglobin

    PubMed Central

    Roughton, F. J. W.

    1965-01-01

    The three chief physicochemical theories of the oxygen-hemoglobin equilibrium in vogue 40 years ago still influence current thought on the problem. Although the Hill theory lost its fundamental basis some 40 years ago, the famous empiric equation to which it gave rise is still much used, as a useful phenomenological expression, only involving two disposable constants. The Haldane theory, of which a difference in aggregation of oxygenated and deoxygenated hemoglobin was a fundamental feature, lay for many years dormant but has recently had an astonishing reawakening through the work on lamprey hemoglobin, which clearly reveals such differences in aggregation. Lamprey hemoglobin might thus be called a "Haldane type" hemoglobin. Adair's four-stage intermediate compound theory still seems applicable in the case of hemoglobins such as those of sheep, whose tetramer molecules do not tend to dissociate into dimers, and which might therefore be called "Adair type" hemoglobins. Horse and human hemoglobins appear to reveal both "Haldane" and "Adair" behaviour. The effects of pH, temperature, and protein concentration on the oxygen-equilibrium of sheep hemoglobin are summarised, and it is shown that, although the equilibrium curves are often isomorphous over their middle range, intensive work at the top and bottom of the curves reveals considerable differences in the relative effects of these factors on the several equilibrium constants of Adair's four intermediate equations. In the last section an account is given of preliminary experimental attempts to interpret the oxygen- and carbon monoxide—equilibrium curves of whole human blood, under physiological conditions in terms of the Adair intermediate compound hypothesis. PMID:5859923

  17. Reflection of processes of non-equilibrium two-phase filtration in oil-saturated hierarchical medium in data of active wave geophysical monitoring

    NASA Astrophysics Data System (ADS)

    Hachay, Olga; Khachay, Andrey; Khachay, Oleg

    2016-04-01

    The processes of oil extraction from deposit are linked with the movement of multi-phase multi-component media, which are characterized by non-equilibrium and non-linear rheological features. The real behavior of layered systems is defined by the complexity of the rheology of moving fluids and the morphology structure of the porous medium, and also by the great variety of interactions between the fluid and the porous medium [Hasanov and Bulgakova, 2003]. It is necessary to take into account these features in order to informatively describe the filtration processes due to the non-linearity, non-equilibrium and heterogeneity that are features of real systems. In this way, new synergetic events can be revealed (namely, a loss of stability when oscillations occur, and the formation of ordered structures). This allows us to suggest new methods for the control and management of complicated natural systems that are constructed on account of these phenomena. Thus the layered system, from which it is necessary to extract the oil, is a complicated dynamical hierarchical system. A comparison is provided of non-equilibrium effects of the influence of independent hydrodynamic and electromagnetic induction on an oil layer and the medium which it surrounds. It is known that by drainage and steeping the hysteresis effect on curves of the relative phase permeability in dependence on the porous medium's water saturation in some cycles of influence (drainage-steep-drainage) is observed. Using the earlier developed 3D method of induction electromagnetic frequency geometric monitoring, we showed the possibility of defining the physical and structural features of a hierarchical oil layer structure and estimating the water saturation from crack inclusions. This effect allows managing the process of drainage and steeping the oil out of the layer by water displacement. An algorithm was constructed for 2D modeling of sound diffraction on a porous fluid-saturated intrusion of a hierarchical

  18. Finite-deformation phase-field chemomechanics for multiphase, multicomponent solids

    NASA Astrophysics Data System (ADS)

    Svendsen, Bob; Shanthraj, Pratheek; Raabe, Dierk

    2018-03-01

    The purpose of this work is the development of a framework for the formulation of geometrically non-linear inelastic chemomechanical models for a mixture of multiple chemical components diffusing among multiple transforming solid phases. The focus here is on general model formulation. No specific model or application is pursued in this work. To this end, basic balance and constitutive relations from non-equilibrium thermodynamics and continuum mixture theory are combined with a phase-field-based description of multicomponent solid phases and their interfaces. Solid phase modeling is based in particular on a chemomechanical free energy and stress relaxation via the evolution of phase-specific concentration fields, order-parameter fields (e.g., related to chemical ordering, structural ordering, or defects), and local internal variables. At the mixture level, differences or contrasts in phase composition and phase local deformation in phase interface regions are treated as mixture internal variables. In this context, various phase interface models are considered. In the equilibrium limit, phase contrasts in composition and local deformation in the phase interface region are determined via bulk energy minimization. On the chemical side, the equilibrium limit of the current model formulation reduces to a multicomponent, multiphase, generalization of existing two-phase binary alloy interface equilibrium conditions (e.g., KKS). On the mechanical side, the equilibrium limit of one interface model considered represents a multiphase generalization of Reuss-Sachs conditions from mechanical homogenization theory. Analogously, other interface models considered represent generalizations of interface equilibrium conditions consistent with laminate and sharp-interface theory. In the last part of the work, selected existing models are formulated within the current framework as special cases and discussed in detail.

  19. Effect of MgO on Liquidus Temperatures in the ZnO-"FeO"-Al2O3-CaO-SiO2-MgO System in Equilibrium with Metallic Iron

    NASA Astrophysics Data System (ADS)

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

    2011-06-01

    The phase equilibria in the ZnO-"FeO"-Al2O3-CaO-SiO2-MgO system have been determined experimentally in equilibrium with metallic iron. Synthetic slags were equilibrated at a high temperature, quenched, and then the compositions of the phases in equilibrium were measured using electron probe X-ray microanalysis. Pseudoternary sections of the form ZnO-"FeO"-(Al2O3 + CaO + SiO2) for CaO/SiO2 = 0.71, (CaO + SiO2)/Al2O3 = 5 and fixed MgO concentrations of 2, 4, and 6 wt pct have been constructed. Wustite (Fe2+,Mg,Zn)O and spinel (Fe2+,Mg,Zn)O·(Al,Fe3+)2O3 are the major primary phases in the temperature and composition ranges investigated. The liquidus temperatures are increased by 140 K in the wustite primary phase field and by 70 K in the spinel primary phase field with the addition of 6 wt pct MgO in the slag. The partitioning of MgO and ZnO between the solid and liquid phases has been discussed.

  20. Experimental study of an X-band phase-locked relativistic backward wave oscillator

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

    Wu, Y.; Science and Technology on High Power Microwave Laboratory, Mianyang 621900; Li, Z. H.

    2015-11-15

    To achieve high power microwave combined with high frequency band, an X-band phase-locked relativistic backward wave oscillator (RBWO) is proposed and investigated theoretically and experimentally using a modulated electron beam. In the device, an overmoded input cavity and a buncher cavity are employed to premodulate the electron beam. Particle-in-cell simulation shows that an input power of 90 kW is sufficient to lock the frequency and phase of 1.5 GW output microwave with the locking bandwidth of 60 MHz. Moreover, phase and frequency locking of an RBWO has been accomplished experimentally with an output power of 1.5 GW. The fluctuation of the relative phase differencemore » between output microwave and input RF signal is less than ±20° with the locking duration of about 50 ns. The input RF power required to lock the oscillator is only 90 kW.« less

  1. Si-Ge-metal ternary phase diagram calculations

    NASA Technical Reports Server (NTRS)

    Fleurial, J. P.; Borshchevsky, A.

    1990-01-01

    Solution crystal growth and doping conditions of Si-Ge alloys used for high-temperature thermoelectric generation are determined here. Liquid-phase epitaxy (LPE) has been successfully employed recently to obtain single-crystalline homogeneous layers of Si-Ge solid solutions from a liquid metal solvent. Knowledge of Si-Ge-metallic solvent ternary phase diagrams is essential for further single-crystal growth development. Consequently, a thermodynamic equilibrium model was used to calculate the phase diagrams of the Si-Ge-M systems, including solid solubilities, where M is Al, Ga, In, Sn, Pb, Sb, or Bi. Good agreement between calculated liquidus and solidus data and experimental DTA and microprobe results was obtained. The results are used to compare the suitability of the different systems for crystal growth (by LPE-type process).

  2. Equilibrium and Non-Equilibrium Condensation Phenomena in Tuneable 3D and 2D Bose Gases

    DTIC Science & Technology

    2016-04-01

    condensed gas " which remains condensed above the expected critical temperature, and performed one of the first studies of the strongly-interacting "unitary...34 Bose gas . With the 2d harmonic trap we showed how the interaction-driven BKT phase is connected with purely statistical theory, and with the 3d...box trap we created the world’s first atomic BEC in a quasi-uniform potential. 15. SUBJECT TERMS EOARD, Bose gas , ultracold, condensation, equilibrium

  3. Experimental Phase Functions of Millimeter-sized Cosmic Dust Grains

    NASA Astrophysics Data System (ADS)

    Muñoz, O.; Moreno, F.; Vargas-Martín, F.; Guirado, D.; Escobar-Cerezo, J.; Min, M.; Hovenier, J. W.

    2017-09-01

    We present the experimental phase functions of three types of millimeter-sized dust grains consisting of enstatite, quartz, and volcanic material from Mount Etna, respectively. The three grains present similar sizes but different absorbing properties. The measurements are performed at 527 nm covering the scattering angle range from 3° to 170°. The measured phase functions show two well-defined regions: (I) soft forward peaks and (II) a continuous increase with the scattering angle at side- and back-scattering regions. This behavior at side- and back-scattering regions is in agreement with the observed phase functions of the Fomalhaut and HR 4796A dust rings. Further computations and measurements (including polarization) for millimeter-sized grains are needed to draw some conclusions about the fluffy or compact structure of the dust grains.

  4. Application of the equilibrium spin technique to a typical low-wing general aviation design

    NASA Technical Reports Server (NTRS)

    Tischler, M. B.; Barlow, J. B.

    1979-01-01

    A graphical implementation of the equilibrium technique for obtaining spin modes from rotary balance data is presented. Using this technique, spin modes were computed for the NASA Low-Wing General Aviation Aircraft. The computed angles of attack are within 10 degrees of the NASA spin tunnel results. The method also provides information on the dynamic nature of spin modes. This technique offers the capability of providing a great deal of information on spin modes and recovery, using data from a single experimental installation. Such a technique could be utilized in the preliminary design phase in order to provide basic information on aircraft spin and recovery characteristics. Results, advantages and limitations of the application of this technique are discussed.

  5. Tokamak Equilibrium Reconstruction with MSE-LS Data in DIII-D

    NASA Astrophysics Data System (ADS)

    Lao, L.; Grierson, B.; Burrell, K. H.

    2016-10-01

    Equilibrium analysis of plasmas in DIII-D using EFIT was upgraded to include the internal magnetic field determined from spectroscopic measurements of motional-Stark-effect line-splitting (MSE-LS). MSE-LS provides measurements of the magnitude of the internal magnetic field, rather than the pitch angle as provided by MSE line-polarization (MSE-LP) used in most tokamaks to date. EFIT MSE-LS reconstruction algorithms and verifications are described. The capability of MSE-LS to provide significant constraints on the equilibrium analysis is evaluated. Reconstruction results with both synthetic and experimental MSE-LS data from 10 DIII-D discharges run over a range of conditions show that MSE-LS measurements can contribute to the equilibrium reconstruction of pressure and safety factor profiles. Adequate MSE-LS measurement accuracy and number of spatial locations are necessary. The 7 available experimental measurements provide useful additional constraints when used with other internal measurements. Using MSE-LS as the only internal measurement yields less current profile information. Work supported by the PPPL Subcontract S013769-F and US DOE under DE-FC02-04ER54698.

  6. Understanding the facet formation mechanisms of Si thin-film solidification through three-dimensional phase-field modeling

    NASA Astrophysics Data System (ADS)

    Chen, G. Y.; Lan, C. W.

    2017-09-01

    Adaptive phase field modeling is used in order to model the formation mechanism of a silicon faceted interface in three dimensions. We investigate the faceting condition for equilibrium shapes and dynamic situations. In this study, we propose a new anisotropic function of surface energy for the phase-field simulations in three-dimension, and negative stiffness is further considered. The morphological evolutions are presented and compare well with experimental findings. The growth mechanism is further discussed.

  7. Equilibrium study for ternary mixtures of biodiesel

    NASA Astrophysics Data System (ADS)

    Doungsri, S.; Sookkumnerd, T.; Wongkoblap, A.; Nuchitprasittichai, A.

    2017-11-01

    The liquid-liquid equilibrium (LLE) data for the ternary mixtures of methanol + fatty acid methyl ester (FAME) + palm oil and FAME + palm oil + glycerol at various temperatures from 35 to 55°C, the tie lines and binodial curves were also investigated and plotted in the equilibrium curve. The experimental results showed that the binodial curves of methanol + FAME + palm oil depended significantly with temperature while the binodial curves of FAME + palm oil + glycerol illustrated insignificant change with temperatures. The interaction parameters between liquid pair obtained for NRTL (Nonrandom Two-Liquid) and UNIQUAC (Universal Quasi-Chemical Theory) models from the experimental data were also investigated. It was found that the correlated parameters of UNIQUAC model for system of FAME + palm oil + glycerol, denoted as a13 and a31, were 580.42K and -123.69K, respectively, while those for system of methanol + FAME + palm oil, denoted as a42 and a24, were 71.48 K and 965.57K, respectively. The ternary LLE data reported here would be beneficial for engineers and scientists to use for prediction of yield and purity of biodiesel for the production. The UNIQUAC model agreed well with the experimental data of ternary mixtures of biodiesel.

  8. Effects of crowders on the equilibrium and kinetic properties of protein aggregation

    NASA Astrophysics Data System (ADS)

    Bridstrup, John; Yuan, Jian-Min

    2016-08-01

    The equilibrium and kinetic properties of protein aggregation systems in the presence of crowders are investigated using simple, illuminating models based on mass-action laws. Our model yields analytic results for equilibrium properties of protein aggregates, which fit experimental data of actin and ApoC-II with crowders reasonably well. When the effects of crowders on rate constants are considered, our kinetic model is in good agreement with experimental results for actin with dextran as the crowder. Furthermore, the model shows that as crowder volume fraction increases, the length distribution of fibrils becomes narrower and shifts to shorter values due to volume exclusion.

  9. Methods for achieving the equilibrium number of phases in mixtures suitable for use in battery electrodes, e.g., for lithiating FeS.sub.2

    DOEpatents

    Guidotti, Ronald A.

    1988-01-01

    In a method for preparing lithiated, particulate FeS.sub.2 useful as a catholyte material in a lithium thermal battery, whereby the latter's voltage regulation properties are improved, comprising admixing FeS.sub.2 and an amount of a lithium-containing compound whereby the resultant total composition falls in an invariant region of the metallurgical phase diagram of its constituent components, an improvement comprises admixing said lithium-containing compound and FeS.sub.2 together with a solid electrolyte compatible with said catholyte, and heating the mixture at a temperature above the melting point of said electrolyte and at which said mixture reaches its thermodynamic equilibrium number of phases.

  10. Determining equilibrium osmolarity in poly(ethylene glycol)/chondrotin sulfate gels mimicking articular cartilage.

    PubMed

    Sircar, S; Aisenbrey, E; Bryant, S J; Bortz, D M

    2015-01-07

    We present an experimentally guided, multi-phase, multi-species polyelectrolyte gel model to make qualitative predictions on the equilibrium electro-chemical properties of articular cartilage. The mixture theory consists of two different types of polymers: poly(ethylene gylcol) (PEG), chondrotin sulfate (ChS), water (acting as solvent) and several different ions: H(+), Na(+), Cl(-). The polymer chains have covalent cross-links whose effect on the swelling kinetics is modeled via Doi rubber elasticity theory. Numerical studies on equilibrium polymer volume fraction and net osmolarity (difference in the solute concentration across the gel) show a complex interplay between ionic bath concentrations, pH, cross-link fraction and the average charge per monomer. Generally speaking, swelling is aided due to a higher average charge per monomer (or a higher particle fraction of ChS, the charged component of the polymer), low solute concentration in the bath, a high pH or a low cross-link fraction. A peculiar case arises at higher values of cross-link fraction, where it is observed that increasing the average charge per monomer leads to gel deswelling. Copyright © 2014 Elsevier Ltd. All rights reserved.

  11. Brain Performance versus Phase Transitions

    NASA Astrophysics Data System (ADS)

    Torres, Joaquín J.; Marro, J.

    2015-07-01

    We here illustrate how a well-founded study of the brain may originate in assuming analogies with phase-transition phenomena. Analyzing to what extent a weak signal endures in noisy environments, we identify the underlying mechanisms, and it results a description of how the excitability associated to (non-equilibrium) phase changes and criticality optimizes the processing of the signal. Our setting is a network of integrate-and-fire nodes in which connections are heterogeneous with rapid time-varying intensities mimicking fatigue and potentiation. Emergence then becomes quite robust against wiring topology modification—in fact, we considered from a fully connected network to the Homo sapiens connectome—showing the essential role of synaptic flickering on computations. We also suggest how to experimentally disclose significant changes during actual brain operation.

  12. Instability of Insulators near Quantum Phase Transitions

    NASA Astrophysics Data System (ADS)

    Doron, A.; Tamir, I.; Levinson, T.; Ovadia, M.; Sacépé, B.; Shahar, D.

    2017-12-01

    Thin films of amorphous indium oxide undergo a magnetic field driven superconducting to insulator quantum phase transition. In the insulating phase, the current-voltage characteristics show large current discontinuities due to overheating of electrons. We show that the onset voltage for the discontinuities vanishes as we approach the quantum critical point. As a result, the insulating phase becomes unstable with respect to any applied voltage making it, at least experimentally, immeasurable. We emphasize that unlike previous reports of the absence of linear response near quantum phase transitions, in our system, the departure from equilibrium is discontinuous. Because the conditions for these discontinuities are satisfied in most insulators at low temperatures, and due to the decay of all characteristic energy scales near quantum phase transitions, we believe that this instability is general and should occur in various systems while approaching their quantum critical point. Accounting for this instability is crucial for determining the critical behavior of systems near the transition.

  13. Modeling Closed Equilibrium Systems of H2O-Dissolved CO2-Solid CaCO3.

    PubMed

    Tenno, Toomas; Uiga, Kalev; Mashirin, Alexsey; Zekker, Ivar; Rikmann, Ergo

    2017-04-27

    In many places in the world, including North Estonia, the bedrock is limestone, which consists mainly of CaCO 3 . Equilibrium processes in water involving dissolved CO 2 and solid CaCO 3 play a vital role in many biological and technological systems. The solubility of CaCO 3 in water is relatively low. Depending on the concentration of dissolved CO 2 , the solubility of CaCO 3 changes, which determines several important ground- and wastewater parameters, for example, Ca 2+ concentration and pH. The distribution of ions and molecules in the closed system solid H 2 O-dissolved CO 2 -solid CaCO 3 is described in terms of a structural scheme. Mathematical models were developed for the calculation of pH and concentrations of ions and molecules (Ca 2+ , CO 3 2- , HCO 3 - , H 2 CO 3 , CO 2 , H + , and OH - ) in the closed equilibrium system at different initial concentrations of CO 2 in the water phase using an iteration method. The developed models were then experimentally validated.

  14. Uncertainty Analysis in 3D Equilibrium Reconstruction

    DOE PAGES

    Cianciosa, Mark R.; Hanson, James D.; Maurer, David A.

    2018-02-21

    Reconstruction is an inverse process where a parameter space is searched to locate a set of parameters with the highest probability of describing experimental observations. Due to systematic errors and uncertainty in experimental measurements, this optimal set of parameters will contain some associated uncertainty. This uncertainty in the optimal parameters leads to uncertainty in models derived using those parameters. V3FIT is a three-dimensional (3D) equilibrium reconstruction code that propagates uncertainty from the input signals, to the reconstructed parameters, and to the final model. Here in this paper, we describe the methods used to propagate uncertainty in V3FIT. Using the resultsmore » of whole shot 3D equilibrium reconstruction of the Compact Toroidal Hybrid, this propagated uncertainty is validated against the random variation in the resulting parameters. Two different model parameterizations demonstrate how the uncertainty propagation can indicate the quality of a reconstruction. As a proxy for random sampling, the whole shot reconstruction results in a time interval that will be used to validate the propagated uncertainty from a single time slice.« less

  15. Uncertainty Analysis in 3D Equilibrium Reconstruction

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

    Cianciosa, Mark R.; Hanson, James D.; Maurer, David A.

    Reconstruction is an inverse process where a parameter space is searched to locate a set of parameters with the highest probability of describing experimental observations. Due to systematic errors and uncertainty in experimental measurements, this optimal set of parameters will contain some associated uncertainty. This uncertainty in the optimal parameters leads to uncertainty in models derived using those parameters. V3FIT is a three-dimensional (3D) equilibrium reconstruction code that propagates uncertainty from the input signals, to the reconstructed parameters, and to the final model. Here in this paper, we describe the methods used to propagate uncertainty in V3FIT. Using the resultsmore » of whole shot 3D equilibrium reconstruction of the Compact Toroidal Hybrid, this propagated uncertainty is validated against the random variation in the resulting parameters. Two different model parameterizations demonstrate how the uncertainty propagation can indicate the quality of a reconstruction. As a proxy for random sampling, the whole shot reconstruction results in a time interval that will be used to validate the propagated uncertainty from a single time slice.« less

  16. Experimental invalidation of phase-transition-induced elastic softening in CrN

    NASA Astrophysics Data System (ADS)

    Wang, Shanmin; Yu, Xiaohui; Zhang, Jianzhong; Chen, Miao; Zhu, Jinlong; Wang, Liping; He, Duanwei; Lin, Zhijun; Zhang, Ruifeng; Leinenweber, Kurt; Zhao, Yusheng

    2012-08-01

    We report experimental results of phase stability and incompressibility of CrN. The obtained bulk moduli for cubic and orthorhombic CrN are 257 and 262 GPa, respectively. These results invalidate the conclusion of phase-transition-induced elastic softening recently reported based on nonmagnetic simulations for cubic CrN [Nature Mater.NMAACR1476-112210.1038/nmat2549 8, 947 (2009)]. On the other hand, they provide the only experimental evidence to support the computational models involving the local magnetic moment of Cr atoms [Nature Mater.NMAACR1476-112210.1038/nmat2722 9, 283 (2010)], indicating that atomic spin has a profound influence on the material's elastic properties. We also demonstrate that nonstoichiometry in CrNx has strong effects on its structural stability.

  17. Integral Equation for the Equilibrium State of Colliding Electron Beams

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

    Warnock, Robert L.

    2002-11-11

    We study a nonlinear integral equation for the equilibrium phase distribution of stored colliding electron beams. It is analogous to the Haissinski equation, being derived from Vlasov-Fokker-Planck theory, but is quite different in form. We prove existence of a unique solution, thus the existence of a unique equilibrium state, for sufficiently small current. This is done for the Chao-Ruth model of the beam-beam interaction in one degree of freedom. We expect no difficulty in generalizing the argument to more realistic models.

  18. Structural hierarchy as a key to complex phase selection in Al-Sm

    NASA Astrophysics Data System (ADS)

    Ye, Z.; Zhang, F.; Sun, Y.; Nguyen, M. C.; Zhou, S. H.; Zhou, L.; Meng, F.; Ott, R. T.; Park, E.; Besser, M. F.; Kramer, M. J.; Ding, Z. J.; Mendelev, M. I.; Wang, C. Z.; Napolitano, R. E.; Ho, K. M.

    2017-10-01

    Investigating the unknown structure of the complex cubic phase, previously observed to crystallize from melt-spun amorphous Al-10 at.% Sm alloy, we determine the structure in full site-occupancy detail, highlighting several critical structural features that govern the far-from-equilibrium phase selection pathway. Using an efficient genetic algorithm combining molecular dynamics, density functional theory, and x-ray diffraction, the structure is clearly identified as body-centered cubic I m 3 ¯m (No. 229) with ˜140 atoms per cubic unit cell and a lattice parameter of 1.4 nm. The complex structure is further refined to elucidate the detailed site occupancy, revealing full Sm occupancy on 6b sites and split Sm/Al occupancy on 16f sites. Based on the refined site occupancy associated with the experimentally observed phase, we term this phase ɛ -A l60S m11 (bcc), corresponding to the limiting situation when all 16f sites are occupied by Sm. However, it should be recognized that the range of solubility enabled by split occupancy at Sm sites is an important feature in phase selection under experimental conditions, permitting an avenue for transition with little or no chemical partitioning. Our analysis shows that the ɛ -A l60S m11 (bcc) exhibits a "3-6-6-1" first-shell packing around Sm centers on 16f sites, the same dominant motif exhibited by the undercooled liquid. The coincident motif supports the notion that liquid/glass ordering at high undercooling may give rise to topological invariants between the noncrystalline and crystalline states that provide kinetic pathways to metastable phases that are not accessible during near-equilibrium processing.

  19. Structural hierarchy as a key to complex phase selection in Al-Sm

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

    Ye, Z.; Zhang, F.; Sun, Y.

    Investigating the unknown structure of the complex cubic phase, previously observed to crystallize from melt-spun amorphous Al–10 at.% Sm alloy, we determine the structure in full site-occupancy detail, highlighting several critical structural features that govern the far-from-equilibrium phase selection pathway. Using an efficient genetic algorithm combining molecular dynamics, density functional theory, and x-ray diffraction, the structure is clearly identified as body-centered cubic Im¯3m (No. 229) with ~140 atoms per cubic unit cell and a lattice parameter of 1.4 nm. The complex structure is further refined to elucidate the detailed site occupancy, revealing full Sm occupancy on 6b sites and splitmore » Sm/Al occupancy on 16f sites. Based on the refined site occupancy associated with the experimentally observed phase, we term this phase ε–Al 60Sm 11(bcc), corresponding to the limiting situation when all 16f sites are occupied by Sm. However, it should be recognized that the range of solubility enabled by split occupancy at Sm sites is an important feature in phase selection under experimental conditions, permitting an avenue for transition with little or no chemical partitioning. Our analysis shows that the ε–Al 60Sm 11(bcc) exhibits a “3-6-6-1” first-shell packing around Sm centers on 16f sites, the same dominant motif exhibited by the undercooled liquid. Here, the coincident motif supports the notion that liquid/glass ordering at high undercooling may give rise to topological invariants between the noncrystalline and crystalline states that provide kinetic pathways to metastable phases that are not accessible during near-equilibrium processing.« less

  20. Structural hierarchy as a key to complex phase selection in Al-Sm

    DOE PAGES

    Ye, Z.; Zhang, F.; Sun, Y.; ...

    2017-10-12

    Investigating the unknown structure of the complex cubic phase, previously observed to crystallize from melt-spun amorphous Al–10 at.% Sm alloy, we determine the structure in full site-occupancy detail, highlighting several critical structural features that govern the far-from-equilibrium phase selection pathway. Using an efficient genetic algorithm combining molecular dynamics, density functional theory, and x-ray diffraction, the structure is clearly identified as body-centered cubic Im¯3m (No. 229) with ~140 atoms per cubic unit cell and a lattice parameter of 1.4 nm. The complex structure is further refined to elucidate the detailed site occupancy, revealing full Sm occupancy on 6b sites and splitmore » Sm/Al occupancy on 16f sites. Based on the refined site occupancy associated with the experimentally observed phase, we term this phase ε–Al 60Sm 11(bcc), corresponding to the limiting situation when all 16f sites are occupied by Sm. However, it should be recognized that the range of solubility enabled by split occupancy at Sm sites is an important feature in phase selection under experimental conditions, permitting an avenue for transition with little or no chemical partitioning. Our analysis shows that the ε–Al 60Sm 11(bcc) exhibits a “3-6-6-1” first-shell packing around Sm centers on 16f sites, the same dominant motif exhibited by the undercooled liquid. Here, the coincident motif supports the notion that liquid/glass ordering at high undercooling may give rise to topological invariants between the noncrystalline and crystalline states that provide kinetic pathways to metastable phases that are not accessible during near-equilibrium processing.« less

  1. Haloing in bimodal magnetic colloids: The role of field-induced phase separation

    NASA Astrophysics Data System (ADS)

    Magnet, C.; Kuzhir, P.; Bossis, G.; Meunier, A.; Suloeva, L.; Zubarev, A.

    2012-07-01

    If a suspension of magnetic micrometer-sized and nanosized particles is subjected to a homogeneous magnetic field, the nanoparticles are attracted to the microparticles and form thick anisotropic halos (clouds) around them. Such clouds can hinder the approach of microparticles and result in effective repulsion between them [M. T. López-López, A. Yu. Zubarev, and G. Bossis, Soft Matter10.1039/c0sm00261e 6, 4346 (2010)]. In this paper, we present detailed experimental and theoretical studies of nanoparticle concentration profiles and of the equilibrium shapes of nanoparticle clouds around a single magnetized microsphere, taking into account interactions between nanoparticles. We show that at a strong enough magnetic field, the ensemble of nanoparticles experiences a gas-liquid phase transition such that a dense liquid phase is condensed around the magnetic poles of a microsphere while a dilute gas phase occupies the rest of the suspension volume. Nanoparticle accumulation around a microsphere is governed by two dimensionless parameters—the initial nanoparticle concentration (φ0) and the magnetic-to-thermal energy ratio (α)—and the three accumulation regimes are mapped onto a α-φ0 phase diagram. Our local thermodynamic equilibrium approach gives a semiquantitative agreement with the experiments on the equilibrium shapes of nanoparticle clouds. The results of this work could be useful for the development of the bimodal magnetorheological fluids and of the magnetic separation technologies used in bioanalysis and water purification systems.

  2. Experimental Phase Functions of Millimeter-sized Cosmic Dust Grains

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

    Muñoz, O.; Moreno, F.; Guirado, D.

    We present the experimental phase functions of three types of millimeter-sized dust grains consisting of enstatite, quartz, and volcanic material from Mount Etna, respectively. The three grains present similar sizes but different absorbing properties. The measurements are performed at 527 nm covering the scattering angle range from 3° to 170°. The measured phase functions show two well-defined regions: (i) soft forward peaks and (ii) a continuous increase with the scattering angle at side- and back-scattering regions. This behavior at side- and back-scattering regions is in agreement with the observed phase functions of the Fomalhaut and HR 4796A dust rings. Furthermore » computations and measurements (including polarization) for millimeter-sized grains are needed to draw some conclusions about the fluffy or compact structure of the dust grains.« less

  3. Removal of Oxygen from Electronic Materials by Vapor-Phase Processes

    NASA Technical Reports Server (NTRS)

    Palosz, Witold

    1997-01-01

    Thermochemical analyses of equilibrium partial pressures over oxides with and without the presence of the respective element condensed phase, and hydrogen, chalcogens, hydrogen chalcogenides, and graphite are presented. Theoretical calculations are supplemented with experimental results on the rate of decomposition and/or sublimation/vaporization of the oxides under dynamic vacuum, and on the rate of reaction with hydrogen, graphite, and chalcogens. Procedures of removal of a number of oxides under different conditions are discussed.

  4. Computational methods for reactive transport modeling: A Gibbs energy minimization approach for multiphase equilibrium calculations

    NASA Astrophysics Data System (ADS)

    Leal, Allan M. M.; Kulik, Dmitrii A.; Kosakowski, Georg

    2016-02-01

    We present a numerical method for multiphase chemical equilibrium calculations based on a Gibbs energy minimization approach. The method can accurately and efficiently determine the stable phase assemblage at equilibrium independently of the type of phases and species that constitute the chemical system. We have successfully applied our chemical equilibrium algorithm in reactive transport simulations to demonstrate its effective use in computationally intensive applications. We used FEniCS to solve the governing partial differential equations of mass transport in porous media using finite element methods in unstructured meshes. Our equilibrium calculations were benchmarked with GEMS3K, the numerical kernel of the geochemical package GEMS. This allowed us to compare our results with a well-established Gibbs energy minimization algorithm, as well as their performance on every mesh node, at every time step of the transport simulation. The benchmark shows that our novel chemical equilibrium algorithm is accurate, robust, and efficient for reactive transport applications, and it is an improvement over the Gibbs energy minimization algorithm used in GEMS3K. The proposed chemical equilibrium method has been implemented in Reaktoro, a unified framework for modeling chemically reactive systems, which is now used as an alternative numerical kernel of GEMS.

  5. Particle-scale measurement of PAH aqueous equilibrium partitioning in impacted sediments.

    PubMed

    Ghosh, Upal; Hawthorne, Steven B

    2010-02-15

    This research investigated the particle-scale processes that control aqueous equilibrium partitioning of PAHs in manufactured gas plant (MGP) site sediments. Dominant particle types in impacted sediments (sand, wood, coal/coke, and pitch) were physically separated under a microscope for equilibrium assessments. Solid-phase microextraction (SPME) combined with selected ion monitoring GC/MS and perdeuterated PAH internal standards were used to determine freely dissolved PAH concentrations in small (0.1-1 mL) water samples at concentrations as low as microg/L (for lower molecular weight PAHs) to ng/L (for higher molecular weight PAHs). For every particle class the initial release of PAHs into the aqueous phase was rapid, and an apparent equilibrium was reached in a matter of days. The average ratio of aqueous total PAH concentration for pitch vs coal/coke particles for eight sediment samples was 20. Thus, sediments that had aged in the field for many decades were not at equilibrium and were still going through a slow process of contaminant mass transfer between the different particle types. A possible consequence of this slow aging process is further lowering of the activity of the chemical as mass transfer is achieved to new sorption sites with time. This study also found that the presence of black carbon even at the level of (1)/(3) of sediment organic carbon does not necessarily imply a BC-dominated sorption behavior, rather source pitch particles if present may dominate PAH partitioning. To our knowledge this is the first report of equilibrium partitioning assessment conducted at the sediment particle scale.

  6. Trans-Pacific HDR Satellite Communications Experiment Phase-2: Experimental Network and Demonstration Plan

    NASA Technical Reports Server (NTRS)

    Kadowaki, Naoto; Yoshimura, Naoko; Takahashi, Takashi; Yoshikawa, Makoto; Hsu, Eddie; Bergman, Larry; Bhasin, Kul; Gary, Pat

    1998-01-01

    The trans-Pacific high data rate (TP-HDR) satellite communications experiment was proposed at the Japan-U.S. Cooperation in Space (JUCS) Program Workshop held in Hawaii in 1993 and remote high definition video post-production was demonstrated as the first phase trial. Following the first phase, the second phase experiment is currently prepared. This paper describes the experimental network configuration, application demonstration, and performance evaluation plan of the second phase experiment.

  7. An equilibrium ab initio atomistic thermodynamics study of chlorine adsorption on the Cu(001) surface.

    PubMed

    Suleiman, Ibrahim A; Radny, Marian W; Gladys, Michael J; Smith, Phillip V; Mackie, John C; Kennedy, Eric M; Dlugogorski, Bogdan Z

    2011-06-07

    The effect of chlorine (Cl) chemisorption on the energetics and atomic structure of the Cu(001) surface over a wide range of chlorine pressures and temperatures has been studied using equilibrium ab initio atomistic thermodynamics to elucidate the formation of cuprous chloride (CuCl) as part of the Deacon reaction on copper metal. The calculated surface free energies show that the 1/2 monolayer (ML) c(2 × 2)-Cl phase with chlorine atoms adsorbed at the hollow sites is the most stable structure for a wide range of Cl chemical potential, in agreement with experimental observations. It is also found that at very low pressure and exposure, but elevated temperature, the 1/9 ML and 1/4 ML phases become the most stable. By contrast, a high coverage of Cl does not lead to thermodynamically stable geometries. The subsurface adsorption of Cl atoms, however, dramatically increases the stability of the 1 ML and 2 ML adsorption configurations providing a possible pathway for the formation of the bulk-chloride surface phases in the kinetic regime.

  8. A new vapor-liquid equilibrium apparatus for hydrogen fluoride containing systems

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

    Jongcheon Lee; Hwayong Kim; Jong Sung Lim

    1996-12-31

    A new circulating type apparatus has been constructed to obtain reliable equilibrium PTxy data for hydrogen fluoride (HF) containing system. Equilibrium cell with Pyrex windows protected by Teflon PFA sheets to prevent the corrosion was used. Isothermal vapor-liquid equilibrium data for the 1,1-difluoroethane (HFC-152a) + HF system at 288.23 and 298.35 K were obtained, and compared with PTx measurement results. Experimental data were correlated using Lencka and Anderko equation of state for HF with the Wong-Sandler mixing rule as well as the van der Waals one fluid mixing rule. The Wong-Sandler mixing rule gives better results. 5 refs., 3 figs.

  9. Experimental demonstration of an optical phased array antenna for laser space communications.

    PubMed

    Neubert, W M; Kudielka, K H; Leeb, W R; Scholtz, A L

    1994-06-20

    The feasibility of an optical phased array antenna applicable for spaceborne laser communications was experimentally demonstrated. Heterodyne optical phase-locked loops provide for a defined phase relationship between the collimated output beams of three single-mode fibers. In the far field the beams interfere with a measured efficiency of 99%. The main lobe of the interference pattern can be moved by phase shifting the subaperture output beams. The setup permitted agile beam steering within an angular range of 1 mr and a response time of 0.7 ms. We propose an operational optical phased array antenna fed by seven lasers, featuring high transmit power and redundance.

  10. An experiment on radioactive equilibrium and its modelling using the ‘radioactive dice’ approach

    NASA Astrophysics Data System (ADS)

    Santostasi, Davide; Malgieri, Massimiliano; Montagna, Paolo; Vitulo, Paolo

    2017-07-01

    In this article we describe an educational activity on radioactive equilibrium we performed with secondary school students (17-18 years old) in the context of a vocational guidance stage for talented students at the Department of Physics of the University of Pavia. Radioactive equilibrium is investigated experimentally by having students measure the activity of 214Bi from two different samples, obtained using different preparation procedures from an uraniferous rock. Students are guided in understanding the mathematical structure of radioactive equilibrium through a modelling activity in two parts. Before the lab measurements, a dice game, which extends the traditional ‘radioactive dice’ activity to the case of a chain of two decaying nuclides, is performed by students divided into small groups. At the end of the laboratory work, students design and run a simple spreadsheet simulation modelling the same basic radioactive chain with user defined decay constants. By setting the constants to realistic values corresponding to nuclides of the uranium decay chain, students can deepen their understanding of the meaning of the experimental data, and also explore the difference between cases of non-equilibrium, transient and secular equilibrium.

  11. Development of Simulation Methods in the Gibbs Ensemble to Predict Polymer-Solvent Phase Equilibria

    NASA Astrophysics Data System (ADS)

    Gartner, Thomas; Epps, Thomas; Jayaraman, Arthi

    Solvent vapor annealing (SVA) of polymer thin films is a promising method for post-deposition polymer film morphology control. The large number of important parameters relevant to SVA (polymer, solvent, and substrate chemistries, incoming film condition, annealing and solvent evaporation conditions) makes systematic experimental study of SVA a time-consuming endeavor, motivating the application of simulation and theory to the SVA system to provide both mechanistic insight and scans of this wide parameter space. However, to rigorously treat the phase equilibrium between polymer film and solvent vapor while still probing the dynamics of SVA, new simulation methods must be developed. In this presentation, we compare two methods to study polymer-solvent phase equilibrium-Gibbs Ensemble Molecular Dynamics (GEMD) and Hybrid Monte Carlo/Molecular Dynamics (Hybrid MC/MD). Liquid-vapor equilibrium results are presented for the Lennard Jones fluid and for coarse-grained polymer-solvent systems relevant to SVA. We found that the Hybrid MC/MD method is more stable and consistent than GEMD, but GEMD has significant advantages in computational efficiency. We propose that Hybrid MC/MD simulations be used for unfamiliar systems in certain choice conditions, followed by much faster GEMD simulations to map out the remainder of the phase window.

  12. Adsorption of saturated fatty acid in urea complexation: Kinetics and equilibrium studies

    NASA Astrophysics Data System (ADS)

    Setyawardhani, Dwi Ardiana; Sulistyo, Hary; Sediawan, Wahyudi Budi; Fahrurrozi, Mohammad

    2018-02-01

    Urea complexation is fractionation process for concentrating poly-unsaturated fatty acids (PUFAs) from vegetable oil or animal fats. For process design and optimization in commercial industries, it is necessary to provide kinetics and equilibrium data. Urea inclusion compounds (UICs) as the product is a unique complex form which one molecule (guest) is enclosed within another molecule (host). In urea complexation, the guest-host bonding exists between saturated fatty acids (SFAs) and crystalline urea. This research studied the complexation is analogous to an adsorption process. The Batch adsorption process was developed to obtain the experimental data. The ethanolic urea solution was mixed with SFA in certain compositions and adsorption times. The mixture was heated until it formed homogenous and clear solution, then it cooled very slowly until the first numerous crystal appeared. Adsorption times for the kinetic data were determined since the crystal formed. The temperature was maintained constant at room temperature. Experimental sets of data were observed with adsorption kinetics and equilibrium models. High concentration of saturated fatty acid (SFA) was used to represent adsorption kinetics and equilibrium parameters. Kinetic data were examined with pseudo first-order, pseudo second-order and intra particle diffusion models. Linier, Freundlich and Langmuir isotherm were used to study the equilibrium model of this adsorption. The experimental data showed that SFA adsorption in urea crystal followed pseudo second-order model. The compatibility of the data with Langmuir isotherm showed that urea complexation was a monolayer adsorption.

  13. Stochastic driven systems far from equilibrium

    NASA Astrophysics Data System (ADS)

    Kim, Kyung Hyuk

    We study the dynamics and steady states of two systems far from equilibrium: a 1-D driven lattice gas and a driven Brownian particle with inertia. (1) We investigate the dynamical scaling behavior of a 1-D driven lattice gas model with two species of particles hopping in opposite directions. We confirm numerically that the dynamic exponent is equal to z = 1.5. We show analytically that a quasi-particle representation relates all phase points to a special phase line directly related to the single-species asymmetric simple exclusion process. Quasi-particle two-point correlations decay exponentially, and in such a manner that quasi-particles of opposite charge dynamically screen each other with a special balance. The balance encompasses all over the phase space. These results indicate that the model belongs to the Kardar-Parisi-Zhang (KPZ) universality class. (2) We investigate the non-equilibrium thermodynamics of a Brownian particle with inertia under feedback control of its inertia. We find such open systems can act as a molecular refrigerator due to an entropy pumping mechanism. We extend the fluctuation theorems to the refrigerator. The entropy pumping modifies both the Jarzynski equality and the fluctuation theorems. We discover that the entropy pumping has a dual role of work and heat. We also investigate the thermodynamics of the particle under a hydrodynamic interaction described by a Langevin equation with a multiplicative noise. The Stratonovich stochastic integration prescription involved in the definition of heat is shown to be the unique physical choice.

  14. Punctuated equilibrium as an emergent process and its modified thermodynamic characterization.

    PubMed

    Wosniack, M E; da Luz, M G E; Schulman, L S

    2017-01-07

    We address evolutionary dynamics and consider under which conditions the ecosystem interaction network allows punctuated equilibrium (i.e., alternation between hectic and quasi-stable phases). We focus on the links connecting various species and on the strength and sign of those links. For this study we consider the Tangled Nature model, which allows considerable flexibility and plasticity in the analysis of interspecies interactions. We find that it is necessary to have a proper balance of connectivity and interaction intensities so as to establish the kind of mutual cooperation and competition found in nature. It suggests evolutionary punctuated equilibrium as an emergent process, thus displaying features of complex systems. To explicitly demonstrate this fact we consider an extended form of thermodynamics, defining (for the present context) relevant out-of-equilibrium "collective" functions. We then show how to characterize the punctuated equilibrium through entropy-like and free energy-like quantities. Finally, from a close analogy to thermodynamic systems, we propose a protocol similar to simulated annealing. It is based on controlling the species' rate of mutation during the hectic periods, in this way enhancing the exploration of the genome space (similar to the known behavior of bacteria in stressful environments). This allows the system to more rapidly converge to long-duration quasi-stable phases. Copyright © 2016 Elsevier Ltd. All rights reserved.

  15. On the possibility to develop an advanced non-equilibrium model of depressurisation in two-phase fluids

    NASA Astrophysics Data System (ADS)

    Duc, Linh Do; Horák, Vladimír; Kulish, Vladimir; Lukáč, Tomáš

    2017-01-01

    Carbon dioxide is widely used as the power gas in the gas guns community due to its ease of handling, storability at room temperature, and high vapor pressure depending only upon temperature, but not a tank size, as long as some liquid carbon dioxide remains in the tank. This high vapor pressure can be used as the pressurant, making it what is referred to as a self-pressurising propellant. However, as a two-phase substance, carbon dioxide does have its drawbacks: (1) vaporization of liquefied CO2 inside a tank when shooting rapidly or a lot causes the tank to get cool, resulting in pressure fluctuations that makes the gun's performance and accuracy worse, (2) solid carbon dioxide that is also known as dry ice can appear on the output valve of the tank while shooting and it can cause damage or slow the gun's performance down, if it works its way into some control components, including the barrel of the gun. Hence, it is crucial to obtain a scientific understanding of carbon dioxide behavior and further the discharge characteristics of a wide range of pressure-tank configurations. For the purpose of satisfying this goal, a comprehensive discharge mathematical model for carbon dioxide tank dynamics is required. In this paper, the possibility to develop an advanced non-equilibrium model of depressurization in two-phase fluids is discussed.

  16. Cooperativity in self-limiting equilibrium self-associating systems

    NASA Astrophysics Data System (ADS)

    Freed, Karl F.

    2012-11-01

    A wide variety of highly cooperative self-assembly processes in biological and synthetic systems involve the assembly of a large number (m) of units into clusters, with m narrowly peaked about a large size m0 ≫ 1 and with a second peak centered about the m = 1 unassembled monomers. While very specific models have been proposed for the assembly of, for example, viral capsids and core-shell micelles of ß-casein, no available theory describes a thermodynamically general mechanism for this double peaked, highly cooperative equilibrium assembly process. This study provides a general mechanism for these cooperative processes by developing a minimal Flory-Huggins type theory. Beginning from the simplest non-cooperative, free association model in which the equilibrium constant for addition of a monomer to a cluster is independent of cluster size, the new model merely allows more favorable growth for clusters of intermediate sizes. The theory is illustrated by computing the phase diagram for cases of self-assembly on cooling or heating and for the mass distribution of the two phases.

  17. Application of constrained equilibrium thermodynamics to irradiated alloy systems

    NASA Astrophysics Data System (ADS)

    Holloway, James Paul; Stubbins, James F.

    1984-05-01

    Equilibrium thermodynamics are applied to systems with an excess of point defects to calculate the relative stability of phases. It is possible to model systems with supersaturation levels of vacancies and interstitials, such as those found under irradiation. The calculations reveal the extent to which phase compositional boundaries could shift when one phase or both in a two phase system contain an excess of point defects. Phase boundary shifts in the Ni-Si, Fe-Ni, Ni-Cr, and Fe-Cr systems are examined as a function of the number of excess defects in each phase. It is also found that the critical temperature of the sigma phase in the Fe-Cr system and the fcc-bcc transition in the Fe-Ni are sensitive to excess defect concentrations. These results may apply to local irradiation-induced phase transformations in the presence of solute segregation.

  18. The quasi-equilibrium response of MOS structures: Quasi-static factor

    NASA Astrophysics Data System (ADS)

    Okeke, M.; Balland, B.

    1984-07-01

    The dynamic response of a MOS structure driven into a non-equilibrium behaviour by a voltage ramp is presented. In contrast to Khun's quasi-static technique it is shown that any ramp-driven MOS structure has some degree of non-equilibrium. A quasi staticity factor μAK which serves as a measure of the degree of quasi-equilibrium, has been introduced for the first time. The mathematical model presented in the paper allows a better explanation of the experimental recordings. It is shown that this model could be used to analyse the various features of the response of the structure and that such physical parameters as the generation-rate, trap activation energy, and the effective capture constants could be obtained.

  19. Experimental study of phase equilibria and thermodynamic optimization of the Fe-Zn-O system

    NASA Astrophysics Data System (ADS)

    Degterov, Sergei A.; Pelton, Arthur D.; Jak, Evgueni; Hayes, Peter C.

    2001-08-01

    The Fe-Zn-O phase diagram in air was studied over the temperature range from 900 °C to 1500 °C. The compositions of the phases in quenched samples were obtained by electron probe X-ray microanalysis (EPMA). This experimental technique is not affected by zinc losses resulting from vaporization of zinc at high temperatures. The model for the spinel solid solution was developed within the framework of the compound-energy formalism (CEF). The choice of parameters of the CEF and the sequence of their optimization can have a major influence on the predictions in multicomponent phases. These choices can only be made rationally by reference to the specific model being represented in the CEF. This is discussed for the case of the two-sublattice spinel model. In the limiting case, the proposed model reduces to the model by O’Neill and Navrotsky for spinels. When the CEF is used in combination with the equation of Hillert and Jarl to describe the magnetic contribution to thermodynamic functions of a solution, it is necessary to assign certain values of magnetic properties to all pseudocomponents and to magnetic interaction parameters to obtain the most reasonable approximation of the magnetic properties of a solution. It was shown how this can be done based on very limited experimental data. The same equations can be used when the Murnaghan or the Birch-Murnaghan equation is combined with the CEF to describe the pressure dependence of thermodynamic functions. The polynomial model was used to describe the properties of wustite and zincite, and the modified quasichemical model was used for the liquid slag. All thermodynamic and phase-equilibria data on the Fe-O and Fe-Zn-O systems were critically evaluated, and parameters of the models were optimized to give a self-consistent set of thermodynamic functions of the phases in these systems. All experimental data are reproduced within experimental error limits. These include the thermodynamic properties of phases (such as

  20. Unfolding single RNA molecules: bridging the gap between equilibrium and non-equilibrium statistical thermodynamics.

    PubMed

    Bustamante, Carlos

    2005-11-01

    During the last 15 years, scientists have developed methods that permit the direct mechanical manipulation of individual molecules. Using this approach, they have begun to investigate the effect of force and torque in chemical and biochemical reactions. These studies span from the study of the mechanical properties of macromolecules, to the characterization of molecular motors, to the mechanical unfolding of individual proteins and RNA. Here I present a review of some of our most recent results using mechanical force to unfold individual molecules of RNA. These studies make it possible to follow in real time the trajectory of each molecule as it unfolds and characterize the various intermediates of the reaction. Moreover, if the process takes place reversibly it is possible to extract both kinetic and thermodynamic information from these experiments at the same time that we characterize the forces that maintain the three-dimensional structure of the molecule in solution. These studies bring us closer to the biological unfolding processes in the cell as they simulate in vitro, the mechanical unfolding of RNAs carried out in the cell by helicases. If the unfolding process occurs irreversibly, I show here that single-molecule experiments can still provide equilibrium, thermodynamic information from non-equilibrium data by using recently discovered fluctuation theorems. Such theorems represent a bridge between equilibrium and non-equilibrium statistical mechanics. In fact, first derived in 1997, the first experimental demonstration of the validity of fluctuation theorems was obtained by unfolding mechanically a single molecule of RNA. It is perhaps a sign of the times that important physical results are these days used to extract information about biological systems and that biological systems are being used to test and confirm fundamental new laws in physics.

  1. Adiabatic out-of-equilibrium solutions to the Boltzmann equation in warm inflation

    NASA Astrophysics Data System (ADS)

    Bastero-Gil, Mar; Berera, Arjun; Ramos, Rudnei O.; Rosa, João G.

    2018-02-01

    We show that, in warm inflation, the nearly constant Hubble rate and temperature lead to an adiabatic evolution of the number density of particles interacting with the thermal bath, even if thermal equilibrium cannot be maintained. In this case, the number density is suppressed compared to the equilibrium value but the associated phase-space distribution retains approximately an equilibrium form, with a smaller amplitude and a slightly smaller effective temperature. As an application, we explicitly construct a baryogenesis mechanism during warm inflation based on the out-of-equilibrium decay of particles in such an adiabatically evolving state. We show that this generically leads to small baryon isocurvature perturbations, within the bounds set by the Planck satellite. These are correlated with the main adiabatic curvature perturbations but exhibit a distinct spectral index, which may constitute a smoking gun for baryogenesis during warm inflation. Finally, we discuss the prospects for other applications of adiabatically evolving out-of-equilibrium states.

  2. On magnetoelectric coupling at equilibrium in continua with microstructure

    NASA Astrophysics Data System (ADS)

    Romeo, Maurizio

    2017-10-01

    A theory of micromorphic continua, applied to electromagnetic solids, is exploited to study magnetoelectric effects at equilibrium. Microcurrents are modeled by the microgyration tensor of stationary micromotions, compatibly with the balance equations for null microdeformation. The equilibrium of the continuum subject to electric and magnetic fields is reformulated accounting for electric multipoles which are related to microdeformation by evolution equations. Polarization and magnetization are derived for uniform fields under the micropolar reduction in terms of microstrain and octupole structural parameters. Nonlinear dependance on the electromagnetic fields is evidenced, compatibly with known theoretical and experimental results on magnetoelectric coupling.

  3. Liquid-glass transition in equilibrium

    NASA Astrophysics Data System (ADS)

    Parisi, G.; Seoane, B.

    2014-02-01

    We show in numerical simulations that a system of two coupled replicas of a binary mixture of hard spheres undergoes a phase transition in equilibrium at a density slightly smaller than the glass transition density for an unreplicated system. This result is in agreement with the theories that predict that such a transition is a precursor of the standard ideal glass transition. The critical properties are compatible with those of an Ising system. The relations of this approach to the conventional approach based on configurational entropy are briefly discussed.

  4. Calculation of individual isotope equilibrium constants for geochemical reactions

    USGS Publications Warehouse

    Thorstenson, D.C.; Parkhurst, D.L.

    2004-01-01

    factors. The derivations can be extended to calculation of individual isotope equilibrium constants for ion pairs and equilibrium constants for isotopic species of other chemical elements. The individual isotope approach calculates the same phase isotopic compositions as existing methods, but also provides concentrations of individual species, which are needed in calculations of mass-dependent effects in transport processes. The equilibrium constants derived in this paper are used to calculate the example of gas-water equilibrium for CO2 in an acidic aqueous solution. ?? 2004 Elsevier Ltd.

  5. Swelling equilibrium of dentin adhesive polymers formed on the water-adhesive phase boundary: Experiments and micromechanical model

    PubMed Central

    Misra, Anil; Parthasarathy, Ranganathan; Ye, Qiang; Singh, Viraj; Spencer, Paulette

    2013-01-01

    During their application to the wet, oral environment, dentin adhesives can experience phase separation and composition change which can compromise the quality of the hybrid layer formed at the dentin-adhesive interface. The chemical composition of polymer phases formed in the hybrid layer can be represented using a ternary water-adhesive phase diagram. In this paper, these polymer phases have been characterized using a suite of mechanical tests and swelling experiments. The experimental results were evaluated using granular micromechanics based model that incorporates poro-mechanical effects and polymer-solvent thermodynamics. The variation of the model parameters and model-predicted polymer properties has been studied as a function of composition along the phase boundary. The resulting structure-property correlations provide insight into interactions occurring at the molecular level in the saturated polymer system. These correlations can be used for modeling the mechanical behavior of hybrid layer, and are expected to aid in the design and improvement of water-compatible dentin adhesive polymers. PMID:24076070

  6. Improved modeling of two-dimensional transitions in dense phases on crystalline surfaces. Krypton–graphite system

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

    Ustinov, E. A., E-mail: eustinov@mail.wplus.net

    This paper presents a refined technique to describe two-dimensional phase transitions in dense fluids adsorbed on a crystalline surface. Prediction of parameters of 2D liquid–solid equilibrium is known to be an extremely challenging problem, which is mainly due to a small difference in thermodynamic functions of coexisting phases and lack of accuracy of numerical experiments in case of their high density. This is a serious limitation of various attempts to circumvent this problem. To improve this situation, a new methodology based on the kinetic Monte Carlo method was applied. The methodology involves analysis of equilibrium gas–liquid and gas–solid systems undergoingmore » an external potential, which allows gradual shifting parameters of the phase coexistence. The interrelation of the chemical potential and tangential pressure for each system is then treated with the Gibbs–Duhem equation to obtain the point of intersection corresponding to the liquid/solid–solid equilibrium coexistence. The methodology is demonstrated on the krypton–graphite system below and above the 2D critical temperature. Using experimental data on the liquid–solid and the commensurate–incommensurate transitions in the krypton monolayer derived from adsorption isotherms, the Kr–graphite Lennard–Jones parameters have been corrected resulting in a higher periodic potential modulation.« less

  7. Barium isotope fractionation during witherite (BaCO3) dissolution, precipitation and at equilibrium

    NASA Astrophysics Data System (ADS)

    Mavromatis, Vasileios; van Zuilen, Kirsten; Purgstaller, Bettina; Baldermann, Andre; Nägler, Thomas F.; Dietzel, Martin

    2016-10-01

    This study examines the behavior of Ba isotope fractionation between witherite and fluid during mineral dissolution, precipitation and at chemical equilibrium. Experiments were performed in batch reactors at 25 °C in 10-2 M NaCl solution where the pH was adjusted by continuous bubbling of a water saturated gas phase of CO2 or atmospheric air. During witherite dissolution no Ba isotope fractionation was observed between solid and fluid. In contrast, during witherite precipitation, caused by a pH increase, a preferential uptake of the lighter 134Ba isotopomer in the solid phase was observed. In this case, the isotope fractionation factor αwitherite-fluid is calculated to be 0.99993 ± 0.00004 (or Δ137/134Bawitherite-fluid ≈ -0.07 ± 0.04‰, 2 sd). The most interesting feature of this study, however, is that after the attainment of chemical equilibrium, the Ba isotope composition of the aqueous phase is progressively becoming lighter, indicating a continuous exchange of Ba2+ ions between witherite and fluid. Mass balance calculations indicate that the detachment of Ba from the solid is not only restricted to the outer surface layer of the solid, but affects several (∼7 unit cells) subsurface layers of the crystal. This observation comes in excellent agreement with the concept of a dynamic system at chemical equilibrium in a mineral-fluid system, denoting that the time required for the achievement of isotopic equilibrium in the witherite-fluid system is longer compared to that observed for chemical equilibrium. Overall, these results indicate that the isotopic composition of Ba bearing carbonates in natural environments may be altered due to changes in fluid composition without a net dissolution/precipitation to be observed.

  8. A Pseudo-Vertical Equilibrium Model for Slow Gravity Drainage Dynamics

    NASA Astrophysics Data System (ADS)

    Becker, Beatrix; Guo, Bo; Bandilla, Karl; Celia, Michael A.; Flemisch, Bernd; Helmig, Rainer

    2017-12-01

    Vertical equilibrium (VE) models are computationally efficient and have been widely used for modeling fluid migration in the subsurface. However, they rely on the assumption of instant gravity segregation of the two fluid phases which may not be valid especially for systems that have very slow drainage at low wetting phase saturations. In these cases, the time scale for the wetting phase to reach vertical equilibrium can be several orders of magnitude larger than the time scale of interest, rendering conventional VE models unsuitable. Here we present a pseudo-VE model that relaxes the assumption of instant segregation of the two fluid phases by applying a pseudo-residual saturation inside the plume of the injected fluid that declines over time due to slow vertical drainage. This pseudo-VE model is cast in a multiscale framework for vertically integrated models with the vertical drainage solved as a fine-scale problem. Two types of fine-scale models are developed for the vertical drainage, which lead to two pseudo-VE models. Comparisons with a conventional VE model and a full multidimensional model show that the pseudo-VE models have much wider applicability than the conventional VE model while maintaining the computational benefit of the conventional VE model.

  9. Experimental investigation of the phase equilibria in the carbon dioxide-propane-3 M MDEA system

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

    Jou, F.Y.; Mather, A.E.; Otto, F.D.

    1995-07-01

    The treating of liquefied petroleum gas (LPG) to remove carbon dioxide and hydrogen sulfide using aqueous alkanolamine solutions is an important aspect of gas processing. One of the amines used in the natural gas industry is methyldiethanolamine (MDEA). Measurements of the phase equilibria in the carbon dioxide-propane-3 M MDEA system have been made at 25 and 40 C at pressures up to 15.5 MPa. Vapor-liquid, liquid-liquid, and vapor-liquid-liquid equilibria were determined. The vapor-liquid equilibrium data were compared with the model of Deshmukh and Mather.

  10. Capillary equilibrium and sintering kinetics in dispersed media and catalysts

    NASA Astrophysics Data System (ADS)

    Delannay, Francis

    2016-06-01

    The evolution of an aggregate of particles embedded in a fluid phase, no matter whether a liquid, a vapor, or a mixture of both, is determined by the dependence of the equilibrium interface area on porosity volume fraction. In system with open porosity, this equilibrium can be analyzed using a model representing the particles as a collection of cones of revolution, the number of which is the average particle coordination number. The accuracy of the model has been assessed using in situ X-ray microtomography. The model makes possible the computation of the driving force for sintering, commonly called sintering stress. It allows the mapping of the domains of relative density, coordination number, and dihedral angle that bring about aggregate densification or expansion. The contribution of liquid/vapor interfaces is enlightened, as well as the dependence of the equilibrium fluid phase distribution on particle size. Applied to foams and emulsions, the model provides insight into the relationship between osmotic pressure and coordination. Interface-governed transport mechanisms are considered dominant in the macroscopic viscosity. Both sintering stress and viscosity parameters strongly depend on particle size. The capacity of modeling the simultaneous particle growth is thus essential. The analysis highlights the microstructural parameters and material properties needed for kinetics simulation.

  11. A New Chaotic Flow with Hidden Attractor: The First Hyperjerk System with No Equilibrium

    NASA Astrophysics Data System (ADS)

    Ren, Shuili; Panahi, Shirin; Rajagopal, Karthikeyan; Akgul, Akif; Pham, Viet-Thanh; Jafari, Sajad

    2018-02-01

    Discovering unknown aspects of non-equilibrium systems with hidden strange attractors is an attractive research topic. A novel quadratic hyperjerk system is introduced in this paper. It is noteworthy that this non-equilibrium system can generate hidden chaotic attractors. The essential properties of such systems are investigated by means of equilibrium points, phase portrait, bifurcation diagram, and Lyapunov exponents. In addition, a fractional-order differential equation of this new system is presented. Moreover, an electronic circuit is also designed and implemented to verify the feasibility of the theoretical model.

  12. Stepwise kinetic equilibrium models of quantitative polymerase chain reaction.

    PubMed

    Cobbs, Gary

    2012-08-16

    Numerous models for use in interpreting quantitative PCR (qPCR) data are present in recent literature. The most commonly used models assume the amplification in qPCR is exponential and fit an exponential model with a constant rate of increase to a select part of the curve. Kinetic theory may be used to model the annealing phase and does not assume constant efficiency of amplification. Mechanistic models describing the annealing phase with kinetic theory offer the most potential for accurate interpretation of qPCR data. Even so, they have not been thoroughly investigated and are rarely used for interpretation of qPCR data. New results for kinetic modeling of qPCR are presented. Two models are presented in which the efficiency of amplification is based on equilibrium solutions for the annealing phase of the qPCR process. Model 1 assumes annealing of complementary targets strands and annealing of target and primers are both reversible reactions and reach a dynamic equilibrium. Model 2 assumes all annealing reactions are nonreversible and equilibrium is static. Both models include the effect of primer concentration during the annealing phase. Analytic formulae are given for the equilibrium values of all single and double stranded molecules at the end of the annealing step. The equilibrium values are then used in a stepwise method to describe the whole qPCR process. Rate constants of kinetic models are the same for solutions that are identical except for possibly having different initial target concentrations. Analysis of qPCR curves from such solutions are thus analyzed by simultaneous non-linear curve fitting with the same rate constant values applying to all curves and each curve having a unique value for initial target concentration. The models were fit to two data sets for which the true initial target concentrations are known. Both models give better fit to observed qPCR data than other kinetic models present in the literature. They also give better estimates of

  13. Liquid-Vapor Equilibrium of Multicomponent Cryogenic Systems

    NASA Technical Reports Server (NTRS)

    Thompson, W. Reid; Calado, Jorge C. G.; Zollweg, John A.

    1990-01-01

    Liquid-vapor and solid-vapor equilibria at low to moderate pressures and low temperatures are important in many solar system environments, including the surface and clouds of Titan, the clouds of Uranus and Neptune, and the surfaces of Mars and Triton. The familiar cases of ideal behavior are limiting cases of a general thermodynamic representation for the vapor pressure of each component in a homogeneous multicomponent system. The fundamental connections of laboratory measurements to thermodynamic models are through the Gibbs-Duhem relation and the Gibbs-Helmholtz relation. Using laboratory measurements of the total pressure, temperature, and compositions of the liquid and vapor phases at equilibrium, the values of these parameters can be determined. The resulting model for vapor-liquid equilibrium can then conveniently and accurately be used to calculate pressures, compositions, condensation altitudes, and their dependencies on changing climatic conditions. A specific system being investigated is CH4-C2H6-N2, at conditions relevant to Titan's surface and atmosphere. Discussed are: the modeling of existing data on CH4-N2, with applications to the composition of Titan's condensate clouds; some new measurements on the CH4-C2H6 binary, using a high-precision static/volumetric system, and on the C2H6-N2 binary, using the volumetric system and a sensitive cryogenic flow calorimeter; and describe a new cryogenic phase-equilibrium vessel with which we are beginning a detailed, systematic study of the three constituent binaries and the ternary CH4-C2H6-N2 system at temperatures ranging from 80 to 105 K and pressures from 0.1 to 7 bar.

  14. Experimental study of forced convection heat transport in porous media

    NASA Astrophysics Data System (ADS)

    Pastore, Nicola; Cherubini, Claudia; Rapti, Dimitra; Giasi, Concetta I.

    2018-04-01

    The present study is aimed at extending this thematic issue through heat transport experiments and their interpretation at laboratory scale. An experimental study to evaluate the dynamics of forced convection heat transfer in a thermally isolated column filled with porous medium has been carried out. The behavior of two porous media with different grain sizes and specific surfaces has been observed. The experimental data have been compared with an analytical solution for one-dimensional heat transport for local nonthermal equilibrium condition. The interpretation of the experimental data shows that the heterogeneity of the porous medium affects heat transport dynamics, causing a channeling effect which has consequences on thermal dispersion phenomena and heat transfer between fluid and solid phases, limiting the capacity to store or dissipate heat in the porous medium.

  15. Equilibrium drives of the low and high field side n = 2 plasma response and impact on global confinement

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

    Paz-Soldan, C.; Logan, N. C.; Haskey, S. R.

    The nature of the multi-modal n=2 plasma response and its impact on global confinement is studied as a function of the axisymmetric equilibrium pressure, edge safety factor, collisionality, and L-versus H-mode conditions. Varying the relative phase (ΔΦ UL) between upper and lower in-vessel coils demonstrates that different n=2 poloidal spectra preferentially excite different plasma responses. These different plasma response modes are preferentially detected on the tokamak high-field side (HFS) or low-field side (LFS) midplanes, have different radial extents, couple differently to the resonant surfaces, and have variable impacts on edge stability and global confinement. In all equilibrium conditions studied, themore » observed confinement degradation shares the same ΔΦ UL dependence as the coupling to the resonant surfaces given by both ideal (IPEC) and resistive (MARS-F) MHD computation. Varying the edge safety factor shifts the equilibrium field-line pitch and thus the ΔΦ UL dependence of both the global confinement and the n=2 magnetic response. As edge safety factor is varied, modeling finds that the HFS response (but not the LFS response), the resonant surface coupling, and the edge displacements near the X-point all share the same ΔΦ UL dependence. The LFS response magnitude is strongly sensitive to the core pressure and is insensitive to the collisionality and edge safety factor. This indicates that the LFS measurements are primarily sensitive to a pressure-driven kink-ballooning mode that couples to the core plasma. MHD modeling accurately reproduces these (and indeed all) LFS experimental trends and supports this interpretation. In contrast to the LFS, the HFS magnetic response and correlated global confinement impact is unchanged with plasma pressure, but is strongly reduced in high collisionality conditions in both H- and L-mode. This experimentally suggests the bootstrap current drives the HFS response through the kink-peeling mode drive

  16. Equilibrium drives of the low and high field side n = 2 plasma response and impact on global confinement

    DOE PAGES

    Paz-Soldan, C.; Logan, N. C.; Haskey, S. R.; ...

    2016-03-31

    The nature of the multi-modal n=2 plasma response and its impact on global confinement is studied as a function of the axisymmetric equilibrium pressure, edge safety factor, collisionality, and L-versus H-mode conditions. Varying the relative phase (ΔΦ UL) between upper and lower in-vessel coils demonstrates that different n=2 poloidal spectra preferentially excite different plasma responses. These different plasma response modes are preferentially detected on the tokamak high-field side (HFS) or low-field side (LFS) midplanes, have different radial extents, couple differently to the resonant surfaces, and have variable impacts on edge stability and global confinement. In all equilibrium conditions studied, themore » observed confinement degradation shares the same ΔΦ UL dependence as the coupling to the resonant surfaces given by both ideal (IPEC) and resistive (MARS-F) MHD computation. Varying the edge safety factor shifts the equilibrium field-line pitch and thus the ΔΦ UL dependence of both the global confinement and the n=2 magnetic response. As edge safety factor is varied, modeling finds that the HFS response (but not the LFS response), the resonant surface coupling, and the edge displacements near the X-point all share the same ΔΦ UL dependence. The LFS response magnitude is strongly sensitive to the core pressure and is insensitive to the collisionality and edge safety factor. This indicates that the LFS measurements are primarily sensitive to a pressure-driven kink-ballooning mode that couples to the core plasma. MHD modeling accurately reproduces these (and indeed all) LFS experimental trends and supports this interpretation. In contrast to the LFS, the HFS magnetic response and correlated global confinement impact is unchanged with plasma pressure, but is strongly reduced in high collisionality conditions in both H- and L-mode. This experimentally suggests the bootstrap current drives the HFS response through the kink-peeling mode drive

  17. Proper Orthogonal Decomposition on Experimental Multi-phase Flow in a Pipe

    NASA Astrophysics Data System (ADS)

    Viggiano, Bianca; Tutkun, Murat; Cal, Raúl Bayoán

    2016-11-01

    Multi-phase flow in a 10 cm diameter pipe is analyzed using proper orthogonal decomposition. The data were obtained using X-ray computed tomography in the Well Flow Loop at the Institute for Energy Technology in Kjeller, Norway. The system consists of two sources and two detectors; one camera records the vertical beams and one camera records the horizontal beams. The X-ray system allows measurement of phase holdup, cross-sectional phase distributions and gas-liquid interface characteristics within the pipe. The mathematical framework in the context of multi-phase flows is developed. Phase fractions of a two-phase (gas-liquid) flow are analyzed and a reduced order description of the flow is generated. Experimental data deepens the complexity of the analysis with limited known quantities for reconstruction. Comparison between the reconstructed fields and the full data set allows observation of the important features. The mathematical description obtained from the decomposition will deepen the understanding of multi-phase flow characteristics and is applicable to fluidized beds, hydroelectric power and nuclear processes to name a few.

  18. Experimental study on natural circulation precooling of cryogenic pump system with gas phase inlet reflux configuration

    NASA Astrophysics Data System (ADS)

    Chen, G. B.; Zhong, Y. K.; Zheng, X. L.; Li, Q. F.; Xie, X. M.; Gan, Z. H.; Huang, Y. H.; Tang, K.; Kong, B.; Qiu, L. M.

    2003-12-01

    A novel gas-phase inlet configuration in the natural circulation system instead of the liquid-phase inlet is introduced to cool down a cryogenic pump system from room temperature to cryogenic temperatures, effectively. The experimental apparatus is illustrated and test process is described. Heat transfer and pressure drop data during the cool-down process are recorded and portrayed. By contrast with liquid-phase inlet configuration, experimental results demonstrate that the natural circulation with the gas-phase inlet configuration is an easier and more controllable way to cool down the pump system and maintain it at cryogenic temperatures.

  19. Non-equilibrium time evolution of higher order cumulants of conserved charges and event-by-event analysis

    NASA Astrophysics Data System (ADS)

    Kitazawa, Masakiyo; Asakawa, Masayuki; Ono, Hirosato

    2014-01-01

    We investigate the time evolution of higher order cumulants of conserved charges in a volume with the diffusion master equation. Applying the result to the diffusion of non-Gaussian fluctuations in the hadronic stage of relativistic heavy ion collisions, we show that the fourth-order cumulant of net-electric charge at LHC energy is suppressed compared with the recently observed second-order cumulant at ALICE, if the higher order cumulants at hadronization are suppressed compared with their values in the hadron phase in equilibrium. The significance of the experimental information on the rapidity window dependence of various cumulants in investigating the history of the dynamical evolution of the hot medium created in relativistic heavy ion collisions is emphasized.

  20. Argumentation Practices in Classroom: Pre-service teachers' conceptual understanding of chemical equilibrium

    NASA Astrophysics Data System (ADS)

    Kaya, Ebru

    2013-05-01

    This study examines the impact of argumentation practices on pre-service teachers' understanding of chemical equilibrium. The sample consisted of 100 pre-service teachers in two classes of a public university. One of these classes was assigned as experimental and the other as control group, randomly. In the experimental group, the subject of chemical equilibrium was taught by using argumentative practices and the participants were encouraged to participate in the lessons actively. However, the instructor taught the same subject by using the lecturing method without engaging argumentative activities in the control group. The Chemical Equilibrium Concept Test and Written Argumentation Survey were administered to all participants to assess their conceptual understanding and the quality of their arguments, respectively. The analysis of covariance results indicate that argumentation practices significantly improved conceptual understanding of the experimental group when compared to the control group. Furthermore, the results show that the pre-service teachers exposed to argumentative practices constructed more quality arguments than those in the control group after the instruction. Based on these results, it can be concluded that the instruction based on argumentative practices is effective in concept teaching in science education. Therefore, argumentation should be explicitly taught in teacher education besides elementary and secondary education.

  1. Coupling of Higgs and Leggett modes in non-equilibrium superconductors.

    PubMed

    Krull, H; Bittner, N; Uhrig, G S; Manske, D; Schnyder, A P

    2016-06-21

    In equilibrium systems amplitude and phase collective modes are decoupled, as they are mutually orthogonal excitations. The direct detection of these Higgs and Leggett collective modes by linear-response measurements is not possible, because they do not couple directly to the electromagnetic field. In this work, using numerical exact simulations we show for the case of two-gap superconductors, that optical pump-probe experiments excite both Higgs and Leggett modes out of equilibrium. We find that this non-adiabatic excitation process introduces a strong interaction between the collective modes, which is absent in equilibrium. Moreover, we propose a type of pump-probe experiment, which allows to probe and coherently control the Higgs and Leggett modes, and thus the order parameter directly. These findings go beyond two-band superconductors and apply to general collective modes in quantum materials.

  2. Solid-liquid like phase transition in a confined granular suspension

    NASA Astrophysics Data System (ADS)

    Sakai, Nariaki; Lechenault, Frederic; Adda Bedia, Mokhtar

    We present an experimental study of a liquid-solid like phase transition in a two-dimensional granular media. Particles are placed in a vertical Hele-Show cell filled with a denser solution of cesium-chloride. Thus, when the cell is rotated around its axis, hydrostatic pressure exerts a centripetal force on the particles which confines them towards the center. This force is in competition with gravity, thus by modifying the rotation rate, it is possible to transform continuously and reversibly the sample from a disordered loose state to an ordered packed state. The system presents many similarities with thermal systems at equilibrium like density and interface fluctuations, and the transition between the two phases goes through a coexistence state, where there is nucleation and growth of locally ordered domains which are captured by the correlation function of the hexatic order parameter. We discuss the possibility to extend the grand-canonical formalism to out-of equilibrium systems, in order to uncover a state equation between the density and the pressure in the medium.

  3. Phase-field crystal modeling of compositional domain formation in ultrathin films.

    PubMed

    Muralidharan, Srevatsan; Haataja, Mikko

    2010-09-17

    Bulk-immiscible binary systems often form stress-induced miscible alloy phases when deposited on a substrate. Both alloying and surface dislocation formation lead to the decrease of the elastic strain energy, and the competition between these two strain-relaxation mechanisms gives rise to the emergence of pseudomorphic compositional nanoscale domains, often coexisting with a partially coherent single phase. In this work, we develop a phase-field crystal model for compositional patterning in monolayer aggregates of binary metallic systems. We first demonstrate that the model naturally incorporates the competition between alloying and misfit dislocations, and quantify the effects of misfit and line tension on equilibrium domain size. Then, we quantitatively relate the parameters of the phase-field crystal model to a specific system, CoAg/Ru(0001), and demonstrate that the simulations capture experimentally observed morphologies.

  4. Van der Waals model for phase transitions in thermoresponsive surface films.

    PubMed

    McCoy, John D; Curro, John G

    2009-05-21

    Phase transitions in polymeric surface films are studied with a simple model based on the van der Waals equation of state. Each chain is modeled by a single bead attached to the surface by an entropic-Hooke's law spring. The surface coverage is controlled by adjusting the chemical potential, and the equilibrium density profile is calculated with density functional theory. The interesting feature of this model is the multivalued nature of the density profile seen at low temperature. This van der Waals loop behavior is resolved with a Maxwell construction between a high-density phase near the wall and a low-density phase in a "vertical" phase transition. Signatures of the phase transition in experimentally measurable quantities are then found. Numerical calculations are presented for isotherms of surface pressure, for the Poisson ratio, and for the swelling ratio.

  5. The Blacktail Creek Tuff: an analytical and experimental study of rhyolites from the Heise volcanic field, Yellowstone hotspot system

    NASA Astrophysics Data System (ADS)

    Bolte, Torsten; Holtz, Francois; Almeev, Renat; Nash, Barbara

    2015-02-01

    The magma storage conditions of the 6.62 Ma Blacktail Creek Tuff eruption, belonging to the Heise volcanic field (6.62-4.45 Ma old) of the Yellowstone hotspot system, have been investigated by combining thermobarometric and experimental approaches. The results from different geothermometers (e.g., Fe-Ti oxides, feldspar pairs, apatite and zircon solubility, and Ti in quartz) indicate a pre-eruptive temperature in the range 825-875 °C. The temperature estimated using two-pyroxene pairs varies in a range of 810-950 °C, but the pyroxenes are probably not in equilibrium with each other, and the analytical results of melt inclusion in pyroxenes indicate a complex history for clinopyroxene, which hosts two compositionally different inclusion types. One natural Blacktail Creek Tuff rock sample has been used to determine experimentally the equilibrium phase assemblages in the pressure range 100-500 MPa and a water activity range 0.1-1.0. The experiments have been performed at fluid-present conditions, with a fluid phase composed of H2O and CO2, as well as at fluid-absent conditions. The stability of the quartzo-feldspathic phases is similar in both types of experiments, but the presence of mafic minerals such as biotite and clinopyroxene is strongly dependent on the experimental approach. Possible explanations are given for this discrepancy which may have strong impacts on the choice of appropriate experimental approaches for the determination of magma storage conditions. The comparison of the composition of natural phases and of experimentally synthesized phases confirms magma storage temperatures of 845-875 °C. Melt water contents of 1.5-2.5 wt% H2O are required to reproduce the natural Blacktail Creek Tuff mineral assemblage at these temperatures. Using the Ti-in-quartz barometer and the Qz-Ab-Or proportions of natural matrix glasses, coexisting with quartz, plagioclase and sanidine, the depth of magma storage is estimated to be in a pressure range between 130 and

  6. Sorption equilibrium, thermodynamics and pH-indicator properties of cresyl violet dye/bentonite composite system.

    PubMed

    Georgieva, Nedyalka; Yaneva, Zvezdelina; Dermendzhieva, Diyana

    2017-09-01

    The aim of the present study was to develop cresyl violet (CV)/bentonite composite system, to investigate the equilibrium sorption of the fluorescent dye on bentonite, to determine the characteristic equilibrium and thermodynamic parameters of the system by appropriate empirical isotherm models and to assess its pH-indicator properties. The absorption characteristics of CV solutions were investigated by UV/VIS spectrophotometer. Equilibrium experiments were conducted and the experimental data were modelled by six mathematical isotherm models. The analyses of the experimental data showed that bentonite exhibited significantly high capacity - 169.92 mg/g, towards CV. The encapsulation efficiency was 85%. The Langmuir, Flory-Huggins and El-Awady models best represented the experimental results. The free Gibbs energy of adsorption (ΔG o ) was calculated on the basis of the values of the equilibrium coefficients determined by the proposed models. The values of ΔG determined by the Langmuir, Temkin and Flory-Huggins models are within the range -20 to -40 kJ/mol, which indicates that the adsorption process is spontaneous and chemisorption takes place due to charge sharing or transfer from the dye molecules to the sorbent surface as a coordinate type of bond. The investigations of the obtained CV/bentonite hybrid systems for application as pH-markers showed satisfactory results.

  7. The Equilibrium State of Colliding Electron Beams

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

    Warnock, R

    2003-12-12

    We study a nonlinear integral equation that is a necessary condition on the equilibrium phase space distribution function of stored, colliding electron beams. It is analogous to the Haissinski equation, being derived from Vlasov-Fokker-Planck theory, but is quite different in form. The equation is analyzed for the case of the Chao-Ruth model of the beam-beam interaction in one degree of freedom, a so-called strong-strong model with nonlinear beam-beam force. We prove existence of a unique solution, for sufficiently small beam current, by an application of the implicit function theorem. We have not yet proved that this solution is positive, asmore » would be required to establish existence of an equilibrium. There is, however, numerical evidence of a positive solution. We expect that our analysis can be extended to more realistic models.« less

  8. Molecular-dynamics study of propane-hydrate dissociation: Fluctuation-dissipation and non-equilibrium analysis.

    PubMed

    Ghaani, Mohammad Reza; English, Niall J

    2018-03-21

    Equilibrium and non-equilibrium molecular-dynamics (MD) simulations have been performed to investigate thermal-driven break-up of planar propane-hydrate interfaces in contact with liquid water over the 260-320 K range. Two types of hydrate-surface water-lattice molecular termination were adopted, at the hydrate edge with water, for comparison: a 001-direct surface cleavage and one with completed cages. Statistically significant differences in melting temperatures and initial break-up rates were observed between both interface types. Dissociation rates were observed to be strongly dependent on temperature, with higher rates at larger over-temperatures vis-à-vis melting. A simple coupled mass and heat transfer model, developed previously, was applied to fit the observed dissociation profiles, and this helps us to identify clearly two distinct hydrate-decomposition régimes; following a highly temperature-dependent break-up phase, a second well-defined stage is essentially independent of temperature, in which the remaining nanoscale, de facto two-dimensional system's lattice framework is intrinsically unstable. Further equilibrium MD-analysis of the two-phase systems at their melting point, with consideration of the relaxation times gleaned from the auto-correlation functions of fluctuations in a number of enclathrated guest molecules, led to statistically significant differences between the two surface-termination cases; a consistent correlation emerged in both cases between the underlying, non-equilibrium, thermal-driven dissociation rates sampled directly from melting with that from an equilibrium-MD fluctuation-dissipation approach.

  9. Molecular-dynamics study of propane-hydrate dissociation: Fluctuation-dissipation and non-equilibrium analysis

    NASA Astrophysics Data System (ADS)

    Ghaani, Mohammad Reza; English, Niall J.

    2018-03-01

    Equilibrium and non-equilibrium molecular-dynamics (MD) simulations have been performed to investigate thermal-driven break-up of planar propane-hydrate interfaces in contact with liquid water over the 260-320 K range. Two types of hydrate-surface water-lattice molecular termination were adopted, at the hydrate edge with water, for comparison: a 001-direct surface cleavage and one with completed cages. Statistically significant differences in melting temperatures and initial break-up rates were observed between both interface types. Dissociation rates were observed to be strongly dependent on temperature, with higher rates at larger over-temperatures vis-à-vis melting. A simple coupled mass and heat transfer model, developed previously, was applied to fit the observed dissociation profiles, and this helps us to identify clearly two distinct hydrate-decomposition régimes; following a highly temperature-dependent break-up phase, a second well-defined stage is essentially independent of temperature, in which the remaining nanoscale, de facto two-dimensional system's lattice framework is intrinsically unstable. Further equilibrium MD-analysis of the two-phase systems at their melting point, with consideration of the relaxation times gleaned from the auto-correlation functions of fluctuations in a number of enclathrated guest molecules, led to statistically significant differences between the two surface-termination cases; a consistent correlation emerged in both cases between the underlying, non-equilibrium, thermal-driven dissociation rates sampled directly from melting with that from an equilibrium-MD fluctuation-dissipation approach.

  10. Thermal non-equilibrium in porous medium adjacent to vertical plate: ANN approach

    NASA Astrophysics Data System (ADS)

    Ahmed, N. J. Salman; Ahamed, K. S. Nazim; Al-Rashed, Abdullah A. A. A.; Kamangar, Sarfaraz; Athani, Abdulgaphur

    2018-05-01

    Thermal non-equilibrium in porous medium is a condition that refers to temperature discrepancy in solid matrix and fluid of porous medium. This type of flow is complex flow requiring complex set of partial differential equations that govern the flow behavior. The current work is undertaken to predict the thermal non-equilibrium behavior of porous medium adjacent to vertical plate using artificial neural network. A set of neurons in 3 layers are trained to predict the heat transfer characteristics. It is found that the thermal non-equilibrium heat transfer behavior in terms of Nusselt number of fluid as well as solid phase can be predicted accurately by using well-trained neural network.

  11. DEPARTURE OF HIGH-TEMPERATURE IRON LINES FROM THE EQUILIBRIUM STATE IN FLARING SOLAR PLASMAS

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

    Kawate, T.; Keenan, F. P.; Jess, D. B., E-mail: t.kawate@qub.ac.uk

    2016-07-20

    The aim of this study is to clarify if the assumption of ionization equilibrium and a Maxwellian electron energy distribution is valid in flaring solar plasmas. We analyze the 2014 December 20 X1.8 flare, in which the Fe xxi 187 Å, Fe xxii 253 Å, Fe xxiii 263 Å, and Fe xxiv 255 Å emission lines were simultaneously observed by the EUV Imaging Spectrometer on board the Hinode satellite. Intensity ratios among these high-temperature Fe lines are compared and departures from isothermal conditions and ionization equilibrium examined. Temperatures derived from intensity ratios involving these four lines show significant discrepancies atmore » the flare footpoints in the impulsive phase, and at the looptop in the gradual phase. Among these, the temperature derived from the Fe xxii/Fe xxiv intensity ratio is the lowest, which cannot be explained if we assume a Maxwellian electron distribution and ionization equilibrium, even in the case of a multithermal structure. This result suggests that the assumption of ionization equilibrium and/or a Maxwellian electron energy distribution can be violated in evaporating solar plasma around 10 MK.« less

  12. Trans-Pacific HDR Satellite Communications Experiment Phase-2 Project Plan and Experimental Network

    NASA Technical Reports Server (NTRS)

    Hsu, Eddie; Kadowaki, Naoto; Yoshimura, Naoko; Takahashi, Takashi; Yoshikawa, Makoto; Bergman, Larry; Bhasin, Kul

    2000-01-01

    The trans-Pacific high data rate (TP-HDR) satellite communications experiment was proposed at the Japan-U.S. Cooperation in Space (JUCS) Program Workshop held in Hawaii in 1993 and remote high definition video post-production was demonstrated as the first phase trial. ATM-based 45 Mbps trans-Pacific link was established in the first phase, and the following experiments with 155 Mbps was planned as the phase 2. This paper describes the experimental network configuration and project plan of TP-HDR experiment phase 2. Additional information is provided in the original.

  13. Improved methods for achieving the equilibrium number of phases in mixtures suitable for use in battery electrodes e. g. , for lithiating FeS/sub 2/

    DOEpatents

    Guidotti, R.A.

    1986-06-10

    A method is disclosed for preparing lithiated, particulate FeS/sub 2/ useful as a catholyte material in a lithium thermal battery, whereby the latter's voltage regulation properties are improved. The method comprises admixing FeS/sub 2/ and an amount of a lithium-containing compound, whereby the resultant total composition falls in an invariant region of the metallurgical phase diagram of its constituent components. Said lithium-containing compound and FeS/sub 2/ are admixed together with a solid electrolyte compatible with said catholyte, and the mixture is heated at a temperature above the melting point of said electrolyte and at which said mixture reaches its thermodynamic equilibrium number of phases.

  14. Chemical partitioning for the Co--Pr system: First-principles, experiments and energetic calculations to investigate the hard magnetic phase

    DOE PAGES

    Zhou, S. H.; Kramer, M. J.; Meng, F. Q.; ...

    2015-11-14

    Co 5Pr-D2 d is promising permanent magnet. Due to its peritectic formation feature, there is a synthetic challenge to produce single Co 5Pr-D2 d phase. The object of our study is to assess thermodynamic pathways for crystalline phases under far-from-equilibrium conditions by combining first-principles calculations and experimental measurements into a robust description of the thermodynamic behavior. The energetic calculations, temperature and time dependent phase selections are predicted under varying degrees of chemical partitioning. Our calculation to assess the chemical partitioning-temperatures indicates that the major magnetic compounds: Co 17Pr 2-α, Co 5Pr-D2 d, Co 19Pr 5-β, and Co 7Pr 2-χ formmore » from a congruent manner to eutectic reactions with decreasing cooling rate. The compositions of the compounds from these highly driven liquids can be far from equilibrium.« less

  15. Argumentation Practices in Classroom: Pre-Service Teachers' Conceptual Understanding of Chemical Equilibrium

    ERIC Educational Resources Information Center

    Kaya, Ebru

    2013-01-01

    This study examines the impact of argumentation practices on pre-service teachers' understanding of chemical equilibrium. The sample consisted of 100 pre-service teachers in two classes of a public university. One of these classes was assigned as experimental and the other as control group, randomly. In the experimental group, the subject of…

  16. Vapor-liquid equilibrium thermodynamics of N2 + CH4 - Model and Titan applications

    NASA Technical Reports Server (NTRS)

    Thompson, W. R.; Zollweg, John A.; Gabis, David H.

    1992-01-01

    A thermodynamic model is presented for vapor-liquid equilibrium in the N2 + CH4 system, which is implicated in calculations of the Titan tropospheric clouds' vapor-liquid equilibrium thermodynamics. This model imposes constraints on the consistency of experimental equilibrium data, and embodies temperature effects by encompassing enthalpy data; it readily calculates the saturation criteria, condensate composition, and latent heat for a given pressure-temperature profile of the Titan atmosphere. The N2 content of condensate is about half of that computed from Raoult's law, and about 30 percent greater than that computed from Henry's law.

  17. Phase behaviour in complementary DNA-coated gold nanoparticles and fd-viruses mixtures: a numerical study.

    PubMed

    Chiappini, Massimiliano; Eiser, Erika; Sciortino, Francesco

    2017-01-01

    A new gel-forming colloidal system based on a binary mixture of fd-viruses and gold nanoparticles functionalized with complementary DNA single strands has been recently introduced. Upon quenching below the DNA melt temperature, such a system results in a highly porous gel state, that may be developed in a new functional material of tunable porosity. In order to shed light on the gelation mechanism, we introduce a model closely mimicking the experimental one and we explore via Monte Carlo simulations its equilibrium phase diagram. Specifically, we model the system as a binary mixture of hard rods and hard spheres mutually interacting via a short-range square-well attractive potential. In the experimental conditions, we find evidence of a phase separation occurring either via nucleation-and-growth or via spinodal decomposition. The spinodal decomposition leads to the formation of small clusters of bonded rods and spheres whose further diffusion and aggregation leads to the formation of a percolating network in the system. Our results are consistent with the hypothesis that the mixture of DNA-coated fd-viruses and gold nanoparticles undergoes a non-equilibrium gelation via an arrested spinodal decomposition mechanism.

  18. Allowance for effects of thermodynamic nonideality in sedimentation equilibrium distributions reflecting protein dimerization.

    PubMed

    Wills, Peter R; Scott, David J; Winzor, Donald J

    2012-03-01

    This reexamination of a high-speed sedimentation equilibrium distribution for α-chymotrypsin under slightly acidic conditions (pH 4.1, I(M) 0.05) has provided experimental support for the adequacy of nearest-neighbor considerations in the allowance for effects of thermodynamic nonideality in the characterization of protein self-association over a moderate concentration range (up to 8 mg/mL). A widely held but previously untested notion about allowance for thermodynamic nonideality effects is thereby verified experimentally. However, it has also been shown that a greater obstacle to better characterization of protein self-association is likely to be the lack of a reliable estimate of monomer net charge, a parameter that has a far more profound effect on the magnitude of the measured equilibrium constant than any deficiency in current procedures for incorporating the effects of thermodynamic nonideality into the analysis of sedimentation equilibrium distributions reflecting reversible protein self-association. Copyright © 2011 Elsevier Inc. All rights reserved.

  19. Kinetics and Equilibrium of Age-Induced Precipitation in Cu-4 At. Pct Ti Binary Alloy

    NASA Astrophysics Data System (ADS)

    Semboshi, Satoshi; Amano, Shintaro; Fu, Jie; Iwase, Akihiro; Takasugi, Takayuki

    2017-03-01

    Transformation kinetics and phase equilibrium of metastable and stable precipitates in age-hardenable Cu-4 at. pct Ti binary alloy have been investigated by monitoring the microstructural evolution during isothermal aging at temperatures between 693 K (420 °C) and 973 K (700 °C). The microstructure of the supersaturated solid solution evolves in four stages: compositional modulation due to spinodal decomposition, continuous precipitation of the needle-shaped metastable β'-Cu4Ti with a tetragonal structure, discontinuous precipitation of cellular components containing stable β-Cu4Ti lamellae with an orthorhombic structure, and eventually precipitation saturation at equilibrium. In specimens aged below 923 K (650 °C), the stable β-Cu4Ti phase is produced only due to the cellular reaction, whereas it can be also directly obtained from the intergranular needle-shaped β'-Cu4Ti precipitates in specimens aged at 973 K (700 °C). The precipitation kinetics and phase equilibrium observed for the specimens aged between 693 K (420 °C) and 973 K (700 °C) were characterized in accordance with a time-temperature-transformation (TTT) diagram and a Cu-Ti partial phase diagram, which were utilized to determine the alloy microstructure, strength, and electrical conductivity.

  20. Thermodynamic Investigation of the Effect of Interface Curvature on the Solid-Liquid Equilibrium and Eutectic Point of Binary Mixtures.

    PubMed

    Liu, Fanghui; Zargarzadeh, Leila; Chung, Hyun-Joong; Elliott, Janet A W

    2017-10-12

    Thermodynamic phase behavior is affected by curved interfaces in micro- and nanoscale systems. For example, capillary freezing point depression is associated with the pressure difference between the solid and liquid phases caused by interface curvature. In this study, the thermal, mechanical, and chemical equilibrium conditions are derived for binary solid-liquid equilibrium with a curved solid-liquid interface due to confinement in a capillary. This derivation shows the equivalence of the most general forms of the Gibbs-Thomson and Ostwald-Freundlich equations. As an example, the effect of curvature on solid-liquid equilibrium is explained quantitatively for the water/glycerol system. Considering the effect of a curved solid-liquid interface, a complete solid-liquid phase diagram is developed over a range of concentrations for the water/glycerol system (including the freezing of pure water or precipitation of pure glycerol depending on the concentration of the solution). This phase diagram is compared with the traditional phase diagram in which the assumption of a flat solid-liquid interface is made. We show the extent to which nanoscale interface curvature can affect the composition-dependent freezing and precipitating processes, as well as the change in the eutectic point temperature and concentration with interface curvature. Understanding the effect of curvature on solid-liquid equilibrium in nanoscale capillaries has applications in the food industry, soil science, cryobiology, nanoporous materials, and various nanoscience fields.

  1. Reactive Gas transport in soil: Kinetics versus Local Equilibrium Approach

    NASA Astrophysics Data System (ADS)

    Geistlinger, Helmut; Jia, Ruijan

    2010-05-01

    Gas transport through the unsaturated soil zone was studied using an analytical solution of the gas transport model that is mathematically equivalent to the Two-Region model. The gas transport model includes diffusive and convective gas fluxes, interphase mass transfer between the gas and water phase, and biodegradation. The influence of non-equilibrium phenomena, spatially variable initial conditions, and transient boundary conditions are studied. The objective of this paper is to compare the kinetic approach for interphase mass transfer with the standard local equilibrium approach and to find conditions and time-scales under which the local equilibrium approach is justified. The time-scale of investigation was limited to the day-scale, because this is the relevant scale for understanding gas emission from the soil zone with transient water saturation. For the first time a generalized mass transfer coefficient is proposed that justifies the often used steady-state Thin-Film mass transfer coefficient for small and medium water-saturated aggregates of about 10 mm. The main conclusion from this study is that non-equilibrium mass transfer depends strongly on the temporal and small-scale spatial distribution of water within the unsaturated soil zone. For regions with low water saturation and small water-saturated aggregates (radius about 1 mm) the local equilibrium approach can be used as a first approximation for diffusive gas transport. For higher water saturation and medium radii of water-saturated aggregates (radius about 10 mm) and for convective gas transport, the non-equilibrium effect becomes more and more important if the hydraulic residence time and the Damköhler number decrease. Relative errors can range up to 100% and more. While for medium radii the local equilibrium approach describes the main features both of the spatial concentration profile and the time-dependence of the emission rate, it fails completely for larger aggregates (radius about 100 mm

  2. Experimental phase-space-based optical amplification of scar modes.

    PubMed

    Michel, C; Tascu, S; Doya, V; Aschiéri, P; Blanc, W; Legrand, O; Mortessagne, F

    2012-04-01

    Wave billiards which are chaotic in the geometrical limit are known to support nongeneric spatially localized modes called scar modes. The interaction of the scar modes with gain has been recently investigated in optics in microcavity lasers and vertical-cavity surface-emitting lasers. Exploiting the localization properties of scar modes in their wave-analogous phase-space representation, we report experimental results of scar mode selection by gain in a doped D-shaped optical fiber.

  3. An Initial Non-Equilibrium Porous-Media Model for CFD Simulation of Stirling Regenerators

    NASA Technical Reports Server (NTRS)

    Tew, Roy; Simon, Terry; Gedeon, David; Ibrahim, Mounir; Rong, Wei

    2006-01-01

    The objective of this paper is to define empirical parameters (or closwre models) for an initial thermai non-equilibrium porous-media model for use in Computational Fluid Dynamics (CFD) codes for simulation of Stirling regenerators. The two CFD codes currently being used at Glenn Research Center (GRC) for Stirling engine modeling are Fluent and CFD-ACE. The porous-media models available in each of these codes are equilibrium models, which assmne that the solid matrix and the fluid are in thermal equilibrium at each spatial location within the porous medium. This is believed to be a poor assumption for the oscillating-flow environment within Stirling regenerators; Stirling 1-D regenerator models, used in Stirling design, we non-equilibrium regenerator models and suggest regenerator matrix and gas average temperatures can differ by several degrees at a given axial location end time during the cycle. A NASA regenerator research grant has been providing experimental and computational results to support definition of various empirical coefficients needed in defining a noa-equilibrium, macroscopic, porous-media model (i.e., to define "closure" relations). The grant effort is being led by Cleveland State University, with subcontractor assistance from the University of Minnesota, Gedeon Associates, and Sunpower, Inc. Friction-factor and heat-transfer correlations based on data taken with the NASAlSunpower oscillating-flow test rig also provide experimentally based correlations that are useful in defining parameters for the porous-media model; these correlations are documented in Gedeon Associates' Sage Stirling-Code Manuals. These sources of experimentally based information were used to define the following terms and parameters needed in the non-equilibrium porous-media model: hydrodynamic dispersion, permeability, inertial coefficient, fluid effective thermal conductivity (including themal dispersion and estimate of tortuosity effects}, and fluid-solid heat transfer

  4. Dynamics of polymerization induced phase separation in reactive polymer blends

    NASA Astrophysics Data System (ADS)

    Lee, Jaehyung

    Mechanisms and dynamics of phase decomposition following polymerization induced phase separation (PIPS) of reactive polymer blends have been investigated experimentally and theoretically. The phenomenon of PIPS is a non-equilibrium and non-linear dynamic process. The mechanism of PIPS has been thought to be a nucleation and growth (NG) type originally, however, newer results indicate spinodal decomposition (SD). In PIPS, the coexistence curve generally passes through the reaction temperature at off-critical compositions, thus phase separation has to be initiated first in the metastable region where nucleation occurs. When the system farther drifts from the metastable to unstable region, the NG structure transforms to the SD bicontinuous morphology. The crossover behavior of PIPS may be called nucleation initiated spinodal decomposition (NISD). The formation of newer domains between the existing ones is responsible for the early stage of PIPS. Since PIPS is non- equilibrium kinetic process, it would not be surprising to discern either or both structures. The phase separation dynamics of DGEBA/CTBN mixtures having various kinds of curing agents from low reactivity to high reactivity and various amount of curing agents were examined at various reaction temperatures. The phase separation behavior was monitored by a quantity of scattered light intensity experimentally and by a quantity of collective structure factor numerically. Prior to the study of phase separation dynamics, a preliminary investigation on the isothermal cure behavior of the mixtures were executed in order to determine reaction kinetics parameters. The cure behavior followed the overall second order reaction kinetics. Next, based on the knowledge obtained from the phase separation dynamics study of DGEBA/CTBN mixtures, the phase separation dynamics of various composition of DGEBA/R45EPI mixtures having MDA as a curing agent were investigated. The phase separation behavior was quite dependent upon the

  5. Computing diffusivities from particle models out of equilibrium

    NASA Astrophysics Data System (ADS)

    Embacher, Peter; Dirr, Nicolas; Zimmer, Johannes; Reina, Celia

    2018-04-01

    A new method is proposed to numerically extract the diffusivity of a (typically nonlinear) diffusion equation from underlying stochastic particle systems. The proposed strategy requires the system to be in local equilibrium and have Gaussian fluctuations but it is otherwise allowed to undergo arbitrary out-of-equilibrium evolutions. This could be potentially relevant for particle data obtained from experimental applications. The key idea underlying the method is that finite, yet large, particle systems formally obey stochastic partial differential equations of gradient flow type satisfying a fluctuation-dissipation relation. The strategy is here applied to three classic particle models, namely independent random walkers, a zero-range process and a symmetric simple exclusion process in one space dimension, to allow the comparison with analytic solutions.

  6. Light-induced electronic non-equilibrium in plasmonic particles.

    PubMed

    Kornbluth, Mordechai; Nitzan, Abraham; Seideman, Tamar

    2013-05-07

    We consider the transient non-equilibrium electronic distribution that is created in a metal nanoparticle upon plasmon excitation. Following light absorption, the created plasmons decohere within a few femtoseconds, producing uncorrelated electron-hole pairs. The corresponding non-thermal electronic distribution evolves in response to the photo-exciting pulse and to subsequent relaxation processes. First, on the femtosecond timescale, the electronic subsystem relaxes to a Fermi-Dirac distribution characterized by an electronic temperature. Next, within picoseconds, thermalization with the underlying lattice phonons leads to a hot particle in internal equilibrium that subsequently equilibrates with the environment. Here we focus on the early stage of this multistep relaxation process, and on the properties of the ensuing non-equilibrium electronic distribution. We consider the form of this distribution as derived from the balance between the optical absorption and the subsequent relaxation processes, and discuss its implication for (a) heating of illuminated plasmonic particles, (b) the possibility to optically induce current in junctions, and (c) the prospect for experimental observation of such light-driven transport phenomena.

  7. Process for operating equilibrium controlled reactions

    DOEpatents

    Nataraj, Shankar; Carvill, Brian Thomas; Hufton, Jeffrey Raymond; Mayorga, Steven Gerard; Gaffney, Thomas Richard; Brzozowski, Jeffrey Richard

    2001-01-01

    A cyclic process for operating an equilibrium controlled reaction in a plurality of reactors containing an admixture of an adsorbent and a reaction catalyst suitable for performing the desired reaction which is operated in a predetermined timed sequence wherein the heating and cooling requirements in a moving reaction mass transfer zone within each reactor are provided by indirect heat exchange with a fluid capable of phase change at temperatures maintained in each reactor during sorpreaction, depressurization, purging and pressurization steps during each process cycle.

  8. Metastable and equilibrium phase diagrams of unconjugated bilirubin IXα as functions of pH in model bile systems: Implications for pigment gallstone formation

    PubMed Central

    Berman, Marvin D.

    2014-01-01

    Metastable and equilibrium phase diagrams for unconjugated bilirubin IXα (UCB) in bile are yet to be determined for understanding the physical chemistry of pigment gallstone formation. Also, UCB is a molecule of considerable biomedical importance because it is a potent antioxidant and an inhibitor of atherogenesis. We employed principally a titrimetric approach to obtain metastable and equilibrium UCB solubilities in model bile systems composed of taurine-conjugated bile salts, egg yolk lecithin (mixed long-chain phosphatidylcholines), and cholesterol as functions of total lipid concentration, biliary pH values, and CaCl2 plus NaCl concentrations. Metastable and equilibrium precipitation pH values were obtained, and average pKa values of the two carboxyl groups of UCB were calculated. Added lecithin and increased temperature decreased UCB solubility markedly, whereas increases in bile salt concentrations and molar levels of urea augmented solubility. A wide range of NaCl and cholesterol concentrations resulted in no specific effects, whereas added CaCl2 produced large decreases in UCB solubilities at alkaline pH values only. UV-visible absorption spectra were consistent with both hydrophobic and hydrophilic interactions between UCB and bile salts that were strongly influenced by pH. Reliable literature values for UCB compositions of native gallbladder biles revealed that biles from hemolytic mice and humans with black pigment gallstones are markedly supersaturated with UCB and exhibit more acidic pH values, whereas biles from nonstone control animals and patients with cholesterol gallstone are unsaturated with UCB. PMID:25359538

  9. Experimental studies on equilibrium adsorption isosteres and determination of the thermodynamic quantities of polar media on alumina Al2O3

    NASA Astrophysics Data System (ADS)

    Yonova, Albena

    2017-03-01

    The present work is a revieif of theoretical and experimental study on the adsorption performance of the adsorbent Alumina (Al2O3) used in the adsorption system. An experimental investigation on the equilibrium adsorption isosteres at low pressure (< 1 atm) of working pairs Al2O3/H2O and Al2O3/C2H6O2 is carried out. The isovolume measurement method is adopted in the test setup to directly measure the saturated vapor pressures of working pairs at vapor-liquid equilibrium (dG=0 and dμi=0). Quantity adsorbed is determined from pressure, volume and temperature using gas law. The isosteric heat of adsorption is calculated from the slope of the plot of lnP versus 1/T different amounts of adsorbate onto adsorbent as follows: 0,01 vol% Al2O3/H2O; 0,03 vol% Al2O3/H2O; 0,1 vol% Al2O3/H2O; 0,01 vol% Al2O3/C2H6O2; 0,03 vol% Al2O3/C2H6O2; 0,1 vol% Al2O3/C2H6O2. This study shows that adsorption working pair Al2O3 C2H6O2 has better adsorption performances than those of the A2O3/H2O. Surface acidity! is a most important property! far both adsorption and catalysis and therefore is examined structure of active sites of alumina surface. Thermodynamic parameters such as isosteric heat of adsorption, isosteric enthalpy and entropy of adsorption are critical design variables in estimating the performance and predicting the mechanism of an adsorption process and are also one of the basic requirements for the characterization and optimization of an adsorption process

  10. Topological Quantum Phase Transition in Synthetic Non-Abelian Gauge Potential: Gauge Invariance and Experimental Detections

    PubMed Central

    Sun, Fadi; Yu, Xiao-Lu; Ye, Jinwu; Fan, Heng; Liu, Wu-Ming

    2013-01-01

    The method of synthetic gauge potentials opens up a new avenue for our understanding and discovering novel quantum states of matter. We investigate the topological quantum phase transition of Fermi gases trapped in a honeycomb lattice in the presence of a synthetic non-Abelian gauge potential. We develop a systematic fermionic effective field theory to describe a topological quantum phase transition tuned by the non-Abelian gauge potential and explore its various important experimental consequences. Numerical calculations on lattice scales are performed to compare with the results achieved by the fermionic effective field theory. Several possible experimental detection methods of topological quantum phase transition are proposed. In contrast to condensed matter experiments where only gauge invariant quantities can be measured, both gauge invariant and non-gauge invariant quantities can be measured by experimentally generating various non-Abelian gauges corresponding to the same set of Wilson loops. PMID:23846153

  11. Hydrostatic Paradox: Experimental Verification of Pressure Equilibrium

    ERIC Educational Resources Information Center

    Kodejška, C.; Ganci, S.; Ríha, J.; Sedlácková, H.

    2017-01-01

    This work is focused on the experimental verification of the balance between the atmospheric pressure acting on the sheet of paper, which encloses the cylinder completely or partially filled with water from below, where the hydrostatic pressure of the water column acts against the atmospheric pressure. First of all this paper solves a theoretical…

  12. Experimental generation of Hermite-Gauss and Ince-Gauss beams through kinoform phase holograms

    NASA Astrophysics Data System (ADS)

    Mellado-Villaseñor, Gabriel; Aguirre-Olivas, Dilia; Sánchez-de-la-Llave, David; Arrizón, Victor

    2015-08-01

    We generate Hermite-Gauss and Ince-Gauss beams by using kinoform phase holograms encoded onto a liquid crystal display. The phase transmittance of this holograms coincide with the phases of such beams. Scale versions of the desired beams appear at the Fourier domain of the KPHs. When an appropriated pupil size is employed, the method synthesizes HG and IG beams with relatively high accuracy and high efficiency. It is noted that experimental and numerical results are agreement with the theory.

  13. Global dynamics of non-equilibrium gliding in animals.

    PubMed

    Yeaton, Isaac J; Socha, John J; Ross, Shane D

    2017-03-17

    Gliding flight-moving horizontally downward through the air without power-has evolved in a broad diversity of taxa and serves numerous ecologically relevant functions such as predator escape, expanding foraging locations, and finding mates, and has been suggested as an evolutionary pathway to powered flight. Historically, gliding has been conceptualized using the idealized conditions of equilibrium, in which the net aerodynamic force on the glider balances its weight. While this assumption is appealing for its simplicity, recent studies of glide trajectories have shown that equilibrium gliding is not the norm for most species. Furthermore, equilibrium theory neglects the aerodynamic differences between species, as well as how a glider can modify its glide path using control. To investigate non-equilibrium glide behavior, we developed a reduced-order model of gliding that accounts for self-similarity in the equations of motion, such that the lift and drag characteristics alone determine the glide trajectory. From analysis of velocity polar diagrams of horizontal and vertical velocity from several gliding species, we find that pitch angle, the angle between the horizontal and chord line, is a control parameter that can be exploited to modulate glide angle and glide speed. Varying pitch results in changing locations of equilibrium glide configurations in the velocity polar diagram that govern passive glide dynamics. Such analyses provide a new mechanism of interspecies comparison and tools to understand experimentally-measured kinematics data and theory. In addition, this analysis suggests that the lift and drag characteristics of aerial and aquatic autonomous gliders can be engineered to passively alter glide trajectories with minimal control effort.

  14. Fluctuation-dissipation relation and stationary distribution of an exactly solvable many-particle model for active biomatter far from equilibrium.

    PubMed

    Netz, Roland R

    2018-05-14

    An exactly solvable, Hamiltonian-based model of many massive particles that are coupled by harmonic potentials and driven by stochastic non-equilibrium forces is introduced. The stationary distribution and the fluctuation-dissipation relation are derived in closed form for the general non-equilibrium case. Deviations from equilibrium are on one hand characterized by the difference of the obtained stationary distribution from the Boltzmann distribution; this is possible because the model derives from a particle Hamiltonian. On the other hand, the difference between the obtained non-equilibrium fluctuation-dissipation relation and the standard equilibrium fluctuation-dissipation theorem allows us to quantify non-equilibrium in an alternative fashion. Both indicators of non-equilibrium behavior, i.e., deviations from the Boltzmann distribution and deviations from the equilibrium fluctuation-dissipation theorem, can be expressed in terms of a single non-equilibrium parameter α that involves the ratio of friction coefficients and random force strengths. The concept of a non-equilibrium effective temperature, which can be defined by the relation between fluctuations and the dissipation, is by comparison with the exactly derived stationary distribution shown not to hold, even if the effective temperature is made frequency dependent. The analysis is not confined to close-to-equilibrium situations but rather is exact and thus holds for arbitrarily large deviations from equilibrium. Also, the suggested harmonic model can be obtained from non-linear mechanical network systems by an expansion in terms of suitably chosen deviatory coordinates; the obtained results should thus be quite general. This is demonstrated by comparison of the derived non-equilibrium fluctuation dissipation relation with experimental data on actin networks that are driven out of equilibrium by energy-consuming protein motors. The comparison is excellent and allows us to extract the non-equilibrium

  15. Fluctuation-dissipation relation and stationary distribution of an exactly solvable many-particle model for active biomatter far from equilibrium

    NASA Astrophysics Data System (ADS)

    Netz, Roland R.

    2018-05-01

    An exactly solvable, Hamiltonian-based model of many massive particles that are coupled by harmonic potentials and driven by stochastic non-equilibrium forces is introduced. The stationary distribution and the fluctuation-dissipation relation are derived in closed form for the general non-equilibrium case. Deviations from equilibrium are on one hand characterized by the difference of the obtained stationary distribution from the Boltzmann distribution; this is possible because the model derives from a particle Hamiltonian. On the other hand, the difference between the obtained non-equilibrium fluctuation-dissipation relation and the standard equilibrium fluctuation-dissipation theorem allows us to quantify non-equilibrium in an alternative fashion. Both indicators of non-equilibrium behavior, i.e., deviations from the Boltzmann distribution and deviations from the equilibrium fluctuation-dissipation theorem, can be expressed in terms of a single non-equilibrium parameter α that involves the ratio of friction coefficients and random force strengths. The concept of a non-equilibrium effective temperature, which can be defined by the relation between fluctuations and the dissipation, is by comparison with the exactly derived stationary distribution shown not to hold, even if the effective temperature is made frequency dependent. The analysis is not confined to close-to-equilibrium situations but rather is exact and thus holds for arbitrarily large deviations from equilibrium. Also, the suggested harmonic model can be obtained from non-linear mechanical network systems by an expansion in terms of suitably chosen deviatory coordinates; the obtained results should thus be quite general. This is demonstrated by comparison of the derived non-equilibrium fluctuation dissipation relation with experimental data on actin networks that are driven out of equilibrium by energy-consuming protein motors. The comparison is excellent and allows us to extract the non-equilibrium

  16. Chemical Principles Revisited: Chemical Equilibrium.

    ERIC Educational Resources Information Center

    Mickey, Charles D.

    1980-01-01

    Describes: (1) Law of Mass Action; (2) equilibrium constant and ideal behavior; (3) general form of the equilibrium constant; (4) forward and reverse reactions; (5) factors influencing equilibrium; (6) Le Chatelier's principle; (7) effects of temperature, changing concentration, and pressure on equilibrium; and (8) catalysts and equilibrium. (JN)

  17. Equilibrium swelling properties of polyampholytic hydrogels

    NASA Astrophysics Data System (ADS)

    English, Anthony E.; Mafé, Salvador; Manzanares, José A.; Yu, Xiahong; Grosberg, Alexander Yu.; Tanaka, Toyoichi

    1996-06-01

    The role of counter ions and ion dissociation in establishing the equilibrium swelling of balanced and unbalanced polyampholytic hydrogels has been investigated experimentally and theoretically. The swelling dependence on both the net charge offset and the external bath salt concentration has been examined using an acrylamide based polyampholytic hydrogels. By careful consideration of the swelling kinetics, we illustrate the effects of ion dissociation equilibria and counter ion shielding in polyampholytic hydrogels near their balance point where both polyelectrolyte and polyampholyte effects are present. The theory considers a Flory type swelling model where the Coulombic interactions between fixed ions in the hydrogel resemble those of an ionic solid with a Debye screening factor. Theoretical predictions from this model are in qualitative agreement with our experimental results.

  18. Determination and theoretical aspects of the equilibrium between dissolved organic matter and hydrophobic organic micropollutants in water (Kdoc).

    PubMed

    Krop, H B; van Noort, P C; Govers, H A

    2001-01-01

    Literature on the equilibrium constant for distribution between dissolved organic carbon (DOC) (Kdoc) data of strongly hydrophobic organic contaminants were collected and critically analyzed. About 900 Kdoc entries for experimental values were retrieved and tabulated, including those factors that can influence them. In addition, quantitative structure-activity relationship (QSAR) prediction equations were retrieved and tabulated. Whether a partition or association process between the contaminant and DOC takes place could not be fully established, but indications toward an association process are strong in several cases. Equilibrium between a contaminant and DOC in solution was shown to be achieved within a minute. When the equilibrium shifts in time, this was caused by either a physical or chemical change of the DOC, affecting the lighter fractions most. Adsorption isotherms turned out to be linear in the contaminant concentration for the relevant DOC concentration up to 100 mg of C/L. Eighteen experimental methods have been developed for the determination of the pertinent distribution constant. Experimental Kdoc values revealed the expected high correlation with partition coefficients over n-octanol and water (Kow) for all experimental methods, except for the HPLC and apparent solubility (AS) method. Only fluorescence quenching (FQ) and solid-phase microextraction (SPME) methods could quantify fast equilibration. Only 21% of the experimental values had a 95% confidence interval, which was statistically significantly different from zero. Variation in Kdoc values was shown to be high, caused mainly by the large variation of DOC in water samples. Even DOC from one sample gave different equilibrium constants for different DOC fractions. Measured Kdoc values should, therefore, be regarded as average values. Kdoc was shown to increase on increasing molecular mass, indicating that the molecular mass distribution is a proper normalization function for the average Kdoc at

  19. Exploring the Clapeyron Equation and the Phase Rule Using a Mechanical Drawing Toy

    ERIC Educational Resources Information Center

    Darvesh, Katherine V.

    2013-01-01

    The equilibrium between phases is a key concept from the introductory physical chemistry curriculum. Phase diagrams display which phase is the most stable at a given temperature and pressure. If more than one phase has the lowest Gibbs energy, then those phases are in equilibrium under those conditions. An activity designed to demonstrate the…

  20. Experimental data for the slug two-phase flow characteristics in horizontal pipeline.

    PubMed

    Mohmmed, Abdalellah O; Nasif, Mohammad S; Al-Kayiem, Hussain H

    2018-02-01

    The data presented in this article were the basis for the study reported in the research articles entitled "Statistical assessment of experimental observation on the slug body length and slug translational velocity in a horizontal pipe" (Al-Kayiem et al., 2017) [1] which presents an experimental investigation of the slug velocity and slug body length for air-water tow phase flow in horizontal pipe. Here, in this article, the experimental set-up and the major instruments used for obtaining the computed data were explained in details. This data will be presented in the form of tables and videos.

  1. Non-equilibrium simulation of CH4 production through the depressurization method from gas hydrate reservoirs

    NASA Astrophysics Data System (ADS)

    Qorbani, Khadijeh; Kvamme, Bjørn

    2016-04-01

    Natural gas hydrates (NGHs) in nature are formed from various hydrate formers (i.e. aqueous, gas, and adsorbed phases). As a result, due to Gibbs phase rule and the combined first and second laws of thermodynamics CH4-hydrate cannot reach thermodynamic equilibrium in real reservoir conditions. CH4 is the dominant component in NGH reservoirs. It is formed as a result of biogenic degradation of biological material in the upper few hundred meters of subsurface. It has been estimated that the amount of fuel-gas reserve in NGHs exceed the total amount of fossil fuel explored until today. Thus, these reservoirs have the potential to satisfy the energy requirements of the future. However, released CH4 from dissociated NGHs could find its way to the atmosphere and it is a far more aggressive greenhouse gas than CO2, even though its life-time is shorter. Lack of reliable field data makes it difficult to predict the production potential, as well as safety of CH4 production from NGHs. Computer simulations can be used as a tool to investigate CH4 production through different scenarios. Most hydrate simulators within academia and industry treat hydrate phase transitions as an equilibrium process and those which employ the kinetic approach utilize simple laboratory data in their models. Furthermore, it is typical to utilize a limited thermodynamic description where only temperature and pressure projections are considered. Another widely used simplification is to assume only a single route for the hydrate phase transitions. The non-equilibrium nature of hydrate indicates a need for proper kinetic models to describe hydrate dissociation and reformation in the reservoir with respect to thermodynamics variables, CH4 mole-fraction, pressure and temperature. The RetrasoCodeBright (RCB) hydrate simulator has previously been extended to model CH4-hydrate dissociation towards CH4 gas and water. CH4-hydrate is added to the RCB data-base as a pseudo mineral. Phase transitions are treated

  2. Energy Flow in Dense Off-Equilibrium Plasma

    DTIC Science & Technology

    2016-07-15

    akT e in our system100 i e T T Teller 1966 Smoking Gun Experiment: Laser Breakdown in COLD gas In going from room to liquid Nitrogen temperature...oflaser breakdown have revealed a new phase of off-equilibrium plasma that has a tensile strength similar to a liquid , and reduced ion-electron...approved for public release. Part 1: Energy Balance in Sonoluminescing Dense Plasma Sonoluminescence occurs from rapid implosion of gas bubbles caused to

  3. Experimental observation of carrier-envelope-phase effects by multicycle pulses

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

    Jha, Pankaj K.; Scully, Marlan O.; Mechanical and Aerospace Engineering and the Princeton Institute for the Science and Technology of Materials, Princeton University, Princeton, New Jersey 08544

    2011-03-15

    We present an experimental and theoretical study of carrier-envelope-phase (CEP) effects on the population transfer between two bound atomic states interacting with pulses consisting of many cycles. Using intense radio-frequency pulse with Rabi frequency of the order of the atomic transition frequency, we investigate the influence of the CEP on the control of phase-dependent multiphoton transitions between the Zeeman sublevels of the ground state of {sup 87}Rb. Our scheme has no limitation on the duration of the pulses. Extending the CEP control to longer pulses creates interesting possibilities to generate pulses with accuracy that is better than the period ofmore » optical oscillations.« less

  4. Vibrational non-equilibrium in the hydrogen-oxygen reaction. Comparison with experiment

    NASA Astrophysics Data System (ADS)

    Skrebkov, Oleg V.

    2015-03-01

    A theoretical model is proposed for the chemical and vibrational kinetics of hydrogen oxidation based on consistent accounting of the vibrational non-equilibrium of the HO2 radical that forms as a result of the bimolecular recombination H+O2 → HO2. In the proposed model, the chain branching H+O2 = O+OH and inhibiting H+O2+M = HO2+M formal reactions are treated (in the terms of elementary processes) as a single multi-channel process of forming, intramolecular energy redistribution between modes, relaxation, and unimolecular decay of the comparatively long-lived vibrationally excited HO2 radical, which is able to react and exchange energy with the other components of the mixture. The model takes into account the vibrational non-equilibrium of the starting (primary) H2 and O2 molecules, as well as the most important molecular intermediates HO2, OH, O2(1Δ), and the main reaction product H2O. It is shown that the hydrogen-oxygen reaction proceeds in the absence of vibrational equilibrium, and the vibrationally excited HO2(v) radical acts as a key intermediate in a fundamentally important chain branching process and in the generation of electronically excited species O2(1Δ), O(1D), and OH(2Σ+). The calculated results are compared with the shock tube experimental data for strongly diluted H2-O2 mixtures at 1000 < T < 2500 K, 0.5 < p < 4 atm. It is demonstrated that this approach is promising from the standpoint of reconciling the predictions of the theoretical model with experimental data obtained by different authors for various compositions and conditions using different methods. For T < 1500 K, the nature of the hydrogen-oxygen reaction is especially non-equilibrium, and the vibrational non-equilibrium of the HO2 radical is the essence of this process. The quantitative estimation of the vibrational relaxation characteristic time of the HO2 radical in its collisions with H2 molecules has been obtained as a result of the comparison of different experimental data on

  5. Evaluation of Magnetic Diagnostics for MHD Equilibrium Reconstruction of LHD Discharges

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

    Sontag, Aaron C; Hanson, James D.; Lazerson, Sam

    2011-01-01

    Equilibrium reconstruction is the process of determining the set of parameters of an MHD equilibrium that minimize the difference between expected and experimentally observed signals. This is routinely performed in axisymmetric devices, such as tokamaks, and the reconstructed equilibrium solution is then the basis for analysis of stability and transport properties. The V3FIT code [1] has been developed to perform equilibrium reconstruction in cases where axisymmetry cannot be assumed, such as in stellarators. The present work is focused on using V3FIT to analyze plasmas in the Large Helical Device (LHD) [2], a superconducting, heliotron type device with over 25 MWmore » of heating power that is capable of achieving both high-beta ({approx}5%) and high density (>1 x 10{sup 21}/m{sup 3}). This high performance as well as the ability to drive tens of kiloamperes of toroidal plasma current leads to deviations in the equilibrium state from the vacuum flux surfaces. This initial study examines the effectiveness of using magnetic diagnostics as the observed signals in reconstructing experimental plasma parameters for LHD discharges. V3FIT uses the VMEC [3] 3D equilibrium solver to calculate an initial equilibrium solution with closed, nested flux surfaces based on user specified plasma parameters. This equilibrium solution is then used to calculate the expected signals for specified diagnostics. The differences between these expected signal values and the observed values provides a starting {chi}{sup 2} value. V3FIT then varies all of the fit parameters independently, calculating a new equilibrium and corresponding {chi}{sup 2} for each variation. A quasi-Newton algorithm [1] is used to find the path in parameter space that leads to a minimum in {chi}{sup 2}. Effective diagnostic signals must vary in a predictable manner with the variations of the plasma parameters and this signal variation must be of sufficient amplitude to be resolved from the signal noise. Signal

  6. Solvent isotope-induced equilibrium perturbation for isocitrate lyase.

    PubMed

    Quartararo, Christine E; Hadi, Timin; Cahill, Sean M; Blanchard, John S

    2013-12-23

    Isocitrate lyase (ICL) catalyzes the reversible retro-aldol cleavage of isocitrate to generate glyoxylate and succinate. ICL is the first enzyme of the glyoxylate shunt, which allows for the anaplerosis of citric acid cycle intermediates under nutrient limiting conditions. In Mycobacterium tuberculosis, the source of ICL for these studies, ICL is vital for the persistence phase of the bacterium's life cycle. Solvent kinetic isotope effects (KIEs) in the direction of isocitrate cleavage ((D₂O)V = 2.0 ± 0.1, and (D₂O)[V/K(isocitrate)] = 2.2 ± 0.3) arise from the initial deprotonation of the C2 hydroxyl group of isocitrate or the protonation of the aci-acid of the succinate product of the isocitrate aldol cleavage by a solvent-derived proton. This KIE suggested that an equilibrium mixture of all protiated isocitrate, glyoxylate, and succinate prepared in D₂O would undergo transient changes in equilibrium concentrations as a result of the solvent KIE and solvent-derived deuterium incorporation into both succinate and isocitrate. No change in the isotopic composition of glyoxylate was expected or observed. We have directly monitored the changing concentrations of all isotopic species of all reactants and products using a combination of nuclear magnetic resonance (NMR) spectroscopy and mass spectrometry. Continuous monitoring of glyoxylate by ¹H NMR spectroscopy shows a clear equilibrium perturbation in D₂O. The final equilibrium isotopic composition of reactants in D₂O revealed dideuterated succinate, protiated glyoxylate, and monodeuterated isocitrate, with the transient appearance and disappearance of monodeuterated succinate. A model for the equilibrium perturbation of substrate species and their time-dependent isotopic composition is presented.

  7. Solvent Isotope-induced Equilibrium Perturbation for Isocitrate Lyase

    PubMed Central

    Quartararo, Christine E.; Hadi, Timin; Cahill, Sean M.; Blanchard, John S.

    2014-01-01

    Isocitrate lyase (ICL) catalyzes the reversible retro-aldol cleavage of isocitrate to generate glyoxylate and succinate. ICL is the first enzyme of the glyoxylate shunt, which allows for the anaplerosis of citric acid cycle intermediates under nutrient limiting conditions. In Mycobacterium tuberculosis, the source of ICL for these studies, ICL is vital for the persistence phase of the bacteria’s life cycle. Solvent kinetic isotope effects (KIEs) in the direction of isocitrate cleavage of D2OV = 2.0 ± 0.1 and D2O[V/Kisocitrate] = 2.2 ± 0.3 arise from the initial deprotonation of the C2 hydroxyl group of isocitrate or the protonation of the aci-acid of succinate product of the isocitrate aldol cleavage by a solvent-derived proton. This KIE suggested that an equilibrium mixture of all protiated isocitrate, glyoxylate and succinate prepared in D2O, would undergo transient changes in equilibrium concentrations as a result of the solvent KIE and solvent-derived deuterium incorporation into both succinate and isocitrate. No change in the isotopic composition of glyoxylate was expected or observed. We have directly monitored the changing concentrations of all isotopic species of all reactants and products using a combination of NMR spectroscopy and mass spectrometry. Continuous monitoring of glyoxylate by 1H NMR spectroscopy shows a clear equilibrium perturbation in D2O. The final equilibrium isotopic composition of reactants in D2O revealed di-deuterated succinate, protiated glyoxylate, and mono-deuterated isocitrate, with the transient appearance and disappearance of mono-deuterated succinate. A model for the equilibrium perturbation of substrate species, and their time-dependent isotopic composition is presented. PMID:24261638

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

    NASA Astrophysics Data System (ADS)

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

    2018-04-01

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

  9. Equilibrium evolution in oscillating-field current-drive experiments

    NASA Astrophysics Data System (ADS)

    McCollam, K. J.; Anderson, J. K.; Blair, A. P.; Craig, D.; Den Hartog, D. J.; Ebrahimi, F.; O'Connell, R.; Reusch, J. A.; Sarff, J. S.; Stephens, H. D.; Stone, D. R.; Brower, D. L.; Deng, B. H.; Ding, W. X.

    2010-08-01

    Oscillating-field current drive (OFCD) is a proposed method of steady-state toroidal plasma sustainment in which ac poloidal and toroidal loop voltages are applied to produce a dc plasma current. OFCD is added to standard, inductively sustained reversed-field pinch plasmas in the Madison Symmetric Torus [R. N. Dexter et al., Fusion Technol. 19, 131 (1991)]. Equilibrium profiles and fluctuations during a single cycle are measured and analyzed for different relative phases between the two OFCD voltages and for OFCD off. For OFCD phases leading to the most added plasma current, the measured energy confinement is slightly better than that for OFCD off. By contrast, the phase of the maximum OFCD helicity-injection rate also has the maximum decay rate, which is ascribed to transport losses during discrete magnetic-fluctuation events induced by OFCD. Resistive-magnetohydrodynamic simulations of the experiments reproduce the observed phase dependence of the added current.

  10. Non-equilibrium thermionic electron emission for metals at high temperatures

    NASA Astrophysics Data System (ADS)

    Domenech-Garret, J. L.; Tierno, S. P.; Conde, L.

    2015-08-01

    Stationary thermionic electron emission currents from heated metals are compared against an analytical expression derived using a non-equilibrium quantum kappa energy distribution for the electrons. The latter depends on the temperature decreasing parameter κ ( T ) , which decreases with increasing temperature and can be estimated from raw experimental data and characterizes the departure of the electron energy spectrum from equilibrium Fermi-Dirac statistics. The calculations accurately predict the measured thermionic emission currents for both high and moderate temperature ranges. The Richardson-Dushman law governs electron emission for large values of kappa or equivalently, moderate metal temperatures. The high energy tail in the electron energy distribution function that develops at higher temperatures or lower kappa values increases the emission currents well over the predictions of the classical expression. This also permits the quantitative estimation of the departure of the metal electrons from the equilibrium Fermi-Dirac statistics.

  11. The effects of the macrotetralide actin antibiotics on the equilibrium extraction of alkali metal salts into organic solvents.

    PubMed

    Eisenman, G; Ciani, S; Szabo, G

    1969-12-01

    In order to clarify the mechanism by which neutral molecules such as the macrotetralide actin antibiotics make phospholipid bilayer membranes selectively permeable to cations, we have studied, both theoretically and experimentally, the extraction by these antibiotics of cations from aqueous solutions into organic solvents. The experiments involve merely shaking an organic solvent phase containing the antibiotic with aqueous solutions containing various cationic salts of a lipid-soluble colored anion. The intensity of color of the organic phase is then measured spectrophotometrically to indicate how much salt has been extracted. From such measurements of the equilibrium extraction of picrate and dinitrophenolate salts of Li, Na, K, Rb, Cs, and NH4 into n-hexane, dichloromethane, and hexane-dichloromethane mixtures, we have verified that the chemical reactions are as simple as previously postulated, at least for nonactin, monactin, dinactin, and trinactin. The equilibrium constant for the extraction of each cation by a given macrotetralide actin antibiotic was also found to be measurable with sufficient precision for meaningful differences among the members of this series of antibiotics to be detected. It is noteworthy that the ratios of selectivities among the various cations were discovered to be characteristic of a given antibiotic and to be completely independent of the solvent used. This finding and others reported here indicate that the size and shape of the complex formed between the macrotetralide and a given cation is the same, regardless of the species of cation bound. For such "isosteric" complexes, notable simplifications of the theory become possible which enable us to predict not only the electrical properties of a membrane made of the same solvent and having the thinness of the phospholipid bilayer but also, and more importantly, the electrical properties of the phospholipid bilayer membrane itself. These predictions will be compared with experimental

  12. A hyperjerk memristive system with infinite equilibrium points

    NASA Astrophysics Data System (ADS)

    Prousalis, Dimitrios A.; Volos, Christos K.; Stouboulos, Ioannis N.; Kyprianidis, Ioannis M.

    2017-09-01

    A novel 4-D dynamical memristive system is presented in this work. The specificity of the model is that it develops a line of equilibrium points and it has hyperjerk dynamics in a particular range of the parameters space. The behavior of the suggested system is investigated through numerical simulations, by using phase portraits, Lyapunov exponents, bifurcation diagrams. Also, its circuital implementation confirms the memristive system's expected dynamics.

  13. Overview: Homogeneous nucleation from the vapor phase-The experimental science.

    PubMed

    Wyslouzil, Barbara E; Wölk, Judith

    2016-12-07

    Homogeneous nucleation from the vapor phase has been a well-defined area of research for ∼120 yr. In this paper, we present an overview of the key experimental and theoretical developments that have made it possible to address some of the fundamental questions first delineated and investigated in C. T. R. Wilson's pioneering paper of 1897 [C. T. R. Wilson, Philos. Trans. R. Soc., A 189, 265-307 (1897)]. We review the principles behind the standard experimental techniques currently used to measure isothermal nucleation rates, and discuss the molecular level information that can be extracted from these measurements. We then highlight recent approaches that interrogate the vapor and intermediate clusters leading to particle formation, more directly.

  14. The magic triangle goes MAD: experimental phasing with a bromine derivative

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

    Beck, Tobias, E-mail: tbeck@shelx.uni-ac.gwdg.de; Gruene, Tim; Sheldrick, George M.

    2010-04-01

    5-Amino-2, 4, 6-tribromoisophthalic acid is used as a phasing tool for protein structure determination by MAD phasing. It is the second representative of a novel class of compounds for heavy-atom derivatization that combine heavy atoms with amino and carboxyl groups for binding to proteins. Experimental phasing is an essential technique for the solution of macromolecular structures. Since many heavy-atom ion soaks suffer from nonspecific binding, a novel class of compounds has been developed that combines heavy atoms with functional groups for binding to proteins. The phasing tool 5-amino-2, 4, 6-tribromoisophthalic acid (B3C) contains three functional groups (two carboxylate groups andmore » one amino group) that interact with proteins via hydrogen bonds. Three Br atoms suitable for anomalous dispersion phasing are arranged in an equilateral triangle and are thus readily identified in the heavy-atom substructure. B3C was incorporated into proteinase K and a multiwavelength anomalous dispersion (MAD) experiment at the Br K edge was successfully carried out. Radiation damage to the bromine–carbon bond was investigated. A comparison with the phasing tool I3C that contains three I atoms for single-wavelength anomalous dispersion (SAD) phasing was also carried out.« less

  15. Experimentally reproduced textures and mineral chemistries of high-titanium mare basalts

    NASA Technical Reports Server (NTRS)

    Usselman, T. M.; Lofgren, G. E.; Williams, R. J.; Donaldson, C. H.

    1975-01-01

    Many of the textures, morphologies, and mineral chemistries of the high-titanium mare basalts have been experimentally duplicated using single-stage cooling histories. Lunar high-titanium mare basalts are modeled in a 1 m thick gravitationally differentiating flow based on cooling rates, thermal models, and modal olivine contents. The low-pressure equilibrium phase relations of a synthetic high-titanium basalt composition were investigated as a function of oxygen fugacity, and petrographic criteria are developed for the recognition of phenocrysts which were present in the liquid at the time of eruption.

  16. The Approach to Equilibrium: Detailed Balance and the Master Equation

    ERIC Educational Resources Information Center

    Alexander, Millard H.; Hall, Gregory E.; Dagdigian, Paul J.

    2011-01-01

    The approach to the equilibrium (Boltzmann) distribution of populations of internal states of a molecule is governed by inelastic collisions in the gas phase and with surfaces. The set of differential equations governing the time evolution of the internal state populations is commonly called the master equation. An analytic solution to the master…

  17. N-Methyl Inversion and Accurate Equilibrium Structures in Alkaloids: Pseudopelletierine.

    PubMed

    Vallejo-López, Montserrat; Écija, Patricia; Vogt, Natalja; Demaison, Jean; Lesarri, Alberto; Basterretxea, Francisco J; Cocinero, Emilio J

    2017-11-21

    A rotational spectroscopy investigation has resolved the conformational equilibrium and structural properties of the alkaloid pseudopelletierine. Two different conformers, which originate from inversion of the N-methyl group from an axial to an equatorial position, have been unambiguously identified in the gas phase, and nine independent isotopologues have been recorded by Fourier-transform microwave spectroscopy in a jet expansion. Both conformers share a chair-chair configuration of the two bridged six-membered rings. The conformational equilibrium is displaced towards the axial form, with a relative population in the supersonic jet of N axial /N equatorial ≈2/1. An accurate equilibrium structure has been determined by using the semiexperimental mixed-estimation method and alternatively computed by quantum-chemical methods up to the coupled-cluster level of theory. A comparison with the N-methyl inversion equilibria in related tropanes is also presented. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. Strontium isotope fractionation during strontianite (SrCO3) dissolution, precipitation and at equilibrium

    NASA Astrophysics Data System (ADS)

    Mavromatis, Vasileios; Harrison, Anna L.; Eisenhauer, Anton; Dietzel, Martin

    2017-12-01

    In this study we examine the behavior of stable Sr isotopes between strontianite [SrCO3] and reactive fluid during mineral dissolution, precipitation, and at chemical equilibrium. Experiments were performed in batch reactors at 25 °C in 0.01 M NaCl solutions wherein the pH was adjusted by bubbling of a water saturated gas phase of pure CO2 or atmospheric air. The equilibrium Sr isotope fractionation between strontianite and fluid after dissolution of the solid under 1 atm CO2 atmosphere was estimated as Δ88/86SrSrCO3-fluid = δ88/86Sr SrCO3 - δ88/86Srfluid = -0.05 ± 0.01‰. On the other hand, during strontianite precipitation, an enrichment of the fluid phase in 88Sr, the heavy isotopomer, was observed. The evolution of the δ88/86Srfluid during strontianite precipitation can be modeled using a Rayleigh distillation approach and the estimated, kinetically driven, fractionation factor αSrCO3-fluid between solid and fluid is calculated to be 0.99985 ± 0.00003 corresponding to Δ88/86SrSrCO3-fluid = -0.15‰. The obtained results further support that under chemical equilibrium conditions between solid and fluid a continuous exchange of isotopes occurs until the system approaches isotopic equilibrium. This isotopic exchange is not limited to the outer surface layer of the strontianite crystal, but extends to ∼7-8 unit cells below the crystal surface. The behavior of Sr isotopes in this study is in excellent agreement with the concept of dynamic equilibrium and it suggests that the time needed for achievement of chemical equilibrium is generally shorter compared to that for isotopic equilibrium. Thus it is suggested that in natural Sr-bearing carbonates an isotopic change may still occur close to thermodynamic equilibrium, despite no observable change in aqueous elemental concentrations. As such, a secondary and ongoing change of Sr isotope signals in carbonate minerals caused by isotopic re-equilibration with fluids has to be considered in order to use Sr

  19. Equilibrium Contact Angle and Adsorption Layer Properties with Surfactants.

    PubMed

    Thiele, Uwe; Snoeijer, Jacco H; Trinschek, Sarah; John, Karin

    2018-06-19

    The three-phase contact line of a droplet on a smooth surface can be characterized by the Young equation. It relates the interfacial energies to the macroscopic contact angle θ e . On the mesoscale, wettability is modeled by a film-height-dependent wetting energy f( h). Macro- and mesoscale descriptions are consistent if γ cos θ e = γ + f( h a ), where γ and h a are the liquid-gas interface energy and the thickness of the equilibrium liquid adsorption layer, respectively. Here, we derive a similar consistency condition for the case of a liquid covered by an insoluble surfactant. At equilibrium, the surfactant is spatially inhomogeneously distributed, implying a nontrivial dependence of θ e on surfactant concentration. We derive macroscopic and mesoscopic descriptions of a contact line at equilibrium and show that they are consistent only if a particular dependence of the wetting energy on the surfactant concentration is imposed. This is illustrated by a simple example of dilute surfactants, for which we show excellent agreement between theory and time-dependent numerical simulations.

  20. Computational methods for reactive transport modeling: An extended law of mass-action, xLMA, method for multiphase equilibrium calculations

    NASA Astrophysics Data System (ADS)

    Leal, Allan M. M.; Kulik, Dmitrii A.; Kosakowski, Georg; Saar, Martin O.

    2016-10-01

    We present an extended law of mass-action (xLMA) method for multiphase equilibrium calculations and apply it in the context of reactive transport modeling. This extended LMA formulation differs from its conventional counterpart in that (i) it is directly derived from the Gibbs energy minimization (GEM) problem (i.e., the fundamental problem that describes the state of equilibrium of a chemical system under constant temperature and pressure); and (ii) it extends the conventional mass-action equations with Lagrange multipliers from the Gibbs energy minimization problem, which can be interpreted as stability indices of the chemical species. Accounting for these multipliers enables the method to determine all stable phases without presuming their types (e.g., aqueous, gaseous) or their presence in the equilibrium state. Therefore, the here proposed xLMA method inherits traits of Gibbs energy minimization algorithms that allow it to naturally detect the phases present in equilibrium, which can be single-component phases (e.g., pure solids or liquids) or non-ideal multi-component phases (e.g., aqueous, melts, gaseous, solid solutions, adsorption, or ion exchange). Moreover, our xLMA method requires no technique that tentatively adds or removes reactions based on phase stability indices (e.g., saturation indices for minerals), since the extended mass-action equations are valid even when their corresponding reactions involve unstable species. We successfully apply the proposed method to a reactive transport modeling problem in which we use PHREEQC and GEMS as alternative backends for the calculation of thermodynamic properties such as equilibrium constants of reactions, standard chemical potentials of species, and activity coefficients. Our tests show that our algorithm is efficient and robust for demanding applications, such as reactive transport modeling, where it converges within 1-3 iterations in most cases. The proposed xLMA method is implemented in Reaktoro, a

  1. Phase Equilibrium Investigations of Planetary Materials

    NASA Technical Reports Server (NTRS)

    Grove, T. L.

    1997-01-01

    This grant provided funds to carry out experimental studies designed to illuminate the conditions of melting and chemical differentiation that has occurred in planetary interiors. Studies focused on the conditions of mare basalt generation in the moon's interior and on processes that led to core formation in the Shergottite Parent Body (Mars). Studies also examined physical processes that could lead to the segregation of metal-rich sulfide melts in an olivine-rich solid matrix. The major results of each paper are discussed below and copies of the papers are attached as Appendix I.

  2. Non-equilibrium hydrogen ionization in 2D simulations of the solar atmosphere

    NASA Astrophysics Data System (ADS)

    Leenaarts, J.; Carlsson, M.; Hansteen, V.; Rutten, R. J.

    2007-10-01

    Context: The ionization of hydrogen in the solar chromosphere and transition region does not obey LTE or instantaneous statistical equilibrium because the timescale is long compared with important hydrodynamical timescales, especially of magneto-acoustic shocks. Since the pressure, temperature, and electron density depend sensitively on hydrogen ionization, numerical simulation of the solar atmosphere requires non-equilibrium treatment of all pertinent hydrogen transitions. The same holds for any diagnostic application employing hydrogen lines. Aims: To demonstrate the importance and to quantify the effects of non-equilibrium hydrogen ionization, both on the dynamical structure of the solar atmosphere and on hydrogen line formation, in particular Hα. Methods: We implement an algorithm to compute non-equilibrium hydrogen ionization and its coupling into the MHD equations within an existing radiation MHD code, and perform a two-dimensional simulation of the solar atmosphere from the convection zone to the corona. Results: Analysis of the simulation results and comparison to a companion simulation assuming LTE shows that: a) non-equilibrium computation delivers much smaller variations of the chromospheric hydrogen ionization than for LTE. The ionization is smaller within shocks but subsequently remains high in the cool intershock phases. As a result, the chromospheric temperature variations are much larger than for LTE because in non-equilibrium, hydrogen ionization is a less effective internal energy buffer. The actual shock temperatures are therefore higher and the intershock temperatures lower. b) The chromospheric populations of the hydrogen n = 2 level, which governs the opacity of Hα, are coupled to the ion populations. They are set by the high temperature in shocks and subsequently remain high in the cool intershock phases. c) The temperature structure and the hydrogen level populations differ much between the chromosphere above photospheric magnetic elements

  3. Experimental Investigation of Gas/Slag/Matte/Tridymite Equilibria in the Cu-Fe-O-S-Si System in Controlled Gas Atmospheres: Experimental Results at 1473 K (1200 °C) and P(SO2) = 0.25 atm

    NASA Astrophysics Data System (ADS)

    Fallah-Mehrjardi, Ata; Hidayat, Taufiq; Hayes, Peter C.; Jak, Evgueni

    2017-12-01

    Experimental studies were undertaken to determine the gas/slag/matte/tridymite equilibria in the Cu-Fe-O-S-Si system at 1473 K (1200 °C), P(SO2) = 0.25 atm, and a range of P(O2)'s. The experimental methodology involved high-temperature equilibration using a substrate support technique in controlled gas atmospheres (CO/CO2/SO2/Ar), rapid quenching of equilibrium phases, followed by direct measurement of the chemical compositions of the phases with Electron Probe X-ray Microanalysis (EPMA). The experimental data for slag and matte were presented as a function of copper concentration in matte (matte grade). The data provided are essential for the evaluation of the effect of oxygen potential under controlled atmosphere on the matte grade, liquidus composition of slag and chemically dissolved copper in slag. The new data provide important accurate and reliable quantitative foundation for improvement of the thermodynamic databases for copper-containing systems.

  4. Equilibrium radionuclide gated angiography in patients with tricuspid regurgitation

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

    Handler, B.; Pavel, D.G.; Pietras, R.

    Equilibrium gated radionuclide angiography was performed in 2 control groups (15 patients with no organic heart disease and 24 patients with organic heart disease but without right- or left-sided valvular regurgitation) and in 9 patients with clinical tricuspid regurgitation. The regurgitant index, or ratio of left to right ventricular stroke counts, was significantly lower in patients with tricuspid regurgitation than in either control group. Time-activity variation over the liver was used to compute a hepatic expansion fraction which was significantly higher in patients with tricuspid regurgitation than in either control group. Fourier analysis of time-activity variation in each pixel wasmore » used to generate amplitude and phase images. Only pixels with values for amplitude at least 7% of the maximum in the image were retained in the final display. All patients with tricuspid regurgitation had greater than 100 pixels over the liver automatically retained by the computer. These pixels were of phase comparable to that of the right atrium and approximately 180 degrees out of phase with the right ventricle. In contrast, no patient with no organic heart disease and only 1 of 24 patients with organic heart disease had any pixels retained by the computer. In conclusion, patients with tricuspid regurgitation were characterized on equilibrium gated angiography by an abnormally low regurgitant index (7 of 9 patients) reflecting increased right ventricular stroke volume, increased hepatic expansion fraction (7 of 9 patients), and increased amplitude of count variation over the liver in phase with the right atrium (9 of 9 patients).« less

  5. Behavior of a PCM at Varying Heating Rates: Experimental and Theoretical Study with an Aim at Temperature Moderation in Radionuclide Concrete Encasements

    NASA Astrophysics Data System (ADS)

    Medved', Igor; Trník, Anton

    2018-07-01

    Phase-change materials (PCMs) can store/release thermal energy within a small temperature range. This is of interest in various industrial applications, for example, in civil engineering (heating/cooling of buildings) or cold storage applications. Another application may be the moderation of temperature increases in concrete encasements of radionuclides during their decay. The phase-change behavior of a material is determined by its heat capacity and the peak it exhibits near a phase change. We analyze the behavior of such peaks for a selected PCM at heating rates varying between 0.1°C\\cdot min^{-1} and 1°C\\cdot min^{-1}, corresponding in real situations to different decay rates of radionuclides. We show that experimentally measured peaks can be plausibly described by an equilibrium theory that enables us to calculate the latent heat and phase-change temperature from experimental data.

  6. Analysis and experimental demonstration of conformal adaptive phase-locked fiber array for laser communications and beam projection applications

    NASA Astrophysics Data System (ADS)

    Liu, Ling

    The primary goal of this research is the analysis, development, and experimental demonstration of an adaptive phase-locked fiber array system for free-space optical communications and laser beam projection applications. To our knowledge, the developed adaptive phase-locked system composed of three fiber collimators (subapertures) with tip-tilt wavefront phase control at each subaperture represents the first reported fiber array system that implements both phase-locking control and adaptive wavefront tip-tilt control capabilities. This research has also resulted in the following innovations: (a) The first experimental demonstration of a phase-locked fiber array with tip-tilt wave-front aberration compensation at each fiber collimator; (b) Development and demonstration of the fastest currently reported stochastic parallel gradient descent (SPGD) system capable of operation at 180,000 iterations per second; (c) The first experimental demonstration of a laser communication link based on a phase-locked fiber array; (d) The first successful experimental demonstration of turbulence and jitter-induced phase distortion compensation in a phase-locked fiber array optical system; (e) The first demonstration of laser beam projection onto an extended target with a randomly rough surface using a conformal adaptive fiber array system. Fiber array optical systems, the subject of this study, can overcome some of the draw-backs of conventional monolithic large-aperture transmitter/receiver optical systems that are usually heavy, bulky, and expensive. The primary experimental challenges in the development of the adaptive phased-locked fiber-array included precise (<5 microrad) alignment of the fiber collimators and development of fast (100kHz-class) phase-locking and wavefront tip-tilt control systems. The precise alignment of the fiber collimator array is achieved through a specially developed initial coarse alignment tool based on high precision piezoelectric picomotors and a

  7. Validation of vibration-dissociation coupling models in hypersonic non-equilibrium separated flows

    NASA Astrophysics Data System (ADS)

    Shoev, G.; Oblapenko, G.; Kunova, O.; Mekhonoshina, M.; Kustova, E.

    2018-03-01

    The validation of recently developed models of vibration-dissociation coupling is discussed in application to numerical solutions of the Navier-Stokes equations in a two-temperature approximation for a binary N2/N flow. Vibrational-translational relaxation rates are computed using the Landau-Teller formula generalized for strongly non-equilibrium flows obtained in the framework of the Chapman-Enskog method. Dissociation rates are calculated using the modified Treanor-Marrone model taking into account the dependence of the model parameter on the vibrational state. The solutions are compared to those obtained using traditional Landau-Teller and Treanor-Marrone models, and it is shown that for high-enthalpy flows, the traditional and recently developed models can give significantly different results. The computed heat flux and pressure on the surface of a double cone are in a good agreement with experimental data available in the literature on low-enthalpy flow with strong thermal non-equilibrium. The computed heat flux on a double wedge qualitatively agrees with available data for high-enthalpy non-equilibrium flows. Different contributions to the heat flux calculated using rigorous kinetic theory methods are evaluated. Quantitative discrepancy of numerical and experimental data is discussed.

  8. Metastable and equilibrium phase diagrams of unconjugated bilirubin IXα as functions of pH in model bile systems: Implications for pigment gallstone formation.

    PubMed

    Berman, Marvin D; Carey, Martin C

    2015-01-01

    Metastable and equilibrium phase diagrams for unconjugated bilirubin IXα (UCB) in bile are yet to be determined for understanding the physical chemistry of pigment gallstone formation. Also, UCB is a molecule of considerable biomedical importance because it is a potent antioxidant and an inhibitor of atherogenesis. We employed principally a titrimetric approach to obtain metastable and equilibrium UCB solubilities in model bile systems composed of taurine-conjugated bile salts, egg yolk lecithin (mixed long-chain phosphatidylcholines), and cholesterol as functions of total lipid concentration, biliary pH values, and CaCl2 plus NaCl concentrations. Metastable and equilibrium precipitation pH values were obtained, and average pKa values of the two carboxyl groups of UCB were calculated. Added lecithin and increased temperature decreased UCB solubility markedly, whereas increases in bile salt concentrations and molar levels of urea augmented solubility. A wide range of NaCl and cholesterol concentrations resulted in no specific effects, whereas added CaCl2 produced large decreases in UCB solubilities at alkaline pH values only. UV-visible absorption spectra were consistent with both hydrophobic and hydrophilic interactions between UCB and bile salts that were strongly influenced by pH. Reliable literature values for UCB compositions of native gallbladder biles revealed that biles from hemolytic mice and humans with black pigment gallstones are markedly supersaturated with UCB and exhibit more acidic pH values, whereas biles from nonstone control animals and patients with cholesterol gallstone are unsaturated with UCB. Copyright © 2015 the American Physiological Society.

  9. Nucleation via an unstable intermediate phase.

    PubMed

    Sear, Richard P

    2009-08-21

    The pathway for crystallization from dilute vapors and solutions is often observed to take a detour via a liquid or concentrated-solution phase. For example, in moist subzero air, droplets of liquid water form, which then freeze. In this example and in many others, an intermediate phase (here liquid water) is dramatically accelerating the kinetics of a phase transition between two other phases (water vapor and ice). Here we study this phenomenon via exact computer simulations of a simple lattice model. Surprisingly, we find that the rate of nucleation of the new equilibrium phase is actually fastest when the intermediate phase is slightly unstable in the bulk, i.e., has a slightly higher free energy than the phase we start in. Nucleation occurs at a concave part of the surface and microscopic amounts of the intermediate phase can form there even before the phase is stable in the bulk. As the nucleus of the equilibrium phase is microscopic, this allows nucleation to occur effectively in the intermediate phase before it is stable in the bulk.

  10. Experimental evidence for stochastic switching of supercooled phases in NdNiO3 nanostructures

    NASA Astrophysics Data System (ADS)

    Kumar, Devendra; Rajeev, K. P.; Alonso, J. A.

    2018-03-01

    A first-order phase transition is a dynamic phenomenon. In a multi-domain system, the presence of multiple domains of coexisting phases averages out the dynamical effects, making it nearly impossible to predict the exact nature of phase transition dynamics. Here, we report the metal-insulator transition in samples of sub-micrometer size NdNiO3 where the effect of averaging is minimized by restricting the number of domains under study. We observe the presence of supercooled metallic phases with supercooling of 40 K or more. The transformation from the supercooled metallic to the insulating state is a stochastic process that happens at different temperatures and times in different experimental runs. The experimental results are understood without incorporating material specific properties, suggesting that the behavior is of universal nature. The size of the sample needed to observe individual switching of supercooled domains, the degree of supercooling, and the time-temperature window of switching are expected to depend on the parameters such as quenched disorder, strain, and magnetic field.

  11. Flux line non-equilibrium relaxation kinetics following current quenches in disordered type-II superconductors

    NASA Astrophysics Data System (ADS)

    Chaturvedi, Harshwardhan; Assi, Hiba; Dobramysl, Ulrich; Pleimling, Michel; Täuber, Uwe

    We investigate the relaxation dynamics of magnetic vortex lines in disordered type-II superconductors following rapid changes in the external driving current by means of Langevin molecular dynamics simulations for an elastic line model. A system of driven interacting flux lines in a sample with randomly distributed point pinning centers is initially relaxed to a moving non-equilibrium steady state. The current is then instantaneously decreased, such that the final stationary state resides either still in the moving regime, or in the pinned Bragg glass phase. The ensuing non-equilibrium relaxation kinetics of the vortices is studied in detail by measuring the mean flux line gyration radius and the two-time transverse height autocorrelation function. The latter allows us to investigate the physical aging properties for quenches from the moving into the glassy phase, and to compare with non-equilibrium relaxation features obtained with different initial configurations. Research supported by the U.S. Department of Energy, Office of Basic Energy Sciences, Division of Materials Sciences and Engineering under Award DE-FG02-09ER46613.

  12. Computation of thermodynamic equilibrium in systems under stress

    NASA Astrophysics Data System (ADS)

    Vrijmoed, Johannes C.; Podladchikov, Yuri Y.

    2016-04-01

    Metamorphic reactions may be partly controlled by the local stress distribution as suggested by observations of phase assemblages around garnet inclusions related to an amphibolite shear zone in granulite of the Bergen Arcs in Norway. A particular example presented in fig. 14 of Mukai et al. [1] is discussed here. A garnet crystal embedded in a plagioclase matrix is replaced on the left side by a high pressure intergrowth of kyanite and quartz and on the right side by chlorite-amphibole. This texture apparently represents disequilibrium. In this case, the minerals adapt to the low pressure ambient conditions only where fluids were present. Alternatively, here we compute that this particular low pressure and high pressure assemblage around a stressed rigid inclusion such as garnet can coexist in equilibrium. To do the computations we developed the Thermolab software package. The core of the software package consists of Matlab functions that generate Gibbs energy of minerals and melts from the Holland and Powell database [2] and aqueous species from the SUPCRT92 database [3]. Most up to date solid solutions are included in a general formulation. The user provides a Matlab script to do the desired calculations using the core functions. Gibbs energy of all minerals, solutions and species are benchmarked versus THERMOCALC, PerpleX [4] and SUPCRT92 and are reproduced within round off computer error. Multi-component phase diagrams have been calculated using Gibbs minimization to benchmark with THERMOCALC and Perple_X. The Matlab script to compute equilibrium in a stressed system needs only two modifications of the standard phase diagram script. Firstly, Gibbs energy of phases considered in the calculation is generated for multiple values of thermodynamic pressure. Secondly, for the Gibbs minimization the proportion of the system at each particular thermodynamic pressure needs to be constrained. The user decides which part of the stress tensor is input as thermodynamic

  13. The phenotypic equilibrium of cancer cells: From average-level stability to path-wise convergence.

    PubMed

    Niu, Yuanling; Wang, Yue; Zhou, Da

    2015-12-07

    The phenotypic equilibrium, i.e. heterogeneous population of cancer cells tending to a fixed equilibrium of phenotypic proportions, has received much attention in cancer biology very recently. In the previous literature, some theoretical models were used to predict the experimental phenomena of the phenotypic equilibrium, which were often explained by different concepts of stabilities of the models. Here we present a stochastic multi-phenotype branching model by integrating conventional cellular hierarchy with phenotypic plasticity mechanisms of cancer cells. Based on our model, it is shown that: (i) our model can serve as a framework to unify the previous models for the phenotypic equilibrium, and then harmonizes the different kinds of average-level stabilities proposed in these models; and (ii) path-wise convergence of our model provides a deeper understanding to the phenotypic equilibrium from stochastic point of view. That is, the emergence of the phenotypic equilibrium is rooted in the stochastic nature of (almost) every sample path, the average-level stability just follows from it by averaging stochastic samples. Copyright © 2015 Elsevier Ltd. All rights reserved.

  14. Simulation studies of phase inversion in agitated vessels using a Monte Carlo technique.

    PubMed

    Yeo, Leslie Y; Matar, Omar K; Perez de Ortiz, E Susana; Hewitt, Geoffrey F

    2002-04-15

    A speculative study on the conditions under which phase inversion occurs in agitated liquid-liquid dispersions is conducted using a Monte Carlo technique. The simulation is based on a stochastic model, which accounts for fundamental physical processes such as drop deformation, breakup, and coalescence, and utilizes the minimization of interfacial energy as a criterion for phase inversion. Profiles of the interfacial energy indicate that a steady-state equilibrium is reached after a sufficiently large number of random moves and that predictions are insensitive to initial drop conditions. The calculated phase inversion holdup is observed to increase with increasing density and viscosity ratio, and to decrease with increasing agitation speed for a fixed viscosity ratio. It is also observed that, for a fixed viscosity ratio, the phase inversion holdup remains constant for large enough agitation speeds. The proposed model is therefore capable of achieving reasonable qualitative agreement with general experimental trends and of reproducing key features observed experimentally. The results of this investigation indicate that this simple stochastic method could be the basis upon which more advanced models for predicting phase inversion behavior can be developed.

  15. Energy thresholds of discrete breathers in thermal equilibrium and relaxation processes.

    PubMed

    Ming, Yi; Ling, Dong-Bo; Li, Hui-Min; Ding, Ze-Jun

    2017-06-01

    So far, only the energy thresholds of single discrete breathers in nonlinear Hamiltonian systems have been analytically obtained. In this work, the energy thresholds of discrete breathers in thermal equilibrium and the energy thresholds of long-lived discrete breathers which can remain after a long time relaxation are analytically estimated for nonlinear chains. These energy thresholds are size dependent. The energy thresholds of discrete breathers in thermal equilibrium are the same as the previous analytical results for single discrete breathers. The energy thresholds of long-lived discrete breathers in relaxation processes are different from the previous results for single discrete breathers but agree well with the published numerical results known to us. Because real systems are either in thermal equilibrium or in relaxation processes, the obtained results could be important for experimental detection of discrete breathers.

  16. Critical contribution of nonlinear chromatography to the understanding of retention mechanism in reversed-phase liquid chromatography

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

    Gritti, Fabrice; Guiochon, Georges A

    2005-11-01

    The retention of most compounds in RPLC proceeds through a combination of several independent mechanisms. We review a series of recent studies made on the behavior of several commercial C{sub 18}-bonded stationary phases and of the complex, mixed retention mechanisms that were observed in RPLC. These studies are essentially based on the acquisition of adsorption isotherm data, on the modeling, and on the interpretation of these data. Because linear chromatography deals only with the initial slope of the global, overall, or apparent isotherm, it is unable fully to describe the complete adsorption mechanism. It cannot even afford clues as tomore » the existence of several overlaid retention mechanisms. More specifically, it cannot account for the consequences of the surface heterogeneity of the packing material. The acquisition of equilibrium data in a wide concentration range is required for this purpose. Frontal analysis (FA) of selected probes gives data that can be modeled into equilibrium isotherms of these probes and that can also be used to calculate their adsorption or affinity energy distribution (AED). The combination of these data, the detailed study of the best constants of the isotherm model, the determination of the influence of experimental parameters (e.g., buffer pH and pI, temperature) on the isotherm constants provide important clues regarding the heterogeneity of the adsorbent surface and the main properties of the adsorption mechanisms. The comparison of similar data obtained for the adsorption of neutral and ionizable compounds, treated with the same approach, and the investigation of the influence on the thermodynamics of phase equilibrium of the experimental conditions (temperature, average pressure, mobile phase composition, nature of the organic modifier, and, for ionizable compounds, of the ionic strength, the nature, the concentration of the buffer, and its pH) brings further information. This review provides original conclusions

  17. Phase diagram for a two-dimensional, two-temperature, diffusive XY model.

    PubMed

    Reichl, Matthew D; Del Genio, Charo I; Bassler, Kevin E

    2010-10-01

    Using Monte Carlo simulations, we determine the phase diagram of a diffusive two-temperature conserved order parameter XY model. When the two temperatures are equal the system becomes the equilibrium XY model with the continuous Kosterlitz-Thouless (KT) vortex-antivortex unbinding phase transition. When the two temperatures are unequal the system is driven by an energy flow from the higher temperature heat-bath to the lower temperature one and reaches a far-from-equilibrium steady state. We show that the nonequilibrium phase diagram contains three phases: A homogenous disordered phase and two phases with long range, spin texture order. Two critical lines, representing continuous phase transitions from a homogenous disordered phase to two phases of long range order, meet at the equilibrium KT point. The shape of the nonequilibrium critical lines as they approach the KT point is described by a crossover exponent φ=2.52±0.05. Finally, we suggest that the transition between the two phases with long-range order is first-order, making the KT-point where all three phases meet a bicritical point.

  18. Experimental demonstration of a two-phase population extinction hazard

    PubMed Central

    Drake, John M.; Shapiro, Jeff; Griffen, Blaine D.

    2011-01-01

    Population extinction is a fundamental biological process with applications to ecology, epidemiology, immunology, conservation biology and genetics. Although a monotonic relationship between initial population size and mean extinction time is predicted by virtually all theoretical models, attempts at empirical demonstration have been equivocal. We suggest that this anomaly is best explained with reference to the transient properties of ensembles of populations. Specifically, we submit that under experimental conditions, many populations escape their initially vulnerable state to reach quasi-stationarity, where effects of initial conditions are erased. Thus, extinction of populations initialized far from quasi-stationarity may be exposed to a two-phase extinction hazard. An empirical prediction of this theory is that the fit Cox proportional hazards regression model for the observed survival time distribution of a group of populations will be shown to violate the proportional hazards assumption early in the experiment, but not at later times. We report results of two experiments with the cladoceran zooplankton Daphnia magna designed to exhibit this phenomenon. In one experiment, habitat size was also varied. Statistical analysis showed that in one of these experiments a transformation occurred so that very early in the experiment there existed a transient phase during which the extinction hazard was primarily owing to the initial population size, and that this was gradually replaced by a more stable quasi-stationary phase. In the second experiment, only habitat size unambiguously displayed an effect. Analysis of data pooled from both experiments suggests that the overall extinction time distribution in this system results from the mixture of extinctions during the initial rapid phase, during which the effects of initial population size can be considerable, and a longer quasi-stationary phase, during which only habitat size has an effect. These are the first results

  19. Direct Observation of Dynamical Quantum Phase Transitions in an Interacting Many-Body System

    NASA Astrophysics Data System (ADS)

    Jurcevic, P.; Shen, H.; Hauke, P.; Maier, C.; Brydges, T.; Hempel, C.; Lanyon, B. P.; Heyl, M.; Blatt, R.; Roos, C. F.

    2017-08-01

    The theory of phase transitions represents a central concept for the characterization of equilibrium matter. In this work we study experimentally an extension of this theory to the nonequilibrium dynamical regime termed dynamical quantum phase transitions (DQPTs). We investigate and measure DQPTs in a string of ions simulating interacting transverse-field Ising models. During the nonequilibrium dynamics induced by a quantum quench we show for strings of up to 10 ions the direct detection of DQPTs by revealing nonanalytic behavior in time. Moreover, we provide a link between DQPTs and the dynamics of other quantities such as the magnetization, and we establish a connection between DQPTs and entanglement production.

  20. Direct Observation of Dynamical Quantum Phase Transitions in an Interacting Many-Body System.

    PubMed

    Jurcevic, P; Shen, H; Hauke, P; Maier, C; Brydges, T; Hempel, C; Lanyon, B P; Heyl, M; Blatt, R; Roos, C F

    2017-08-25

    The theory of phase transitions represents a central concept for the characterization of equilibrium matter. In this work we study experimentally an extension of this theory to the nonequilibrium dynamical regime termed dynamical quantum phase transitions (DQPTs). We investigate and measure DQPTs in a string of ions simulating interacting transverse-field Ising models. During the nonequilibrium dynamics induced by a quantum quench we show for strings of up to 10 ions the direct detection of DQPTs by revealing nonanalytic behavior in time. Moreover, we provide a link between DQPTs and the dynamics of other quantities such as the magnetization, and we establish a connection between DQPTs and entanglement production.

  1. Formation of Minor Phases in a Nickel-Based Disk Superalloy

    NASA Technical Reports Server (NTRS)

    Gabb, T. P.; Garg, A.; Miller, D. R.; Sudbrack, C. K.; Hull, D. R.; Johnson, D.; Rogers, R. B.; Gayda, J.; Semiatin, S. L.

    2012-01-01

    The minor phases of powder metallurgy disk superalloy LSHR were studied. Samples were consistently heat treated at three different temperatures for long times to approximate equilibrium. Additional heat treatments were also performed for shorter times, to then assess non-equilibrium conditions. Minor phases including MC carbides, M23C6 carbides, M3B2 borides, and sigma were identified. Their transformation temperatures, lattice parameters, compositions, average sizes and total area fractions were determined, and compared to estimates of an existing phase prediction software package. Parameters measured at equilibrium sometimes agreed reasonably well with software model estimates, with potential for further improvements. Results for shorter times representing non-equilibrium indicated significant potential for further extension of the software to such conditions, which are more commonly observed during heat treatments and service at high temperatures for disk applications.

  2. Silicon Oxysulfide, OSiS: Rotational Spectrum, Quantum-Chemical Calculations, and Equilibrium Structure.

    PubMed

    Thorwirth, Sven; Mück, Leonie Anna; Gauss, Jürgen; Tamassia, Filippo; Lattanzi, Valerio; McCarthy, Michael C

    2011-06-02

    Silicon oxysulfide, OSiS, and seven of its minor isotopic species have been characterized for the first time in the gas phase at high spectral resolution by means of Fourier transform microwave spectroscopy. The equilibrium structure of OSiS has been determined from the experimental data using calculated vibration-rotation interaction constants. The structural parameters (rO-Si = 1.5064 Å and rSi-S = 1.9133 Å) are in very good agreement with values from high-level quantum chemical calculations using coupled-cluster techniques together with sophisticated additivity and extrapolation schemes. The bond distances in OSiS are very short in comparison with those in SiO and SiS. This unexpected finding is explained by the partial charges calculated for OSiS via a natural population analysis. The results suggest that electrostatic effects rather than multiple bonding are the key factors in determining bonding in this triatomic molecule. The data presented provide the spectroscopic information needed for radio astronomical searches for OSiS.

  3. Microphysics of liquid complex plasmas in equilibrium and non-equilibrium systems

    NASA Astrophysics Data System (ADS)

    Piel, Alexander; Block, Dietmar; Melzer, André; Mulsow, Matthias; Schablinski, Jan; Schella, André; Wieben, Frank; Wilms, Jochen

    2018-05-01

    The dynamic evolution of the microscopic structure of solid and liquid phases of complex plasmas is studied experimentally and by means of molecular dynamics (MD) simulations. In small finite systems, the cooperative motion can be described in terms of discrete modes. These modes are studied with different experimental approaches. Using diffuse scattered laser light, applying laser tweezer forces to individual particles, and periodic laser pulses, the excitation of modes is investigated. The instantaneous normal mode analysis of experimental data from two-dimensional liquid clusters gives access to the local dynamics of the liquid phase. Our investigations shed light on the role of compressional and shear modes as well as the determination of diffusion constants and melting temperatures in finite systems. Special attention is paid to hydrodynamic situations with a stationary inhomogeneous dust flow. MD simulations allow to study the collective motion in the shell of nearest neighbors, which can be linked to smooth and sudden changes of the macroscopic flow. Finally, the observed micro-motion in all situations above allows to shed light on the preference of shear-like over compressional motion in terms of a minimized potential energy and a dynamic incompressibility.

  4. Adsorption mechanism of acids and bases in reversed-phase liquid chromatography in weak buffered mobile phases designed for liquid chromatography/mass spectrometry.

    PubMed

    Gritti, Fabrice; Guiochon, Georges

    2009-03-06

    The overloaded band profiles of five acido-basic compounds were measured, using weakly buffered mobile phases. Low buffer concentrations were selected to provide a better understanding of the band profiles recorded in LC/MS analyses, which are often carried out at low buffer concentrations. In this work, 10 microL samples of a 50 mM probe solution were injected into C(18)-bonded columns using a series of five buffered mobile phases at (SW)pH between 2 and 12. The retention times and the shapes of the bands were analyzed based on thermodynamic arguments. A new adsorption model that takes into account the simultaneous adsorption of the acidic and the basic species onto the endcapped adsorbent, predicts accurately the complex experimental profiles recorded. The adsorption mechanism of acido-basic compounds onto RPLC phases seems to be consistent with the following microscopic model. No matter whether the acid or the base is the neutral or the basic species, the neutral species adsorbs onto a large number of weak adsorption sites (their saturation capacity is several tens g/L and their equilibrium constant of the order of 0.1 L/g). In contrast, the ionic species adsorbs strongly onto fewer active sites (their saturation capacity is about 1g/L and their equilibrium constant of the order of a few L/g). From a microscopic point of view and in agreement with the adsorption isotherm of the compound measured by frontal analysis (FA) and with the results of Monte-Carlo calculations performed by Schure et al., the first type of adsorption sites are most likely located in between C(18)-bonded chains and the second type of adsorption sites are located deeper in contact with the silica surface. The injected concentration (50 mM) was too low to probe the weakest adsorption sites (saturation capacity of a few hundreds g/L with an equilibrium constant of one hundredth of L/g) that are located at the very interface between the C(18)-bonded layer and the bulk phase.

  5. Equilibrium drives of the low and high field side n  =  2 plasma response and impact on global confinement

    NASA Astrophysics Data System (ADS)

    Paz-Soldan, C.; Logan, N. C.; Haskey, S. R.; Nazikian, R.; Strait, E. J.; Chen, X.; Ferraro, N. M.; King, J. D.; Lyons, B. C.; Park, J.-K.

    2016-05-01

    The nature of the multi-modal n  =  2 plasma response and its impact on global confinement is studied as a function of the axisymmetric equilibrium pressure, edge safety factor, collisionality, and L-versus H-mode conditions. Varying the relative phase (Δ {φ\\text{UL}} ) between upper and lower in-vessel coils demonstrates that different n  =  2 poloidal spectra preferentially excite different plasma responses. These different plasma response modes are preferentially detected on the tokamak high-field side (HFS) or low-field side (LFS) midplanes, have different radial extents, couple differently to the resonant surfaces, and have variable impacts on edge stability and global confinement. In all equilibrium conditions studied, the observed confinement degradation shares the same Δ {φ\\text{UL}} dependence as the coupling to the resonant surfaces given by both ideal (IPEC) and resistive (MARS-F) MHD computation. Varying the edge safety factor shifts the equilibrium field-line pitch and thus the Δ {φ\\text{UL}} dependence of both the global confinement and the n  =  2 magnetic response. As edge safety factor is varied, modeling finds that the HFS response (but not the LFS response), the resonant surface coupling, and the edge displacements near the X-point all share the same Δ {φ\\text{UL}} dependence. The LFS response magnitude is strongly sensitive to the core pressure and is insensitive to the collisionality and edge safety factor. This indicates that the LFS measurements are primarily sensitive to a pressure-driven kink-ballooning mode that couples to the core plasma. MHD modeling accurately reproduces these (and indeed all) LFS experimental trends and supports this interpretation. In contrast to the LFS, the HFS magnetic response and correlated global confinement impact is unchanged with plasma pressure, but is strongly reduced in high collisionality conditions in both H- and L-mode. This experimentally suggests the bootstrap

  6. Numerical and Experimental Investigation of Stratified Gas-Liquid Two-Phase Flow in Horizontal Circular Pipes

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

    Faccini, J.L.H.; Sampaio, P.A.B. de; Su, J.

    This paper reports numerical and experimental investigation of stratified gas-liquid two-phase flow in horizontal circular pipes. The Reynolds averaged Navier Stokes equations (RANS) with the k-{omega} model for a fully developed stratified gas-liquid two-phase flow are solved by using the finite element method. A smooth and horizontal interface surface is assumed without considering the interfacial waves. The continuity of the shear stress across the interface is enforced with the continuity of the velocity being automatically satisfied by the variational formulation. For each given interface position and longitudinal pressure gradient, an inner iteration loop runs to solve the nonlinear equations. Themore » Newton-Raphson scheme is used to solve the transcendental equations by an outer iteration to determine the interface position and pressure gradient for a given pair of volumetric flow rates. The interface position in a 51.2 mm ID circular pipe was measured experimentally by the ultrasonic pulse-echo technique. The numerical results were also compared with experimental results in a 21 mm ID circular pipe reported by Masala [1]. The good agreement between the numerical and experimental results indicates that the k-{omega} model can be applied for the numerical simulation of stratified gas-liquid two-phase flow. (authors)« less

  7. Dehydration kinetics and thermochemistry of selected hydrous phases, and simulated gas release pattern in carbonaceous chondrites

    NASA Technical Reports Server (NTRS)

    Bose, Kunal; Ganguly, J.

    1992-01-01

    As part of our continued program of study on the volatile bearing phases and volatile resource potential of carbonaceous chondrite, results of our experimental studies on the dehydration kinetics of talc as a function of temperature and grain size (50 to 0.5 microns), equilibrium dehydration boundary of talc to 40 kbars, calorimetric study of enthalpy of formation of both natural and synthetic talc as a function of grain size, and preliminary results on the dehydration kinetics of epsomite are reported. In addition, theoretical calculations on the gas release pattern of Murchison meteorite, which is a C2(CM) carbonaceous chondrite, were performed. The kinetic study of talc leads to a dehydration rate constant for 40-50 microns size fraction of k = (3.23 x 10(exp 4))exp(-Q/RT)/min with the activation energy Q = 376 (plus or minus 20) kJ/mole. The dehydration rate was found to increase somewhat with decreasing grain size. The enthalpy of formation of talc from elements was measured to be -5896(10) kJ/mol. There was no measurable effect of grain size on the enthalpy beyond the limits of precision of the calorimetric studies. Also the calorimetric enthalpy of both synthetic and natural talc was found to be essentially the same, within the precision of measurements, although the natural talc had a slightly larger field of stability in our phase equilibrium studies. The high pressure experimental data the dehydration equilibrium of talc (talc = enstatite + coesite + H2O) is in strong disagreement with that calculated from the available thermochemical data, which were constrained to fit the low pressure experimental results. The calculated gas release pattern of Murchison meteorite were in reasonable agreement with that determined by stepwise heating in a gas chromatograph.

  8. Non-equilibrium supramolecular polymerization.

    PubMed

    Sorrenti, Alessandro; Leira-Iglesias, Jorge; Markvoort, Albert J; de Greef, Tom F A; Hermans, Thomas M

    2017-09-18

    Supramolecular polymerization has been traditionally focused on the thermodynamic equilibrium state, where one-dimensional assemblies reside at the global minimum of the Gibbs free energy. The pathway and rate to reach the equilibrium state are irrelevant, and the resulting assemblies remain unchanged over time. In the past decade, the focus has shifted to kinetically trapped (non-dissipative non-equilibrium) structures that heavily depend on the method of preparation (i.e., pathway complexity), and where the assembly rates are of key importance. Kinetic models have greatly improved our understanding of competing pathways, and shown how to steer supramolecular polymerization in the desired direction (i.e., pathway selection). The most recent innovation in the field relies on energy or mass input that is dissipated to keep the system away from the thermodynamic equilibrium (or from other non-dissipative states). This tutorial review aims to provide the reader with a set of tools to identify different types of self-assembled states that have been explored so far. In particular, we aim to clarify the often unclear use of the term "non-equilibrium self-assembly" by subdividing systems into dissipative, and non-dissipative non-equilibrium states. Examples are given for each of the states, with a focus on non-dissipative non-equilibrium states found in one-dimensional supramolecular polymerization.

  9. Is the Reaction Equilibrium Composition in Non-ideal Mixtures Uniquely Determined by the Initial Composition?

    NASA Astrophysics Data System (ADS)

    Sefcik, Jan

    1998-05-01

    Reaction equilibrium can be mathematically described by the equilibrium equation and the reaction equilibrium composition can be calculated by solving this equation. It can be proved by non-elementary thermodynamic arguments that for a generic system with given initial composition, temperature and pressure there is a unique stable equilibrium state corresponding to the global minimum of the Gibbs free energy function. However, when the concept of equilibrium is introduced in undergraduate chemistry and chemical engineering courses, such arguments are generally not accessible. When there is a single reaction equilibrium among mixture components and the components form an ideal mixture, it has been demonstrated by a simple, elegant mathematical argument that there is a unique composition satisfying the equilibrium equation. It has been also suggested that this particular argument extends to non-ideal mixtures by simply incorporating activity coefficients. We show that the argument extension to non-ideal systems is not generally valid. Increasing non-ideality can result in non-monotonicity of the function crucial for the simple uniqueness argument, and only later it leads to non-uniqueness and hence phase separation. The main feature responsible for this is a composition dependence of activity coefficients in non-ideal mixtures.

  10. Kardar-Parisi-Zhang universality in the phase distributions of one-dimensional exciton-polaritons

    NASA Astrophysics Data System (ADS)

    Squizzato, Davide; Canet, Léonie; Minguzzi, Anna

    2018-05-01

    Exciton-polaritons under driven-dissipative conditions exhibit a condensation transition that belongs to a different universality class from that of equilibrium Bose-Einstein condensates. By numerically solving the generalized Gross-Pitaevskii equation with realistic experimental parameters, we show that one-dimensional exciton-polaritons display fine features of Kardar-Parisi-Zhang (KPZ) dynamics. Beyond the scaling exponents, we show that their phase distribution follows the Tracy-Widom form predicted for KPZ growing interfaces. We moreover evidence a crossover to the stationary Baik-Rains statistics. We finally show that these features are unaffected on a certain timescale by the presence of a smooth disorder often present in experimental setups.

  11. Exploring the anisotropic Kondo model in and out of equilibrium with alkaline-earth atoms

    NASA Astrophysics Data System (ADS)

    Kanász-Nagy, Márton; Ashida, Yuto; Shi, Tao; Moca, Cǎtǎlin Paşcu; Ikeda, Tatsuhiko N.; Fölling, Simon; Cirac, J. Ignacio; Zaránd, Gergely; Demler, Eugene A.

    2018-04-01

    We propose a scheme to realize the Kondo model with tunable anisotropy using alkaline-earth atoms in an optical lattice. The new feature of our setup is Floquet engineering of interactions using time-dependent Zeeman shifts, that can be realized either using state-dependent optical Stark shifts or magnetic fields. The properties of the resulting Kondo model strongly depend on the anisotropy of the ferromagnetic interactions. In particular, easy-plane couplings give rise to Kondo singlet formation even though microscopic interactions are all ferromagnetic. We discuss both equilibrium and dynamical properties of the system that can be measured with ultracold atoms, including the impurity spin susceptibility, the impurity spin relaxation rate, as well as the equilibrium and dynamical spin correlations between the impurity and the ferromagnetic bath atoms. We analyze the nonequilibrium time evolution of the system using a variational non-Gaussian approach, which allows us to explore coherent dynamics over both short and long timescales, as set by the bandwidth and the Kondo singlet formation, respectively. In the quench-type experiments, when the Kondo interaction is suddenly switched on, we find that real-time dynamics shows crossovers reminiscent of poor man's renormalization group flow used to describe equilibrium systems. For bare easy-plane ferromagnetic couplings, this allows us to follow the formation of the Kondo screening cloud as the dynamics crosses over from ferromagnetic to antiferromagnetic behavior. On the other side of the phase diagram, our scheme makes it possible to measure quantum corrections to the well-known Korringa law describing the temperature dependence of the impurity spin relaxation rate. Theoretical results discussed in our paper can be measured using currently available experimental techniques.

  12. A chaotic jerk system with non-hyperbolic equilibrium: Dynamics, effect of time delay and circuit realisation

    NASA Astrophysics Data System (ADS)

    Rajagopal, Karthikeyan; Pham, Viet-Thanh; Tahir, Fadhil Rahma; Akgul, Akif; Abdolmohammadi, Hamid Reza; Jafari, Sajad

    2018-04-01

    The literature on chaos has highlighted several chaotic systems with special features. In this work, a novel chaotic jerk system with non-hyperbolic equilibrium is proposed. The dynamics of this new system is revealed through equilibrium analysis, phase portrait, bifurcation diagram and Lyapunov exponents. In addition, we investigate the time-delay effects on the proposed system. Realisation of such a system is presented to verify its feasibility.

  13. Numerical modeling of experimental observations on gas formation and multi-phase flow of carbon dioxide in subsurface formations

    NASA Astrophysics Data System (ADS)

    Pawar, R.; Dash, Z.; Sakaki, T.; Plampin, M. R.; Lassen, R. N.; Illangasekare, T. H.; Zyvoloski, G.

    2011-12-01

    One of the concerns related to geologic CO2 sequestration is potential leakage of CO2 and its subsequent migration to shallow groundwater resources leading to geochemical impacts. Developing approaches to monitor CO2 migration in shallow aquifer and mitigate leakage impacts will require improving our understanding of gas phase formation and multi-phase flow subsequent to CO2 leakage in shallow aquifers. We are utilizing an integrated approach combining laboratory experiments and numerical simulations to characterize the multi-phase flow of CO2 in shallow aquifers. The laboratory experiments involve a series of highly controlled experiments in which CO2 dissolved water is injected in homogeneous and heterogeneous soil columns and tanks. The experimental results are used to study the effects of soil properties, temperature, pressure gradients and heterogeneities on gas formation and migration. We utilize the Finite Element Heat and Mass (FEHM) simulator (Zyvoloski et al, 2010) to numerically model the experimental results. The numerical models capture the physics of CO2 exsolution, multi-phase fluid flow as well as sand heterogeneity. Experimental observations of pressure, temperature and gas saturations are used to develop and constrain conceptual models for CO2 gas-phase formation and multi-phase CO2 flow in porous media. This talk will provide details of development of conceptual models based on experimental observation, development of numerical models for laboratory experiments and modelling results.

  14. Reactive species in non-equilibrium atmospheric-pressure plasmas: Generation, transport, and biological effects

    NASA Astrophysics Data System (ADS)

    Lu, X.; Naidis, G. V.; Laroussi, M.; Reuter, S.; Graves, D. B.; Ostrikov, K.

    2016-05-01

    Non-equilibrium atmospheric-pressure plasmas have recently become a topical area of research owing to their diverse applications in health care and medicine, environmental remediation and pollution control, materials processing, electrochemistry, nanotechnology and other fields. This review focuses on the reactive electrons and ionic, atomic, molecular, and radical species that are produced in these plasmas and then transported from the point of generation to the point of interaction with the material, medium, living cells or tissues being processed. The most important mechanisms of generation and transport of the key species in the plasmas of atmospheric-pressure plasma jets and other non-equilibrium atmospheric-pressure plasmas are introduced and examined from the viewpoint of their applications in plasma hygiene and medicine and other relevant fields. Sophisticated high-precision, time-resolved plasma diagnostics approaches and techniques are presented and their applications to monitor the reactive species and plasma dynamics in the plasma jets and other discharges, both in the gas phase and during the plasma interaction with liquid media, are critically reviewed. The large amount of experimental data is supported by the theoretical models of reactive species generation and transport in the plasmas, surrounding gaseous environments, and plasma interaction with liquid media. These models are presented and their limitations are discussed. Special attention is paid to biological effects of the plasma-generated reactive oxygen and nitrogen (and some other) species in basic biological processes such as cell metabolism, proliferation, survival, etc. as well as plasma applications in bacterial inactivation, wound healing, cancer treatment and some others. Challenges and opportunities for theoretical and experimental research are discussed and the authors' vision for the emerging convergence trends across several disciplines and application domains is presented to

  15. Non-equilibrium thermodynamical description of rhythmic motion patterns of active systems: a canonical-dissipative approach.

    PubMed

    Dotov, D G; Kim, S; Frank, T D

    2015-02-01

    We derive explicit expressions for the non-equilibrium thermodynamical variables of a canonical-dissipative limit cycle oscillator describing rhythmic motion patterns of active systems. These variables are statistical entropy, non-equilibrium internal energy, and non-equilibrium free energy. In particular, the expression for the non-equilibrium free energy is derived as a function of a suitable control parameter. The control parameter determines the Hopf bifurcation point of the deterministic active system and describes the effective pumping of the oscillator. In analogy to the equilibrium free energy of the Landau theory, it is shown that the non-equilibrium free energy decays as a function of the control parameter. In doing so, a similarity between certain equilibrium and non-equilibrium phase transitions is pointed out. Data from an experiment on human rhythmic movements is presented. Estimates for pumping intensity as well as the thermodynamical variables are reported. It is shown that in the experiment the non-equilibrium free energy decayed when pumping intensity was increased, which is consistent with the theory. Moreover, pumping intensities close to zero could be observed at relatively slow intended rhythmic movements. In view of the Hopf bifurcation underlying the limit cycle oscillator model, this observation suggests that the intended limit cycle movements were actually more similar to trajectories of a randomly perturbed stable focus. Copyright © 2015 Elsevier Ireland Ltd. All rights reserved.

  16. Controlling dynamical quantum phase transitions

    NASA Astrophysics Data System (ADS)

    Kennes, D. M.; Schuricht, D.; Karrasch, C.

    2018-05-01

    We study the dynamics arising from a double quantum quench where the parameters of a given Hamiltonian are abruptly changed from being in an equilibrium phase A to a different phase B and back (A →B →A ). As prototype models, we consider the (integrable) transverse Ising field as well as the (nonintegrable) ANNNI model. The return amplitude features nonanalyticities after the first quench through the equilibrium quantum critical point (A →B ), which is routinely taken as a signature of passing through a so-called dynamical quantum phase transition. We demonstrate that nonanalyticities after the second quench (B →A ) can be avoided and reestablished in a recurring manner upon increasing the time T spent in phase B. The system retains an infinite memory of its past state, and one has the intriguing opportunity to control at will whether or not dynamical quantum phase transitions appear after the second quench.

  17. Slit-scanning differential phase-contrast mammography: first experimental results

    NASA Astrophysics Data System (ADS)

    Roessl, Ewald; Daerr, Heiner; Koehler, Thomas; Martens, Gerhard; van Stevendaal, Udo

    2014-03-01

    The demands for a large field-of-view (FOV) and the stringent requirements for a stable acquisition geometry rank among the major obstacles for the translation of grating-based, differential phase-contrast techniques from the laboratory to clinical applications. While for state-of-the-art Full-Field-Digital Mammography (FFDM) FOVs of 24 cm x 30 cm are common practice, the specifications for mechanical stability are naturally derived from the detector pixel size which ranges between 50 and 100 μm. However, in grating-based, phasecontrast imaging, the relative placement of the gratings in the interferometer must be guaranteed to within micro-meter precision. In this work we report on first experimental results on a phase-contrast x-ray imaging system based on the Philips MicroDose L30 mammography unit. With the proposed approach we achieve a FOV of about 65 mm x 175 mm by the use of the slit-scanning technique. The demand for mechanical stability on a micrometer scale was relaxed by the specific interferometer design, i.e., a rigid, actuator-free mount of the phase-grating G1 with respect to the analyzer-grating G2 onto a common steel frame. The image acquisition and formation processes are described and first phase-contrast images of a test object are presented. A brief discussion of the shortcomings of the current approach is given, including the level of remaining image artifacts and the relatively inefficient usage of the total available x-ray source output.

  18. Understanding Chemical Equilibrium: The Role of Gas Phases and Mixing Contributions in the Minimum of Free Energy Plots

    ERIC Educational Resources Information Center

    Tomba, J. Pablo

    2017-01-01

    The use of free energy plots to understand the concept of thermodynamic equilibrium has been shown to be of great pedagogical value in materials science. Although chemical equilibrium is also amenable to this kind of analysis, it is not part of the agenda of materials science textbooks. Something similar is found in chemistry branches, where free…

  19. Recent advances in the CRANK software suite for experimental phasing

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

    Pannu, Navraj S., E-mail: raj@chem.leidenuniv.nl; Waterreus, Willem-Jan; Skubák, Pavol

    2011-04-01

    Recent developments in the CRANK software suite for experimental phasing have led to many more structures being built automatically. For its first release in 2004, CRANK was shown to effectively detect and phase anomalous scatterers from single-wavelength anomalous diffraction data. Since then, CRANK has been significantly improved and many more structures can be built automatically with single- or multiple-wavelength anomalous diffraction or single isomorphous replacement with anomalous scattering data. Here, the new algorithms that have been developed that have led to these substantial improvements are discussed and CRANK’s performance on over 100 real data sets is shown. The latest versionmore » of CRANK is freely available for download at http://www.bfsc.leidenuniv.nl/software/crank/ and from CCP4 (http://www.ccp4.ac.uk/)« less

  20. Non-Equilibrium Phenomena in High Power Beam Materials Processing

    NASA Astrophysics Data System (ADS)

    Tosto, Sebastiano

    2004-03-01

    The paper concerns some aspects of non-equilibrium materials processing with high power beams. Three examples show that the formation of metastable phases plays a crucial role to understand the effects of beam-matter interaction: (i) modeling of pulsed laser induced thermal sputtering; (ii) formation of metastable phases during solidification of the melt pool; (i) possibility of carrying out heat treatments by low power irradiation ``in situ''. The case (i) deals with surface evaporation and boiling processes in presence of superheating. A computer simulation model of thermal sputtering by vapor bubble nucleation in molten phase shows that non-equilibrium processing enables the rise of large surface temperature gradients in the boiling layer and the possibility of sub-surface temperature maximum. The case (ii) concerns the heterogeneous welding of Cu and AISI 304L stainless steel plates by electron beam irradiation. Microstructural investigation of the molten zone has shown that dwell times of the order of 10-1-10-3 s, consistent with moderate cooling rates in the range 10^3-10^5 K/s, entail the formation of metastable Cu-Fe phases. The case (iii) concerns electron beam welding and post-welding treatments of 2219 Al base alloy. Electron microscopy and positron annihilation have explained why post-weld heat transients induced by low power irradiation of specimens in the as welded condition enable ageing effects usually expected after some hours of treatment in furnace. The problem of microstructural instability is particularly significant for a correct design of components manufactured with high power beam technologies and subjected to severe acceptance standards to ensure advanced performances during service life.

  1. Experimental investigations of turbulent temperature fluctuations and phase angles in ASDEX Upgrade

    NASA Astrophysics Data System (ADS)

    Freethy, Simon

    2017-10-01

    A complete experimental understanding of the turbulent fluctuations in tokamak plasmas is essential for providing confidence in the extrapolation of heat transport models to future experimental devices and reactors. Guided by ``predict first'' nonlinear gyrokinetic simulations with the GENE code, two new turbulence diagnostics were designed and have been installed on ASDEX Upgrade (AUG) to probe the fundamentals of ion-scale turbulent electron heat transport. The first, a 30-channel correlation ECE (CECE) radiometer, measures radial profiles (0.5 phase angle between turbulent density and temperature fluctuations. Design predictions are followed by a more traditional ``post-diction'' validation study with GENE. Using a cutting edge synthetic diagnostic GENE shows a factor 1.6 - 2 over-prediction of the fluctuation amplitude, while matching both ion and electron heat fluxes within experimental error. Detailed sensitivity scans are underway to understand the robustness of this disagreement and a detailed assessment of the experimental errors has been carried out. The discrepancy opens questions about the role of multi-scale turbulence physics, but also indicates the need for the comparison of more experimental turbulence properties to have a more complete validation hierarchy. In an effort to understand the discrepancy, predictions of the nT-phase and the radial correlation length have been made along with an assessment of their sensitivity to experimental errors. Comparison to experimental measurements will be discussed. This work is supported in part by the US DOE under Grants DE-SC0006419 and DE-SC0017381. This work has also received

  2. Non-equilibrium supramolecular polymerization

    PubMed Central

    Sorrenti, Alessandro; Leira-Iglesias, Jorge; Markvoort, Albert J.

    2017-01-01

    Supramolecular polymerization has been traditionally focused on the thermodynamic equilibrium state, where one-dimensional assemblies reside at the global minimum of the Gibbs free energy. The pathway and rate to reach the equilibrium state are irrelevant, and the resulting assemblies remain unchanged over time. In the past decade, the focus has shifted to kinetically trapped (non-dissipative non-equilibrium) structures that heavily depend on the method of preparation (i.e., pathway complexity), and where the assembly rates are of key importance. Kinetic models have greatly improved our understanding of competing pathways, and shown how to steer supramolecular polymerization in the desired direction (i.e., pathway selection). The most recent innovation in the field relies on energy or mass input that is dissipated to keep the system away from the thermodynamic equilibrium (or from other non-dissipative states). This tutorial review aims to provide the reader with a set of tools to identify different types of self-assembled states that have been explored so far. In particular, we aim to clarify the often unclear use of the term “non-equilibrium self-assembly” by subdividing systems into dissipative, and non-dissipative non-equilibrium states. Examples are given for each of the states, with a focus on non-dissipative non-equilibrium states found in one-dimensional supramolecular polymerization. PMID:28349143

  3. Teaching the Concept of Gibbs Energy Minimization through Its Application to Phase-Equilibrium Calculation

    ERIC Educational Resources Information Center

    Privat, Romain; Jaubert, Jean-Noe¨l; Berger, Etienne; Coniglio, Lucie; Lemaitre, Ce´cile; Meimaroglou, Dimitrios; Warth, Vale´rie

    2016-01-01

    Robust and fast methods for chemical or multiphase equilibrium calculation are routinely needed by chemical-process engineers working on sizing or simulation aspects. Yet, while industrial applications essentially require calculation tools capable of discriminating between stable and nonstable states and converging to nontrivial solutions,…

  4. Identifying apparent local stable isotope equilibrium in a complex non-equilibrium system.

    PubMed

    He, Yuyang; Cao, Xiaobin; Wang, Jianwei; Bao, Huiming

    2018-02-28

    Although being out of equilibrium, biomolecules in organisms have the potential to approach isotope equilibrium locally because enzymatic reactions are intrinsically reversible. A rigorous approach that can describe isotope distribution among biomolecules and their apparent deviation from equilibrium state is lacking, however. Applying the concept of distance matrix in graph theory, we propose that apparent local isotope equilibrium among a subset of biomolecules can be assessed using an apparent fractionation difference (|Δα|) matrix, in which the differences between the observed isotope composition (δ') and the calculated equilibrium fractionation factor (1000lnβ) can be more rigorously evaluated than by using a previous approach for multiple biomolecules. We tested our |Δα| matrix approach by re-analyzing published data of different amino acids (AAs) in potato and in green alga. Our re-analysis shows that biosynthesis pathways could be the reason for an apparently close-to-equilibrium relationship inside AA families in potato leaves. Different biosynthesis/degradation pathways in tubers may have led to the observed isotope distribution difference between potato leaves and tubers. The analysis of data from green algae does not support the conclusion that AAs are further from equilibrium in glucose-cultured green algae than in the autotrophic ones. Application of the |Δα| matrix can help us to locate potential reversible reactions or reaction networks in a complex system such as a metabolic system. The same approach can be broadly applied to all complex systems that have multiple components, e.g. geochemical or atmospheric systems of early Earth or other planets. Copyright © 2017 John Wiley & Sons, Ltd.

  5. Equilibrium Gold Nanoclusters Quenched with Biodegradable Polymers

    PubMed Central

    Murthy, Avinash K.; Stover, Robert J.; Borwankar, Ameya U.; Nie, Golay D.; Gourisankar, Sai; Truskett, Thomas M.; Sokolov, Konstantin V.; Johnston, Keith P.

    2013-01-01

    Although sub-100 nm nanoclusters of metal nanoparticles are of interest in many fields including biomedical imaging, sensors and catalysis, it has been challenging to control their morphologies and chemical properties. Herein, a new concept is presented to assemble equilibrium Au nanoclusters of controlled size by tuning the colloidal interactions with a polymeric stabilizer, PLA(1k)-b-PEG(10k)-b-PLA(1k). The nanoclusters form upon mixing a dispersion of ~5 nm Au nanospheres with a polymer solution followed by partial solvent evaporation. A weakly adsorbed polymer quenches the equilibrium nanocluster size and provides steric stabilization. Nanocluster size is tuned from ~20 nm to ~40 nm by experimentally varying the final Au nanoparticle concentration and the polymer/Au ratio, along with the charge on the initial Au nanoparticle surface. Upon biodegradation of the quencher, the nanoclusters reversibly and fully dissociate to individual ~5 nm primary particles. Equilibrium cluster size is predicted semi-quantitatively with a free energy model that balances short-ranged depletion and van der Waals attractions with longer-ranged electrostatic repulsion, as a function of the Au and polymer concentrations. The close spacings of the Au nanoparticles in the clusters produce strong NIR extinction over a broad range of wavelengths from 650 to 900 nm, which is of practical interest in biomedical imaging. PMID:23230905

  6. Nonflat equilibrium liquid shapes on flat surfaces.

    PubMed

    Starov, Victor M

    2004-01-15

    The hydrostatic pressure in thin liquid layers differs from the pressure in the ambient air. This difference is caused by the actions of surface forces and capillary pressure. The manifestation of the surface force action is the disjoining pressure, which has a very special S-shaped form in the case of partial wetting (aqueous thin films and thin films of aqueous electrolyte and surfactant solutions, both free films and films on solid substrates). In thin flat liquid films the disjoining pressure acts alone and determines their thickness. However, if the film surface is curved then both the disjoining and the capillary pressures act simultaneously. In the case of partial wetting their simultaneous action results in the existence of nonflat equilibrium liquid shapes. It is shown that in the case of S-shaped disjoining pressure isotherm microdrops, microdepressions, and equilibrium periodic films exist on flat solid substrates. Criteria are found for both the existence and the stability of these nonflat equilibrium liquid shapes. It is shown that a transition from thick films to thinner films can go via intermediate nonflat states, microdepressions and periodic films, which both can be more stable than flat films within some range of hydrostatic pressure. Experimental investigations of shapes of the predicted nonflat layers can open new possibilities of determination of disjoining pressure in the range of thickness in which flat films are unstable.

  7. Experimentally enhanced model-based deconvolution of propagation-based phase-contrast data

    NASA Astrophysics Data System (ADS)

    Pichotka, M.; Palma, K.; Hasn, S.; Jakubek, J.; Vavrik, D.

    2016-12-01

    In recent years phase-contrast has become a much investigated modality in radiographic imaging. The radiographic setups employed in phase-contrast imaging are typically rather costly and complex, e.g. high performance Talbot-Laue interferometers operated at synchrotron light sources. In-line phase-contrast imaging states the most pedestrian approach towards phase-contrast enhancement. Utilizing small angle deflection within the imaged sample and the entailed interference of the deflected and un-deflected beam during spatial propagation, in-line phase-contrast imaging only requires a well collimated X-ray source with a high contrast & high resolution detector. Employing high magnification the above conditions are intrinsically fulfilled in cone-beam micro-tomography. As opposed of 2D imaging, where contrast enhancement is generally considered beneficial, in tomographic modalities the in-line phase-contrast effect can be quite a nuisance since it renders the inverse problem posed by tomographic reconstruction inconsistent, thus causing reconstruction artifacts. We present an experimentally enhanced model-based approach to disentangle absorption and in-line phase-contrast. The approach employs comparison of transmission data to a system model computed iteratively on-line. By comparison of the forward model to absorption data acquired in continuous rotation strong local deviations of the data residual are successively identified as likely candidates for in-line phase-contrast. By inducing minimal vibrations (few mrad) to the sample around the peaks of such deviations the transmission signal can be decomposed into a constant absorptive fraction and an oscillating signal caused by phase-contrast which again allows to generate separate maps for absorption and phase-contrast. The contributions of phase-contrast and the corresponding artifacts are subsequently removed from the tomographic dataset. In principle, if a 3D handling of the sample is available, this method also

  8. Integrated Experimental and Modelling Research for Non-Ferrous Smelting and Recycling Systems

    NASA Astrophysics Data System (ADS)

    Jak, Evgueni; Hidayat, Taufiq; Shishin, Denis; Mehrjardi, Ata Fallah; Chen, Jiang; Decterov, Sergei; Hayes, Peter

    The chemistries of industrial pyrometallurgical non-ferrous smelting and recycling processes are becoming increasingly complex. Optimisation of process conditions, charge composition, temperature, oxygen partial pressure, and partitioning of minor elements between phases and different process streams require accurate description of phase equilibria and thermodynamics which are the focus of the present research. The experiments involve high temperature equilibration in controlled gas atmospheres, rapid quenching and direct measurement of equilibrium phase compositions with quantitative microanalytical techniques including electron probe X-ray microanalysis and Laser Ablation ICP-MS. The thermodynamic modelling is undertaken using computer package FactSage with the quasi-chemical model for the liquid slag phase and other advanced models. Experimental and modelling studies are combined into an integrated research program focused on the major elements Cu-Pb-Fe-O-Si-S system, slagging Al, Ca, Mg and other minor elements. The ongoing development of the research methodologies has resulted in significant advances in research capabilities. Examples of applications are given.

  9. First principles study of pressure induced polymorphic phase transition in trimethylamine

    NASA Astrophysics Data System (ADS)

    Abraham, B. Moses; Vaitheeswaran, G.

    2018-04-01

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

  10. Nonequilibrium phase transitions of sheared colloidal microphases: Results from dynamical density functional theory

    NASA Astrophysics Data System (ADS)

    Stopper, Daniel; Roth, Roland

    2018-06-01

    By means of classical density functional theory and its dynamical extension, we consider a colloidal fluid with spherically symmetric competing interactions, which are well known to exhibit a rich bulk phase behavior. This includes complex three-dimensional periodically ordered cluster phases such as lamellae, two-dimensional hexagonally packed cylinders, gyroid structures, or spherical micelles. While the bulk phase behavior has been studied extensively in earlier work, in this paper we focus on such structures confined between planar repulsive walls under shear flow. For sufficiently high shear rates, we observe that microphase separation can become fully suppressed. For lower shear rates, however, we find that, e.g., the gyroid structure undergoes a kinetic phase transition to a hexagonally packed cylindrical phase, which is found experimentally and theoretically in amphiphilic block copolymer systems. As such, besides the known similarities between the latter and colloidal systems regarding the equilibrium phase behavior, our work reveals further intriguing nonequilibrium relations between copolymer melts and colloidal fluids with competing interactions.

  11. Stochastic pumping of non-equilibrium steady-states: how molecules adapt to a fluctuating environment.

    PubMed

    Astumian, R D

    2018-01-11

    In the absence of input energy, a chemical reaction in a closed system ineluctably relaxes toward an equilibrium state governed by a Boltzmann distribution. The addition of a catalyst to the system provides a way for more rapid equilibration toward this distribution, but the catalyst can never, in and of itself, drive the system away from equilibrium. In the presence of external fluctuations, however, a macromolecular catalyst (e.g., an enzyme) can absorb energy and drive the formation of a steady state between reactant and product that is not determined solely by their relative energies. Due to the ubiquity of non-equilibrium steady states in living systems, the development of a theory for the effects of external fluctuations on chemical systems has been a longstanding focus of non-equilibrium thermodynamics. The theory of stochastic pumping has provided insight into how a non-equilibrium steady-state can be formed and maintained in the presence of dissipation and kinetic asymmetry. This effort has been greatly enhanced by a confluence of experimental and theoretical work on synthetic molecular machines designed explicitly to harness external energy to drive non-equilibrium transport and self-assembly.

  12. Phase Stability and Electronic Structure of Prospective Sb-Based Mixed Sulfide and Iodide 3D Perovskite (CH3NH3)SbSI2.

    PubMed

    Li, Tianyang; Wang, Xiaoming; Yan, Yanfa; Mitzi, David B

    2018-06-29

    Lead-free antimony-based mixed sulfide and iodide perovskite phases have recently been reported to be synthesized experimentally and to exhibit reasonable photovoltaic performance. Through a combination of experimental validation and computational analysis, we show no evidence of the formation of the mixed sulfide and iodide perovskite phase, MASbSI 2 (MA = CH 3 NH 3 + ), and instead that the main products are a mixture of the binary and ternary compounds (Sb 2 S 3 and MA 3 Sb 2 I 9 ). Density functional theory calculations also indicate that such a mixed sulfide and iodide perovskite phase should be thermodynamically less stable compared with binary/ternary anion-segregated secondary phases and less likely to be synthesized under equilibrium conditions. Additionally, band structure calculations show that this mixed sulfide and iodide phase, if possible to synthesize (e.g., under nonequilibrium conditions), should have a suitable direct band gap for photovoltaic application.

  13. Improved Simulation of the Pre-equilibrium Triton Emission in Nuclear Reactions Induced by Nucleons

    NASA Astrophysics Data System (ADS)

    Konobeyev, A. Yu.; Fischer, U.; Pereslavtsev, P. E.; Blann, M.

    2014-04-01

    A new approach is proposed for the calculation of non-equilibrium triton energy distributions in nuclear reactions induced by nucleons of intermediate energies. It combines models describing the nucleon pick-up, the coalescence and the triton knock-out processes. Emission and absorption rates for excited particles are represented by the pre-equilibrium hybrid model. The model of Sato, Iwamoto, Harada is used to describe the nucleon pick-up and the coalescence of nucleons from exciton configurations starting from (2p,1h) states. The contribution of the direct nucleon pick-up is described phenomenologically. Multiple pre-equilibrium emission of tritons is accounted for. The calculated triton energy distributions are compared with available experimental data.

  14. Experimental and Model Studies on Continuous Separation of 2-Phenylpropionic Acid Enantiomers by Enantioselective Liquid-Liquid Extraction in Centrifugal Contactor Separators.

    PubMed

    Feng, Xiaofeng; Tang, Kewen; Zhang, Pangliang; Yin, Shuangfeng

    2016-03-01

    Multistage enantioselective liquid-liquid extraction (ELLE) of 2-phenylpropionic acid (2-PPA) enantiomers using hydroxypropyl-β-cyclodextrin (HP-β-CD) as extractant was studied experimentally in a counter-current cascade of centrifugal contactor separators (CCSs). Performance of the process was evaluated by purity (enantiomeric excess, ee) and yield (Y). A multistage equilibrium model was established on the basis of single-stage model for chiral extraction of 2-PPA enantiomers and the law of mass conservation. A series of experiments on the extract phase/washing phase ratio (W/O ratio), extractant concentration, the pH value of aqueous phase, and the number of stages was conducted to verify the multistage equilibrium model. It was found that model predictions were in good agreement with the experimental results. The model was applied to predict and optimize the symmetrical separation of 2-PPA enantiomers. The optimal conditions for symmetric separation involves a W/O ratio of 0.6, pH of 2.5, and HP-β-CD concentration of 0.1 mol L(-1) at a temperature of 278 K, where eeeq (equal enantiomeric excess) can reach up to 37% and Yeq (equal yield) to 69%. By simulation and optimization, the minimum number of stages was evaluated at 98 and 106 for eeeq > 95% and eeeq > 97%. © 2016 Wiley Periodicals, Inc.

  15. Lattice Stability and Interatomic Potential of Non-equilibrium Warm Dense Gold

    NASA Astrophysics Data System (ADS)

    Chen, Z.; Mo, M.; Soulard, L.; Recoules, V.; Hering, P.; Tsui, Y. Y.; Ng, A.; Glenzer, S. H.

    2017-10-01

    Interatomic potential is central to the calculation and understanding of the properties of matter. A manifestation of interatomic potential is lattice stability in the solid-liquid transition. Recently, we have used frequency domain interferometry (FDI) to study the disassembly of ultrafast laser heated warm dense gold nanofoils. The FDI measurement is implemented by a spatial chirped single-shot technique. The disassembly of the sample is characterized by the change in phase shift of the reflected probe resulted from hydrodynamic expansion. The experimental data is compared with the results of two-temperature molecular dynamic simulations based on a highly optimized embedded-atom-method (EAM) interatomic potential. Good agreement is found for absorbed energy densities of 0.9 to 4.3MJ/kg. This provides the first demonstration of the applicability of an EAM interatomic potential in the non-equilibrium warm dense matter regime. The MD simulations also reveal the critical role of pressure waves in solid-liquid transition in ultrafast laser heated nanofoils. This work is supported by DOE Office of Science, Fusion Energy Science under FWP 100182, and SLAC LDRD program.

  16. The Onset of Double Diffusive Convection in a Viscoelastic Fluid-Saturated Porous Layer with Non-Equilibrium Model

    PubMed Central

    Yang, Zhixin; Wang, Shaowei; Zhao, Moli; Li, Shucai; Zhang, Qiangyong

    2013-01-01

    The onset of double diffusive convection in a viscoelastic fluid-saturated porous layer is studied when the fluid and solid phase are not in local thermal equilibrium. The modified Darcy model is used for the momentum equation and a two-field model is used for energy equation each representing the fluid and solid phases separately. The effect of thermal non-equilibrium on the onset of double diffusive convection is discussed. The critical Rayleigh number and the corresponding wave number for the exchange of stability and over-stability are obtained, and the onset criterion for stationary and oscillatory convection is derived analytically and discussed numerically. PMID:24312193

  17. The onset of double diffusive convection in a viscoelastic fluid-saturated porous layer with non-equilibrium model.

    PubMed

    Yang, Zhixin; Wang, Shaowei; Zhao, Moli; Li, Shucai; Zhang, Qiangyong

    2013-01-01

    The onset of double diffusive convection in a viscoelastic fluid-saturated porous layer is studied when the fluid and solid phase are not in local thermal equilibrium. The modified Darcy model is used for the momentum equation and a two-field model is used for energy equation each representing the fluid and solid phases separately. The effect of thermal non-equilibrium on the onset of double diffusive convection is discussed. The critical Rayleigh number and the corresponding wave number for the exchange of stability and over-stability are obtained, and the onset criterion for stationary and oscillatory convection is derived analytically and discussed numerically.

  18. Importance of granulometry on phase evolution and phase-to-phase relationships of experimentally burned impure limestones intended for production of hydraulic lime and/or natural cement

    NASA Astrophysics Data System (ADS)

    Kozlovcev, Petr; Přikryl, Richard; Přikrylová, Jiřina

    2015-04-01

    In contrast to modern ordinary Portland cement production from finely ground raw material blends, ancient burning of hydraulic lime was conducted by burning larger pieces of natural raw material. Due to natural variability of raw material composition, exploitation of different beds from even one formation can result the product with significantly different composition and/or properties. Prague basin (Neoproterozoic to pre-Variscan Palaeozoic of the central part of the Bohemian Massif - the so-called Barrandian area, Czech Republic) represents a classical example of the limestone-rich region with long-term history of limestone burning for quick lime and/or various types of hydraulic binders. Due to the fact that burning of natural hydraulic lime has been abandoned in this region at the turn of 19th/20th c., significant gap in knowledge on the behavior of various limestone types and on the influence of minor variance in composition on the quality of burned product is encountered. Moreover, the importance of employment of larger pieces of raw material for burning for the development of proper phase-to-phase relationships (i.e. development of hydraulic phases below sintering temperature at mutual contacts of minerals) has not been examined before. To fill this gap, a representative specimens of major limestone types from the Prague basin have been selected for experimental study: Upper Silurian limestone types (Přídolí and Kopanina Lms.), and Lower Devonian limestones (Radotín, Kotýs, Řeporyje, Dvorce-Prokop, and Zlíchov Lms.). Petrographic character of the experimental material was examined by polarizing microscopy, cathodoluminescence, scanning electron microscopy with an energy dispersive spectrometer (SEM-EDS), and X-ray diffraction (XRD) of insoluble residue. Based on the data from wet silicate analyses, modal composition of studied impure limestones was computed. Experimental raw material was burned in laboratory electric furnace at 1000 and 1200°C for 3

  19. Multi-period equilibrium/near-equilibrium in electricity markets based on locational marginal prices

    NASA Astrophysics Data System (ADS)

    Garcia Bertrand, Raquel

    In this dissertation we propose an equilibrium procedure that coordinates the point of view of every market agent resulting in an equilibrium that simultaneously maximizes the independent objective of every market agent and satisfies network constraints. Therefore, the activities of the generating companies, consumers and an independent system operator are modeled: (1) The generating companies seek to maximize profits by specifying hourly step functions of productions and minimum selling prices, and bounds on productions. (2) The goals of the consumers are to maximize their economic utilities by specifying hourly step functions of demands and maximum buying prices, and bounds on demands. (3) The independent system operator then clears the market taking into account consistency conditions as well as capacity and line losses so as to achieve maximum social welfare. Then, we approach this equilibrium problem using complementarity theory in order to have the capability of imposing constraints on dual variables, i.e., on prices, such as minimum profit conditions for the generating units or maximum cost conditions for the consumers. In this way, given the form of the individual optimization problems, the Karush-Kuhn-Tucker conditions for the generating companies, the consumers and the independent system operator are both necessary and sufficient. The simultaneous solution to all these conditions constitutes a mixed linear complementarity problem. We include minimum profit constraints imposed by the units in the market equilibrium model. These constraints are added as additional constraints to the equivalent quadratic programming problem of the mixed linear complementarity problem previously described. For the sake of clarity, the proposed equilibrium or near-equilibrium is first developed for the particular case considering only one time period. Afterwards, we consider an equilibrium or near-equilibrium applied to a multi-period framework. This model embodies binary

  20. Phase Equilibria of Sn-Co-Cu Ternary System

    NASA Astrophysics Data System (ADS)

    Chen, Yu-Kai; Hsu, Chia-Ming; Chen, Sinn-Wen; Chen, Chih-Ming; Huang, Yu-Chih

    2012-10-01

    Sn-Co-Cu ternary alloys are promising lead-free solders, and isothermal sections of Sn-Co-Cu phase equilibria are fundamentally important for the alloys' development and applications. Sn-Co-Cu ternary alloys were prepared and equilibrated at 523 K, 1073 K, and 1273 K (250 °C, 800 °C, and 1000 °C), and the equilibrium phases were experimentally determined. In addition to the terminal solid solutions and binary intermetallic compounds, a new ternary compound, Sn3Co2Cu8, was found. The solubilities of Cu in the α-CoSn3 and CoSn2 phases at 523 K (250 °C) are 4.2 and 1.6 at. pct, respectively, while the Cu solubility in the α-Co3Sn2 phase is as high as 20.0 at. pct. The Cu solubility increases with temperature and is around 30.0 at. pct in the β-Co3Sn2 at 1073 K (800 °C). The Co solubility in the η-Cu6Sn5 phase is also significant and is 15.5 at. pct at 523 K (250 °C).