WorldWideScience

Sample records for density glass transition

  1. A density-independent glass transition in biological tissues

    CERN Document Server

    Bi, Dapeng; Schwarz, J M; Manning, M Lisa

    2014-01-01

    Cells must move through tissues in many important biological processes, including embryonic development, cancer metastasis, and wound healing. In these tissues, a cell's motion is often strongly constrained by its neighbors, leading to glassy dynamics. Recent work has demonstrated the existence of a non-equilibrium glass transition in self-propelled particle models for active matter, where the transition is driven by changes in density. However, this may not explain liquid-to-solid transitions in confluent tissues, where there are no gaps between cells and the packing fraction remains fixed and equal to unity. Here we demonstrate the existence of a different type of glass transition that occurs in the well-studied vertex model for confluent tissue monolayers. In this model, the onset of rigidity is governed by changes to single-cell properties such as cell-cell adhesion, cortical tension, and volume compressibility, providing an explanation for a liquid-to-solid transitions in confluent tissues.

  2. Predicting the glass transition temperature as function of crosslink density and polymer interactions in rubber compounds

    Science.gov (United States)

    D'Escamard, Gabriella; De Rosa, Claudio; Auriemma, Finizia

    2016-05-01

    Crosslink sulfur density in rubber compounds and interactions in polymer blends are two of the composition elements that affect the rubber compound properties and glass transition temperature (Tg), which is a marker of polymer properties related to its applications. Natural rubber (NR), butadiene rubber (BR) and styrene-butadiene rubber (SBR) compounds were investigated using calorimetry (DSC) and dynamic mechanical analysis (DMA). The results indicate that the Di Marzio's and Schneider's Models predict with accuracy the dependence of Tg on crosslink density and composition in miscible blends, respectively, and that the two model may represent the base to study the relevant "in service" properties of real rubber compounds.

  3. A simple real space density functional theory of freezing, with implications for the glass transition

    Energy Technology Data Exchange (ETDEWEB)

    Stoessel, J.P.; Wolynes, P.G.

    1989-01-01

    With analogy to the ''highly accurate'' summation of cluster diagrams for hard sphere fluids a la Carnahan-Starling, we present a simple, real space free energy density functional for arbitrary potential systems, based on the generalization of the second virial coefficient to inhomogeneous systems which, when applied to hard sphere, soft-sphere, and Lennard-Jones freezing, yield melting characteristics in remarkable agreement with experiment. Implications for the liquid-glass transition in all three potential systems are also presented. 45 refs., 7 figs., 1 tab.

  4. Phase Transition in the Density of States of Quantum Spin Glasses

    Energy Technology Data Exchange (ETDEWEB)

    Erdős, László, E-mail: lerdos@ist.ac.at [IST Austria (Austria); Schröder, Dominik, E-mail: schroeder.dominik@gmail.com [Ludwig-Maximilians-Universität München (Germany)

    2014-12-15

    We prove that the empirical density of states of quantum spin glasses on arbitrary graphs converges to a normal distribution as long as the maximal degree is negligible compared with the total number of edges. This extends the recent results of Keating et al. (2014) that were proved for graphs with bounded chromatic number and with symmetric coupling distribution. Furthermore, we generalise the result to arbitrary hypergraphs. We test the optimality of our condition on the maximal degree for p-uniform hypergraphs that correspond to p-spin glass Hamiltonians acting on n distinguishable spin- 1/2 particles. At the critical threshold p = n{sup 1/2} we find a sharp classical-quantum phase transition between the normal distribution and the Wigner semicircle law. The former is characteristic to classical systems with commuting variables, while the latter is a signature of noncommutative random matrix theory.

  5. High density fluoride glass calorimeter

    Science.gov (United States)

    Xie, Q.; Scheltzbaum, J.; Akgun, U.

    2014-04-01

    The unprecedented radiation levels in current Large Hadron Collider runs, and plans to even increase the luminosity creates a need for new detector technologies to be investigated. Quartz plates to replace the plastic scintillators in current LHC calorimeters have been proposed in recent reports. Quartz based Cherenkov calorimeters can solve the radiation damage problem, however light production and transfer have proven to be challenging. This report summarizes the results from a computational study on the performance of a high-density glass calorimeter. High-density, scintillating, fluoride glass, CHG3, was used as the active material. This glass has been developed specifically for hadron collider experiments, and is known for fast response time, in addition to high light yield. Here, the details of a Geant4 model for a sampling calorimeter prototype with 20 layers, and its hadronic as well as electromagnetic performances are reported.

  6. Density of States Simulations of Confined Glasses

    Science.gov (United States)

    Faller, Roland; Ghosh, Jayeeta

    2008-03-01

    Glassy systems under confinement have been studied with great enthusiasm and effort for the last decades. They are relevant both fundamentally and technically because there is still debate about the nature of glass transition in small geometries which is important for lithographic processes in the semiconductor and other industries. In this work we are using the Wang-Landau approach also known as Density of States Monte Carlo to study glassy systems in bulk and under confinement. We apply the technique to a model binary Lennard Jones glass as well as the small organic glass former Ortho-terphenyl (OTP). For Lennard Jones glasses we use a well tested model. For OTP we start from a united atom model and then derive systematically a coarse grained representation by replacing each phenyl ring with a bead and using the Iterative Boltzmann Inversion. The properties of bulk Lennard Jones model show very good agreement with literature values. The atomistic and coarse grained representations of ortho-terphenyl in the bulk are in good agreement with experiments. Unsupported freestanding films show a lower glass transition than the bulk value.

  7. Thermodynamic signature of the dynamic glass transition in hard spheres.

    Science.gov (United States)

    Hermes, Michiel; Dijkstra, Marjolein

    2010-03-17

    We use extensive event-driven molecular dynamics simulations to study the thermodynamic, structural and dynamic properties of hard-sphere glasses. We determine the equation of state of the metastable fluid branch for hard spheres with a size polydispersity of 10%. Our results show a clear jump in the slope of the isothermal compressibility. The observation of a thermodynamic signature at the transition from a metastable fluid to a glassy state is analogous to the abrupt change in the specific heat or thermal expansion coefficient as observed for molecular liquids at the glass transition. The dynamic glass transition becomes more pronounced and shifts to higher densities for longer equilibration times.

  8. Scaling and universality in glass transition

    Science.gov (United States)

    de Candia, Antonio; Fierro, Annalisa; Coniglio, Antonio

    2016-05-01

    Kinetic facilitated models and the Mode Coupling Theory (MCT) model B are within those systems known to exhibit a discontinuous dynamical transition with a two step relaxation. We consider a general scaling approach, within mean field theory, for such systems by considering the behavior of the density correlator and the dynamical susceptibility  - 2. Focusing on the Fredrickson and Andersen (FA) facilitated spin model on the Bethe lattice, we extend a cluster approach that was previously developed for continuous glass transitions by Arenzon et al. (Phys. Rev. E 90, 020301(R) (2014)) to describe the decay to the plateau, and consider a damage spreading mechanism to describe the departure from the plateau. We predict scaling laws, which relate dynamical exponents to the static exponents of mean field bootstrap percolation. The dynamical behavior and the scaling laws for both density correlator and dynamical susceptibility coincide with those predicted by MCT. These results explain the origin of scaling laws and the universal behavior associated with the glass transition in mean field, which is characterized by the divergence of the static length of the bootstrap percolation model with an upper critical dimension dc = 8.

  9. Phase transitions and glass transition in a hyperquenched silica–alumina glass

    DEFF Research Database (Denmark)

    Zhang, Y.F.; Zhao, D.H.; Yue, Yuanzheng

    2017-01-01

    We investigate phase transitions, glass transition, and dynamic behavior in the hyperquenched 69SiO2–31Al2O3 (mol%) glass (SA glass). Upon reheating, the SA glass exhibits a series of thermal responses. Subsequent to the sub-Tg enthalpy release, the glass undergoes a large jump in isobaric heat...... capacity (ΔCp) during glass transition, implying the fragile nature of the SA glass. The mullite starts to form before the end of glass transition, indicating that the SA glass is extremely unstable against crystallization. After the mullite formation, the remaining glass phase exhibits an increased Tg...... and a suppressed ΔCp. The formation of cristobalite at 1553 K indicates the dominance of silica in the remaining glass matrix. The cristobalite gradually re-melts as the isothermal heat-treatment temperature is raised from 1823 to 1853 K, which is well below the melting point of cristobalite, while the amount...

  10. Intermolecular forces and the glass transition.

    Science.gov (United States)

    Hall, Randall W; Wolynes, Peter G

    2008-01-17

    Random first-order transition theory is used to determine the role of attractive and repulsive interactions in the dynamics of supercooled liquids. Self-consistent phonon theory, an approximate mean field treatment consistent with random first-order transition theory, is used to treat individual glassy configurations, whereas the liquid phase is treated using common liquid-state approximations. Free energies are calculated using liquid-state perturbation theory. The transition temperature, T*A, the temperature where the onset of activated behavior is predicted by mean field theory; the lower crossover temperature, T*C, where barrierless motions actually occur through fractal or stringy motions (corresponding to the phenomenological mode coupling transition temperature); and T*K, the Kauzmann temperature (corresponding to an extrapolated entropy crisis), are calculated in addition to T*g, the glass transition temperature that corresponds to laboratory cooling rates. Relationships between these quantities agree well with existing experimental and simulation data on van der Waals liquids. Both the isobaric and isochoric behavior in the supercooled regime are studied, providing results for DeltaCV and DeltaCp that can be used to calculate the fragility as a function of density and pressure, respectively. The predicted variations in the alpha-relaxation time with temperature and density conform to the empirical density-temperature scaling relations found by Casalini and Roland. We thereby demonstrate the microscopic origin of their observations. Finally, the relationship first suggested by Sastry between the spinodal temperature and the Kauzmann temperatures, as a function of density, is examined. The present microscopic calculations support the existence of an intersection of these two temperatures at sufficiently low temperatures.

  11. Measurement of Density Inhomogeneity for Glass Pendulum

    Institute of Scientific and Technical Information of China (English)

    LIU Lin-Xia; LIU Qi; SHAO Cheng-Gang; ZHANG Ya-Ting; LUO Jun; Vadim Milyukov

    2008-01-01

    @@ The density inhomogeneity of a glass pendulum is determined by an optical interference method.The relative variations of the densities over a volume with sizes of 5 × 5 × 5mm3 are (0.64±0.97) × 10-5 and (0.99 ± 0.92) ×10-5 for the K9 glass and silica glass pendulum, respectively.These variations of densities contributing to the relative uncertainties of the Newtonian gravitational constant G are 0.20 ppm and 0.21 ppm in our experiment on measurement of G.

  12. Multiple reentrant glass transitions of soft spheres at high densities: monotonicity of the curves of constant relaxation time in jamming phase diagrams depending on temperature over pressure and pressure.

    Science.gov (United States)

    Schmiedeberg, Michael

    2013-05-01

    By using molecular-dynamics simulations, we determine the jamming phase diagrams at high densities for a bidisperse mixture of soft spheres that interact according to repulsive power-law pair potentials. We observe that the relaxation time varies nonmonotonically as a function of density at constant temperature. Therefore, the jamming phase diagrams contain multiple reentrant glass transitions if temperature and density are used as control parameters. However, if we consider a new formulation of the jamming phase diagrams where temperature over pressure and pressure are employed as control parameters, no nonmonotonic behavior is observed.

  13. Electron anions and the glass transition temperature

    Energy Technology Data Exchange (ETDEWEB)

    Johnson, Lewis E.; Sushko, Peter V.; Tomota, Yudai; Hosono, Hideo

    2016-08-24

    Properties of glasses are typically controlled by judicious selection of the glass-forming and glass-modifying constituents. Through an experimental and computational study of the crystalline, molten, and amorphous [Ca12Al14O32]2+ ∙ (e)2, we demonstrate that electron anions in this system behave as glass-modifiers that strongly affect solidification dynamics, the glass transition temperature, and spectroscopic properties of the resultant amorphous material. Concentration of such electron anions is a consequential control parameter: it invokes materials evolution pathways and properties not available in conventional glasses, which opens a new avenue in rational materials design.

  14. Theoretical approaches to the glass transition in simple liquids

    Indian Academy of Sciences (India)

    Chandan Dasgupta

    2005-05-01

    Theoretical approaches to the development of an understanding of the behaviour of simple supercooled liquids near the structural glass transition are reviewed and our work on this problem, based on the density functional theory of freezing and replicated liquid state theory, are summarized in this context. A few directions for further work on this problem are suggested.

  15. Glass transition temperature and conductivity in Li2O and Na2O doped borophosphate glasses

    Science.gov (United States)

    Ashwajeet, J. S.; Sankarappa, T.; Ramanna, R.; Sujatha, T.; Awasthi, A. M.

    2015-08-01

    Two alkali doped Borophosphate glasses in the composition, (B2O3)0.2. (P2O5)0.3. (Na2O)(0.5-x). (Li2O)x, where x = 0.05 to 0.50 were prepared by standard melt quenching method at 1200K. Non-crystalline nature was confirmed by XRD studies. Room temperature density was measured by Archimedes principle. DC conductivity in the temperature range from 300K to 575K has been measured. Samples were DSC studied in the temperature range from 423K to 673K and glass transition temperature was determined. Glass transition temperature passed through minima for Li2O con.2centration between 0.25 and 0.30 mole fractions. Activation energy of conduction has been determined by analyzing temperature variation of conductivity determining Arrhenius law. Conductivity passed through minimum and activation passed through maximum for Li2O content from 0.25 to 0.30 mole fractions. Glass transition temperature passed through minimum for the same range of Li2O content. These results revealed mixed alkali effect taking place in these glasses. It is for the first time borophosphate glasses doped with Li2O and Na2O have been studied for density and dc conductivity and, the mixed alkali effect (MAE) has been observed.

  16. Application of Glass Transition in Food Processing.

    Science.gov (United States)

    Balasubramanian, S; Devi, Apramita; Singh, K K; Bosco, S J D; Mohite, Ashish M

    2016-01-01

    The phenomenon of glass transition has been employed to food products to study their stability. It can be applied as an integrated approach along with water activity and physical and chemical changes in food in processing and storage to determine the food stability. Also associated with the changes during agglomeration crystallization, caking, sticking, collapse, oxidation reactions, nonenzymatic browning, and microbial stability of food system. Various techniques such as Differential Scanning Calorimetry, Nuclear Magnetic Resonance, etc. have been developed to determine the glass transition temperature (Tg) of food system. Also, various theories have been applied to explain the concept of Tg and its relation to changes in food system. This review summarizes the understanding of concept of glass transition, its measurement, and application in food technology.

  17. GLASS TRANSITION OF HYDRATED WHEAT GLIADIN POWDERS

    Institute of Scientific and Technical Information of China (English)

    Shao-min Sun; Li Zhao; Yi-hu Song; Qiang Zheng

    2011-01-01

    Modulated-temperature differential scanning calorimetric and dynamic mechanical analyses and dielectric spectroscopy were used to investigate the glass transition of hydrated wheat gliadin powders with moisture absorption ranged from 2.30 db% to 18.21 db%. Glass transition temperature (Tg) of dry wheat gliadin was estimated according to the GordonTaylor equation. Structural heterogeneity at high degrees of hydration was revealed in dielectric temperature and frequency spectra. The activation energies (Ea) of the two relaxations were calculated from Arrhenius equation.

  18. Comment on "Liquid Limits: The Glass Transition and Liquid-Gas Spinodal Boundaries of Metastable Liquids"

    OpenAIRE

    2000-01-01

    In ref. cond-mat/0005372, Sastry studies by numerical simulations the phase diagram of a simple fragile glass-forming liquid, presenting very interesting and clear results. We apply to this system, at various density values, the analytic approach to structural glass thermodynamics recently introduced and we compare our theoretical predictions on the liquid-glass transition temperature with Sastry's data.

  19. Density of States Simulations of Various Glass Formers

    Science.gov (United States)

    Ghosh, Jayeeta; Faller, Roland

    2008-02-01

    The behavior of glassy systems in bulk and especially in confined geometries has received considerable attention over the last decades because of the technological importance and inherent complexity of the systems near or below the transition temperature. Confined glasses have been studied using different theoretical and experimental techniques which helped shape our understanding; but still huge gaps remain. In this work we are using the Wang-Landau Monte Carlo approach to study different model glasses. General Monte Carlo fails to sample all relevant regions of phase space; the application of this method gives us the opportunity to directly estimate the density of states and consequently any other thermodynamic properties. We can calculate properties in different ensembles using the same simulation runs. This random walk algorithm is designed to visit all energy states with equal probability to produce a flat histogram. We can estimate the density of states on the fly whenever any energy state is visited. We perform multiple simulations in overlapping energy regions and finally join them after proper scaling to obtain the overall density of states; the global density of states of the glass former is then known to within a constant. We apply this technique to a model binary Lennard Jones glass which is a well tested model, as well as for the first time to a realistic glass forming system, the small organic glass former Ortho-terphenyl (OTP). For OTP we start from a united atom model and derive systematically a coarse-grained representation by replacing each phenyl ring with one interaction site. We apply the Iterative Boltzmann Inversion for this purpose. This method relies on the structure of the atomistic model, mainly the radial distribution function (RDF). One needs to Boltzmann invert the atomistic RDF to obtain an initial guess for the non-bonded potential. Then using this potential for the preliminary coarse grained run gives a first set of RDFs to compare

  20. Superconducting Metallic Glass Transition-Edge-Sensors

    Science.gov (United States)

    Hays, Charles C. (Inventor)

    2013-01-01

    A superconducting metallic glass transition-edge sensor (MGTES) and a method for fabricating the MGTES are provided. A single-layer superconducting amorphous metal alloy is deposited on a substrate. The single-layer superconducting amorphous metal alloy is an absorber for the MGTES and is electrically connected to a circuit configured for readout and biasing to sense electromagnetic radiation.

  1. The glass transition of hard spherical colloids

    Energy Technology Data Exchange (ETDEWEB)

    Pusey, P.N. (Royal Signals and Radar Establishment, Malvern (UK)); Van Megen, W. (Royal Melbourne Inst. of Tech. (Australia). Dept. of Applied Physics)

    1990-03-01

    When suspended in a liquid, hard spherical colloidal particles can show fluid, crystalline and glassy phases. A light scattering study of the dynamics of the metastable fluid and glassy phases is reported. Comparison is made with the predictions of mode-coupling theories applied to the glass transition of simple atomic systems. (orig.).

  2. Ideal glass transitions by random pinning

    Science.gov (United States)

    Cammarota, Chiara; Biroli, Giulio

    2012-01-01

    We study the effect of freezing the positions of a fraction c of particles from an equilibrium configuration of a supercooled liquid at a temperature T. We show that within the random first-order transition theory pinning particles leads to an ideal glass transition for a critical fraction c = cK(T) even for moderate supercooling; e.g., close to the Mode-Coupling transition temperature. First we derive the phase diagram in the T - c plane by mean field approximations. Then, by applying a real-space renormalization group method, we obtain the critical properties for |c - cK(T)| → 0, in particular the divergence of length and time scales, which are dominated by two zero-temperature fixed points. We also show that for c = cK(T) the typical distance between frozen particles is related to the static point-to-set length scale of the unconstrained liquid. We discuss what are the main differences when particles are frozen in other geometries and not from an equilibrium configuration. Finally, we explain why the glass transition induced by freezing particles provides a new and very promising avenue of research to probe the glassy state and ascertain, or disprove, the validity of the theories of the glass transition. PMID:22623524

  3. Freezing of low energy excitations in charge density wave glasses.

    Science.gov (United States)

    Staresinic, D; Zaitsev-Zotov, S V; Baklanov, N I; Biljaković, K

    2008-03-07

    Thermally stimulated discharge current measurements were performed to study slow relaxation processes in two canonical charge density wave systems K(0.3)MoO(3) and o-TaS(3). Two relaxation processes were observed and characterized in each system, corroborating the results of dielectric spectroscopy. Our results are consistent with the scenario of the glass transition on the charge density wave superstructure level. In particular, the results directly prove the previously proposed criterion of charge density wave freezing based on the interplay of charge density wave pinning by impurities and screening by free carriers. In addition, we obtained new information on distribution of relaxation parameters, as well as on nonlinear dielectric response both below and above the threshold field for charge density wave sliding.

  4. Microcraters formed in glass by projectiles of various densities

    Science.gov (United States)

    Vedder, J. F.; Mandeville, J.-C.

    1974-01-01

    An experiment was conducted investigating the effect of projectile density on the structure and size of craters in soda lime glass and fused quartz. The projectiles were spheres of polystyrene-divinylbenzene (PS-DVB), aluminum, and iron with velocities between 0.5 and 15 km/sec and diameters between 0.4 and 5 microns. The projectile densities spanned the range expected for primary and secondary particles of micrometer size at the lunar surface, and the velocities spanned the lower range of micrometeoroid velocities and the upper range of secondary projectile velocities. There are changes in crater morphology as the impact velocity increases, and the transitions occur at lower velocities for the projectiles of higher density. The sequence of morphological features of the craters found for PS-DVB impacting soda lime glass for increasing impact velocity, described in a previous work (Mandeville and Vedder, 1971), also occurs in fused quartz and in both targets with the more dense aluminum and iron projectiles. Each transition in morphology occurs at impact velocities generating a certain pressure in the target. High density projectiles require a lower velocity than low-density projectiles to generate a given shock pressure.

  5. Glass and percolation transitions in dense attractive micellar system

    Science.gov (United States)

    Mallamace, F.; Beneduci, R.; Gambadauro, P.; Lombardo, D.; Chen, S. H.

    2001-12-01

    In this work, we study a copolymer-micellar system characterized by clustering processes due to a short-range attractive interaction. This originates a percolation process and a new type of kinetic glass transition. We have studied these intriguing dynamical situations by means of an extensive set of light scattering and viscoelasticity experiments. Obtained data, in both the phenomena, are accounted for by considering in a proper way fractal clustering processes and the related scaling concepts. Near the percolation line the main role in the system structure and dynamics is played by the cluster's partial screening of hydrodynamic interaction, that behaves, on approaching the percolation threshold, dramatic effects on the rheological properties and on the density decay relaxations. The ergodic-nonergodic transition line (glass transition) is studied in terms of the intermediate scattering functions (ISF) in the frame of the mode coupling theory. The measured ISF gives evidence of a logarithmic decay on the density fluctuation followed by a power law behavior. This latter phenomenon is the signature of a high-order glass transition of the A3 type (cusp-like singularity).

  6. Glass transition near the free surface studied by synchrotron radiation

    Energy Technology Data Exchange (ETDEWEB)

    Sikorski, M.

    2008-06-15

    A comprehensive picture of the glass transition near the liquid/vapor interface of the model organic glass former dibutyl phthalate is presented in this work. Several surface-sensitive techniques using x-ray synchrotron radiation were applied to investigate the static and dynamic aspects of the formation of the glassy state from the supercooled liquid. The amorphous nature of dibutyl phthalate close to the free surface was confirmed by grazing incidence X-ray diffraction studies. Results from X-ray reflectivity measurements indicate a uniform electron density distribution close to the interface excluding the possibility of surface freezing down to 175 K. Dynamics on sub-{mu}m length-scales at the surface was studied with coherent synchrotron radiation via x-ray photon correlation spectroscopy. From the analysis of the dispersion relation of the surface modes, viscoelastic properties of the dibutyl phthalate are deduced. The Kelvin-Voigt model of viscoelastic media was found to describe well the properties of the liquid/vapor interface below room temperature. The data show that the viscosity at the interface matches the values reported for bulk dibutyl phthalate. The scaled relaxation rate at the surface agrees with the bulk data above 210 K. Upon approaching the glass transition temperature the free surface was observed to relax considerably faster close to the liquid/vapor interface than in bulk. The concept of higher relaxation rate at the free surface is also supported by the results of the quasielastic nuclear forward scattering experiment, during which dynamics on molecular length scales around the calorimetric glass transition temperature is studied. The data were analyzed using mode-coupling theory of the glass transition and the model of the liquid(glass)/vapor interface, predicting inhomogeneous dynamics near the surface. The quasielastic nuclear forward scattering data can be explained when the molecular mobility is assumed to decrease with the increasing

  7. Spin- and Pair-Density-Wave Glasses

    Directory of Open Access Journals (Sweden)

    David F. Mross

    2015-07-01

    Full Text Available Spontaneous breaking of translational symmetry, known as density-wave order, is common in nature. However, such states are strongly sensitive to impurities or other forms of frozen disorder leading to fascinating glassy phenomena. We analyze impurity effects on a particularly ubiquitous form of broken translation symmetry in solids: a spin-density wave (SDW with spatially modulated magnetic order. Related phenomena occur in pair-density-wave (PDW superconductors where the superconducting order is spatially modulated. For weak disorder, we find that the SDW or PDW order can generically give way to a SDW or PDW glass—new phases of matter with a number of striking properties, which we introduce and characterize here. In particular, they exhibit an interesting combination of conventional (symmetry-breaking and spin-glass (Edwards-Anderson order. This is reflected in the dynamic response of such a system, which—as expected for a glass—is extremely slow in certain variables, but, surprisingly, is fast in others. Our results apply to all uniaxial metallic SDW systems where the ordering vector is incommensurate with the crystalline lattice. In addition, the possibility of a PDW glass has important consequences for some recent theoretical and experimental work on La_{2−x}Ba_{x}Cu_{2}O_{4}.

  8. AR-Glass Fibre-Cement Interfacial Transition Zone

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    The microstructure of ITZ (Interfacial Transition Zone) in single glass fibre-cement was investigated by SEM (Scanning Electron Microscope), EPXM (Electron Probe X-ray Microanalyzer) and ESEM (Environmental Scanning Electron Microscope). The surface morphology of glass fibres and the hydration products in the vicinity of the interfaces were observed.Chemical element (Zr, Ca and Si) distributions over the ITZ thickness were determined by line-scanning with EPXM.The results show that a low-density transition zone existed in the vicinity of glass fibres. The shape of the fibre-cement ITZ was non-symmetrical and its thickness was variable. In the present study, the width of the zone ranged from 1-5μm.Locally, it came to 10μm.Occasionally, some hydration products with high alkalinity were embedded inside the ITZ, and attached on the glass surface,making the ITZ denser and causing local glass to corrode.The test results are helpful for the further understanding of the GRC degradation.

  9. The glass-liquid transition of water on hydrophobic surfaces.

    Science.gov (United States)

    Souda, Ryutaro

    2008-09-28

    Interactions of thin water films with surfaces of graphite and vitrified room-temperature ionic liquid [1-butyl-3-methylimidazolium hexafluorophosphate ([bmim][PF(6)])] were investigated using time-of-flight secondary ion mass spectrometry as a function of temperature and annealing time to elucidate the glass-liquid transition of water at the molecular level. Surface diffusion of water occurs at temperatures higher than 120 K, thereby forming three-dimensional clusters (a two-dimensional layer) on the [bmim][PF(6)] (graphite) surface. The hydrophobic effect of the surface decreases with increasing coverage of water; the bulklike properties evolve up to 40 ML, as evidenced by the occurrence of film dewetting at around the conventional glass transition temperature (140 K). Results also showed that aging is necessary for the water monolayer (a 40 ML water film) to dewet the graphite ([bmim][PF(6)]) surface. The occurrence of aging is explainable by the successive evolution of two distinct liquids during the glass-liquid transition: low density liquid is followed by supercooled liquid water. The water monolayer on graphite is characterized by the preferred orientation of unpaired OH groups toward the surface; this structure is arrested during the aging time despite the occurrence of surface diffusion. However, the water monolayer formed on the [bmim][PF(6)] surface agglomerates immediately after the commencement of surface diffusion. The structure of low density liquid tends to be arrested by the attractive interaction with the neighbors.

  10. Microcraters formed in glass by low density projectiles

    Science.gov (United States)

    Mandeville, J.-C.; Vedder, J. F.

    1971-01-01

    Microcraters were produced in soda-lime glass by the impact of low density projectiles of polystyrene with masses between 0.7 and 62 picograms and velocities between 2 and 14 kilometers per second. The morphology of the craters depends on the velocity and angle of incidence of the projectiles. The transitions in morphology of the craters formed by polystyrene spheres occur at higher velocities than they do for more dense projectiles. For oblique impact, the craters are elongated and shallow with the spallation threshold occuring at higher velocity. For normal incidence, the total displaced mass of the target material per unit of projectile kinetic energy increases slowly with the energy.

  11. Equivalence of glass transition and colloidal glass transition in the hard-sphere limit.

    Science.gov (United States)

    Xu, Ning; Haxton, Thomas K; Liu, Andrea J; Nagel, Sidney R

    2009-12-11

    We show that the slowing of the dynamics in simulations of several model glass-forming liquids is equivalent to the hard-sphere glass transition in the low-pressure limit. In this limit, we find universal behavior of the relaxation time by collapsing molecular-dynamics data for all systems studied onto a single curve as a function of T/p, the ratio of the temperature to the pressure. At higher pressures, there are deviations from this universal behavior that depend on the interparticle potential, implying that additional physical processes must enter into the dynamics of glass formation.

  12. Mutarotational kinetics and glass transition of lactose

    Science.gov (United States)

    Lefort, Ronan; Caron, Vincent; Willart, Jean-François; Descamps, Marc

    2006-11-01

    We report for the first time real time in situ and quantitative measurements of the mutarotation reaction of lactose in the solid state. The experiments have been performed by 13C NMR. We show that mutarotation is initiated on heating the amorphous state, and reaches chemical equilibrium close above the glass transition temperature Tg. We do not observe this transformation when starting from stable crystalline states. The final ratio of α and β anomers is 1:1, which suggests that the energy profile of the mutarotation reaction pathway in the solid state is actually different from the mechanism proposed for aqueous solution. This chemical equipartition is reached before the crystallization into the corresponding 1:1 molecular compound. These new data clearly illustrate the interrelation between the chemical molecular properties, the physical state of the material, and the relaxational dynamics of the glass.

  13. Chiral-glass transition and replica symmetry breaking of a three-dimensional heisenberg spin glass

    Science.gov (United States)

    Hukushima; Kawamura

    2000-02-01

    Extensive equilibrium Monte Carlo simulations are performed for a three-dimensional Heisenberg spin glass with the nearest-neighbor Gaussian coupling to investigate its spin-glass and chiral-glass orderings. The occurrence of a finite-temperature chiral-glass transition without the conventional spin-glass order is established. Critical exponents characterizing the transition are different from those of the standard Ising spin glass. The calculated overlap distribution suggests the appearance of a peculiar type of replica-symmetry breaking in the chiral-glass ordered state.

  14. Glass transition of ionic liquids under high pressure

    Science.gov (United States)

    Ribeiro, Mauro C. C.; Pádua, Agílio A. H.; Gomes, Margarida F. Costa

    2014-06-01

    The glass transition pressure at room temperature, pg, of six ionic liquids based on 1-alkyl-3-methylimidazolium cations and the anions [BF4]-, [PF6]-, and bis(trifluromethanesulfonyl)imide, [NTf2]-, has been obtained from the pressure dependence of the bandwidth of the ruby fluorescence line in diamond anvil cells. Molar volume, Vm(pg), has been estimated by a group contribution model (GCM) developed for the ionic liquids. A density scaling relation, TVγ, has been considered for the states Vm(pg, 295 K) and Vm(Tg, 0.1 MPa) using the simplifying condition that the viscosity at the glass transition is the same at pg at room temperature and at atmospheric pressure at Tg. Assuming a constant γ over this range of density, a reasonable agreement has been found for the γ determined herein and that of a previous density scaling analysis of ionic liquids viscosities under moderate conditions. Further support for the appropriateness of extrapolating the GCM equation of state to the GPa pressure range is provided by comparing the GCM and an equation of state previously derived in the power law density-scaling regime.

  15. Glass Transition Temperature- and Specific Volume- Composition Models for Tellurite Glasses

    Energy Technology Data Exchange (ETDEWEB)

    Riley, Brian J. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Vienna, John D. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States)

    2017-09-01

    This report provides models for predicting composition-properties for tellurite glasses, namely specific gravity and glass transition temperature. Included are the partial specific coefficients for each model, the component validity ranges, and model fit parameters.

  16. Fast Heterogeneous Relaxation Near The Glass Transition

    Science.gov (United States)

    Russina, Margarita

    2000-03-01

    More than a decade ago inelastic neutron scattering studies revealed a surprising characteristic feature in the atomic dynamics near the glass transition, which was often called the betta-process, with reference to predictions of the mode coupling theory (MCT). This process appears on the ps time scale, i.e. fast compared to the ordinary flow viscosity governed relaxation and slow compared to usual atomic vibrations, and its nature remained a puzzle over the years. Although inelastic neutron scattering is ideally suited to observe dynamics on microscopic time and length scales, experimental difficulties due to strong multiple scattering effects prevented the exploration of the spatial character of this process. By a new experimental approach to correct for these spurious contributions with a high precision, we were now able to extend the spatial domain of our observations from just about nearest neighbor atomic distances by close to an order of magnitude larger ones, which length scale includes that of the intermediate range order, which can be expected to reveal most sensitively collective, as opposed to the local, behavior. Our results in the fragile glass forming liquid Ca-K-NO3 show, that the betta-process is a first fast step of the structural relaxation, which confirms a most fundamental prediction of MCT. Furthermore, by investigating the Debye-Waller factor associated with this process, we found that its geometrical nature corresponds to quasi-rigid, correlated displacement of mobile groups of atoms, which move much faster than the ordinary flow of the bulk of the supercooled liquid. This is the first direct experimental evidence for the existence of heterogeneous fast flow processes similar to the string-flow motion recently observed in molecular dynamic simulations of model liquids close to the glass transition.

  17. Configurons: Thermodynamic Parameters and Symmetry Changes at Glass Transition

    Directory of Open Access Journals (Sweden)

    Michael I. Ojovan

    2008-09-01

    Full Text Available Thermodynamic parameters of configurons – elementary excitations resulting from broken bonds in amorphous materials – are found from viscosity-temperature relationships. Glass-liquid transition phenomena and most popular models are described along with the configuron model of glass transition. The symmetry breaking, which occurs as a change of Hausdorff dimension of bonds, is examined at glass-liquid transition. Thermal history effects in the glass-liquid transition are interpreted in terms of configuron relaxation.

  18. A density-independent rigidity transition in biological tissues

    Science.gov (United States)

    Bi, Dapeng; Lopez, J. H.; Schwarz, J. M.; Manning, M. Lisa

    2015-12-01

    Cell migration is important in many biological processes, including embryonic development, cancer metastasis and wound healing. In these tissues, a cell’s motion is often strongly constrained by its neighbours, leading to glassy dynamics. Although self-propelled particle models exhibit a density-driven glass transition, this does not explain liquid-to-solid transitions in confluent tissues, where there are no gaps between cells and therefore the density is constant. Here we demonstrate the existence of a new type of rigidity transition that occurs in the well-studied vertex model for confluent tissue monolayers at constant density. We find that the onset of rigidity is governed by a model parameter that encodes single-cell properties such as cell-cell adhesion and cortical tension, providing an explanation for liquid-to-solid transitions in confluent tissues and making testable predictions about how these transitions differ from those in particulate matter.

  19. High-density scintillating glasses for a proton imaging detector

    Science.gov (United States)

    Tillman, I. J.; Dettmann, M. A.; Herrig, V.; Thune, Z. L.; Zieser, A. J.; Michalek, S. F.; Been, M. O.; Martinez-Szewczyk, M. M.; Koster, H. J.; Wilkinson, C. J.; Kielty, M. W.; Jacobsohn, L. G.; Akgun, U.

    2017-06-01

    High-density scintillating glasses are proposed for a novel proton-imaging device that can improve the accuracy of the hadron therapy. High-density scintillating glasses are needed to build a cost effective, compact calorimeter that can be attached to a gantry. This report summarizes the study on Europium, Terbium, and Cerium-doped scintillating glasses that were developed containing heavy elements such as Lanthanum, Gadolinium, and Tungsten. The density of the samples reach up to 5.9 g/cm3, and their 300-600 nm emission overlaps perfectly with the peak cathode sensitivity of the commercial photo detectors. The developed glasses do not require any special quenching and can be poured easily, which makes them a good candidate for production in various geometries. Here, the glass making conditions, preliminary tests on optical and physical properties of these scintillating, high-density, oxide glasses developed for a novel medical imaging application are reported.

  20. The Glass Transition of Driven Molecular Materials

    Science.gov (United States)

    Descamps, M.; Willart, J. F.; Aumelas, A.

    2008-02-01

    There are many cases of practical interest where materials are maintained in nonequilibrium conditions by some external dynamical forcing: typical examples of these driven materials are provided by irradiation, grinding, extrusion…Contrary to usual phase transitions which are properly addressed by thermal equilibrium states, equilibrium and irreversible thermodynamics, no such general framework is available for driven systems. The purpose of this paper is to show some examples of phase transformations in driven molecular materials. These materials are considered because they are extremely sensitive to external disturbances and are generally very good glass formers. This allows investigating more easily a broad range of the parameters which possibly influence the nature of the end product. We will examine mainly the effect of grinding. Contrary to other materials, metals or minerals, systematic investigations of transformations induced by grinding of molecular materials have not yet been done despite the practical and fundamental interests of such investigations in pharmaceutical and agro-chemical science. We will address several modes of interconversions between crystalline and glassy states of the same compound. We will further discuss specific processing effects on the physical state of the glass itself. It will be shown from these investigations that rationalization and possibilities of prediction are emerging. The use of effective temperature concepts to describe the end product of milling will be discussed. These findings may be of general concern for driven materials of any chemical nature.

  1. Investigation of the atypical glass transition and recrystallization behavior of amorphous prazosin salts.

    Science.gov (United States)

    Kumar, Lokesh; Popat, Dharmesh; Bansal, Arvind K

    2011-08-25

    This manuscript studied the effect of counterion on the glass transition and recrystallization behavior of amorphous salts of prazosin. Three amorphous salts of prazosin, namely, prazosin hydrochloride, prazosin mesylate and prazosin tosylate were prepared by spray drying, and characterized by optical-polarized microscopy, differential scanning calorimetry and powder X-ray diffraction. Modulated differential scanning calorimetry was used to determine the glass transition and recrystallization temperature of amorphous salts. Glass transition of amorphous salts followed the order: prazosin mesylate > prazosin tosylate ~ prazosin hydrochloride. Amorphous prazosin mesylate and prazosin tosylate showed glass transition, followed by recrystallization. In contrast, amorphous prazosin hydrochloride showed glass transition and recrystallization simultaneously. Density Functional Theory, however, suggested the expected order of glass transition as prazosin hydrochloride > prazosin mesylate > prazosin tosylate. The counterintuitive observation of amorphous prazosin hydrochloride having lower glass transition was explained in terms of its lower activation energy (206.1 kJ/mol) for molecular mobility at Tg, compared to that for amorphous prazosin mesylate (448.5 kJ/mol) and prazosin tosylate (490.7 kJ/mol), and was further correlated to a difference in hydrogen bonding strength of the amorphous and the corresponding recrystallized salts. This study has implications in selection of an optimal amorphous salt form for pharmaceutical development.

  2. Predicting the glass transition temperature of bioactive glasses from their molecular chemical composition.

    Science.gov (United States)

    Hill, Robert G; Brauer, Delia S

    2011-10-01

    A recently published paper (M.D. O'Donnell, Acta Biomaterialia 7 (2011) 2264-2269) suggests that it is possible to correlate the glass transition temperature (T(g)) of bioactive glasses with their molar composition, based on iterative least-squares fitting of published T(g) data. However, we show that the glass structure is an important parameter in determining T(g). Phase separation, local structural effects and components (intermediate oxides) which can switch their structural role in the glass network need to be taken into consideration, as they are likely to influence the glass transition temperature of bioactive glasses. Although the model suggested by O'Donnell works reasonably well for glasses within the composition range presented, it is oversimplified and fails for glasses outside certain compositional boundaries.

  3. Study of structural and optical properties of lead borate glasses containing transition metal ion

    Science.gov (United States)

    Sanjay, Kaushik, A.; Kishore, N.; Agarwal, A.; Pal, I.; Dhar, R.

    2012-06-01

    Glasses with compositions xFe2O3.(40-x)PbO.60B2O3: V2O5 (2 mol%) have been prepared by the standard melt-quenching technique. Various properties such as glass transition temperature, density, IR spectra and optical band gap energy have been studied. The structural changes in these glasses have been monitored by IR spectroscopy. The values of optical band gap for indirect allowed and indirect forbidden transitions have been determined using available theories. The Urbach's energy is used to characterize the degree of disorder in amorphous solids.

  4. Comparing the density of states of binary Lennard-Jones glasses in bulk and film

    Science.gov (United States)

    Ghosh, Jayeeta; Faller, Roland

    2008-03-01

    We used Wang-Landau density of states Monte Carlo to study a binary Lennard-Jones glass-forming mixture in bulk and films between noninteracting walls. Thermodynamic properties are calculated using two different ensembles and film data are compared with the bulk. Bulk properties are in good agreement with previous simulations. We confirm the formation of a glass using various properties, e.g., energy, heat capacity, and pressure with temperature. We find a change in slope in the energy per particle and pressure as a function of temperature. We do not find any defined crystal structure. A higher glass transition temperature is found for the film.

  5. Stochastic qualifier of gel and glass transitions in laponite suspensions

    Science.gov (United States)

    Shayeganfar, F.; Jabbari-Farouji, S.; Movahed, M. Sadegh; Jafari, G. R.; Tabar, M. Reza Rahimi

    2010-06-01

    The existence of the important similarities between gelation and glass transition makes it hard to distinguish between the two types of nonergodic states experimentally. Here, we report on a stochastic analysis of the scattered light intensity through a colloidal particles suspension during the gel and glass formation. In this analysis, we exploit the methods developed for complex hierarchical systems, such as turbulence. Using the multiplicative log-normal cascade models, we provide a criterion to distinguish gels from glasses.

  6. Citrate increases glass transition temperature of vitrified sucrose preparations

    NARCIS (Netherlands)

    Kets, E.P.W.; Lipelaar, P.J.; Hoekstra, F.A.; Vromans, H.

    2004-01-01

    The aim of this study was to investigate the effect of sodium citrate on the properties of dried amorphous sucrose glasses. Addition of sodium citrate to a sucrose solution followed by freeze-drying or convective drying resulted in a glass transition temperature (T-g) that was higher than the well-s

  7. An Overview of the Glass Transition Temperature of Synthetic Polymers.

    Science.gov (United States)

    Beck, Keith R.; And Others

    1984-01-01

    Presents an overview of the glass-to-rubber transition, what it is, why it is important, and the major factors that influence it. Indicates that this information should be incorporated into chemistry curricula. (JN)

  8. Glass transition and thermal expansivity of polystyrene thin films

    Energy Technology Data Exchange (ETDEWEB)

    Inoue, R. [Institute for Chemical Research, Kyoto University, Uji, Kyoto-fu 611-0011 (Japan); Kanaya, T. [Institute for Chemical Research, Kyoto University, Uji, Kyoto-fu 611-0011 (Japan)]. E-mail: kanaya@scl.kyoto-u.ac.jp; Miyazaki, T. [Nitto Denko Corporation, 1-1-2 Shimohozumi, Ibaraki, Osaka-fu 567-8680 (Japan); Nishida, K. [Institute for Chemical Research, Kyoto University, Uji, Kyoto-fu 611-0011 (Japan); Tsukushi, I. [Chiba Institute of Technology, Narashino, Chiba-ken 275-0023 (Japan); Shibata, K. [Japan Atomic Energy Research Institute, Tokai, Ibaraki-ken 319-1195 (Japan)

    2006-12-20

    We have studied glass transition temperature and thermal expansivity of polystyrene thin films supported on silicon substrate using X-ray reflectivity and inelastic neutron scattering techniques. In annealing experiments, we have found that the reported apparent negative expansivity of polymer thin films is caused by unrelaxed structure due to insufficient annealing. Using well-annealed films, we have evaluated glass transition temperature T {sub g} and thermal expansivity as a function of film thickness. The glass transition temperature decreases with film thickness and is constant below about 10 nm, suggesting the surface glass transition temperature of 355 K, which is lower than that in bulk. We have also found that the thermal expansivity in the glassy state decreases with film thickness even after annealing. The decrease has been attributed to hardening of harmonic force constant arising from chain confinement in a thin film. This idea has been confirmed in the inelastic neutron scattering measurements.

  9. Glass transition phenomena applied to powdered amorphous food carbohydrates

    OpenAIRE

    Ronkart, Sebastien N; Blecker, Christophe; Deroanne, Claude; Paquot, Michel

    2009-01-01

    Glass transition phenomena applied to powdered amorphous food carbohydrates. During these last fifteen years, some food technologists and scientists have become aware of the importance of the glass transition, a thermal property of glassy or amorphous material, in food preparation processes. Recent studies have successfully correlated this fundamental notion to technofunctional changes within the powder. The aim of this paper is to present in a non exhaustive manner the relationship between g...

  10. Theoretical Insights from Facile Microsecond Simulation of the Glass Transition

    Science.gov (United States)

    Hung, Jui-Hsiang; Patra, Tarak; Simmons, David

    Despite more than half a century of research, the fundamental nature of the glass transition remains one of the major open questions in polymer science and condensed matter physics. Molecular dynamics simulations have provided key insights into this problem, but their ability to firmly establish the underlying nature of glass formation have been limited by the extreme computational difficulty of directly probing the deeply supercooled regime most relevant to this process. Here we describe a new protocol for simulation of the glass transition enabling facile access to in-equilibrium segmental relaxation times approaching and exceeding one microsecond - well into the deeply supercooled regime of most glass-forming liquids. Coupled with a well-validated strategy for extrapolation to experimental timescales, this approach provides vastly improved prediction of experimental glass transition temperatures. Here we combine data acquired through this protocol for the deeply supercooled regime of polymeric, inorganic, organic, and metallic glass formers to robustly test several theories of glass formation and identify microscopic phenomenological features shared across all classes of glass-forming liquid in the deeply supercooled regime. We acknowledge the W. M. Keck Foundation for financial support of this research.

  11. Phase transitions at finite density

    CERN Document Server

    Friman, Bengt

    2012-01-01

    I discuss the analytic structure of thermodynamic quantities for complex values of thermodynamic variables within Landau theory. In particular, the singularities connected with phase transitions of second order, first order and cross over types are examined. A conformal mapping is introduced, which may be used to explore the thermodynamics of strongly interacting matter at finite values of the baryon chemical potential $\\mu$ starting from lattice QCD results at $\\mu^{2}\\leq 0$. This method allows us to improve the convergence of a Taylor expansion about $\\mu=0$ and to enhance the sensitivity to physical singularities in the complex $\\mu$ plane. The technique is illustrated by an application to a second-order transition in a chiral effective model.

  12. Kinetic criteria of glass formation and the pressure dependence of the glass transition temperature.

    Science.gov (United States)

    Schmelzer, Jürn W P

    2012-02-21

    An overview on different attempts of formulation of kinetic criteria of glass formation is given. It is analyzed which of the characteristic time scales-time of observation, time of relaxation, and time of change of external parameters-have to be employed to appropriately develop such criteria. Based on this analysis, a general model-independent kinetic criterion for glass formation is formulated. As a first consequence, it is shown that it is not-as often claimed-the Deborah number which governs glass formation. Based on this general kinetic criterion for glass formation, general expressions for the dependence of the glass transition temperature on pressure (and vice versa) are obtained being essentially ratios of the partial derivatives of the appropriate relaxation times with respect to pressure and temperature, respectively. Employing, as examples, further two different (free volume and entropy based) models for the description of viscous flow and relaxation, respectively, relations similar but, in general, not identical to the classical Ehrenfest relations describing second-order equilibrium phase transitions are obtained. In this way, it can be explained why one of the Ehrenfest's relations is usually fulfilled in glass transition and the other not and why the Prigogine-Defay ratio in glass transition is not equal to one as this is the case with Ehrenfest's ratio in second-order equilibrium phase transitions. © 2012 American Institute of Physics

  13. From Gelation and Glass Transition of Colloidal Systems to Polymers

    Science.gov (United States)

    Han, Charles; Yuan, Guangcui; Cheng, He

    Charles C. Han, Guangcui Yuan and He Cheng Joint Laboratory of Polymer Science and Materials, ICCAS, Beijing, China and Institute for Advanced Study, Shenzhen University, Shenzhen, China Aggregation and gelation behavior of mixed suspensions of polystyrene microspheres and poly(N-isopropylacrylamide) microgels have been studied. In dilute microsphere suspensions, with increasing concentration of microgel (MG), microspheres (MS) first aggregated with each other through the bridging of the microgels, then dispersed individually when saturated adsorption was achieved, and finally depletion clusters formed at even higher concentrations of microgel. In concentrated microsphere suspensions, with saturated MG adsorption, a state transition from attractive glass to repulsive glass can be observed. This type of system can be viewed as a molecular model system which has a long range repulsive interaction potential and a short range attractive potential. A comparison between the glass transition of the colloidal systems and the glass transition of polymeric systems can be made.

  14. Transit Scratchitti Removal and Glass Resurfacing by Controlled Fire Polishing

    Science.gov (United States)

    Jun, Seongchan; Hong, Shane Y.

    Scratchitti vandalism, a new type of graffiti vandalism, in public transits systems and city neighborhood is a serious problem. To solve this problem, an innovative approach was developed-controlled fire polishing, which incorporates a technique of localized softening and surface tension. Intensive heat is positioned near to the scratch marks on the glass panel. The heat melts a thin layer of glass into liquid, changing the glass’s viscosity to a formable state. The glass is melted to a level close to the depth of the scratch, and allowed to cool down naturally. During the cooling process, the surface tension of the melted glass will even out the scratching indent. After cooling, the glass will be as even and smooth as it was originally. The process will enable the reuse of the damaged window/door and eliminate the otherwise waste by replacement new glass.

  15. Brittle to ductile transition in densified silica glass.

    Science.gov (United States)

    Yuan, Fenglin; Huang, Liping

    2014-05-22

    Current understanding of the brittleness of glass is limited by our poor understanding and control over the microscopic structure. In this study, we used a pressure quenching route to tune the structure of silica glass in a controllable manner, and observed a systematic increase in ductility in samples quenched under increasingly higher pressure. The brittle to ductile transition in densified silica glass can be attributed to the critical role of 5-fold Si coordination defects (bonded to 5 O neighbors) in facilitating shear deformation and in dissipating energy by converting back to the 4-fold coordination state during deformation. As an archetypal glass former and one of the most abundant minerals in the Earth's crest, a fundamental understanding of the microscopic structure underpinning the ductility of silica glass will not only pave the way toward rational design of strong glasses, but also advance our knowledge of the geological processes in the Earth's interior.

  16. Spin-glass transition of the three-dimensional Heisenberg spin glass.

    Science.gov (United States)

    Campos, I; Cotallo-Aban, M; Martin-Mayor, V; Perez-Gaviro, S; Tarancon, A

    2006-11-24

    It is shown, by means of Monte Carlo simulation and finite size scaling analysis, that the Heisenberg spin glass undergoes a finite-temperature phase transition in three dimensions. There is a single critical temperature, at which both a spin glass and a chiral glass ordering develop. The Monte Carlo algorithm, adapted from lattice gauge theory simulations, makes it possible to thermalize lattices of size L = 32, larger than in any previous spin-glass simulation in three dimensions. High accuracy is reached thanks to the use of the Marenostrum supercomputer. The large range of system sizes studied allows us to consider scaling corrections.

  17. Models of agglomeration and glass transition

    CERN Document Server

    Kerner, Richard

    2007-01-01

    This book is for any physicist interested in new vistas in the domain of non-crystalline condensed matter, aperiodic and quasi-crystalline networks and especially glass physics and chemistry. Students with an elementary background in thermodynamics and statistical physics will find the book accessible. The physics of glasses is extensively covered, focusing on their thermal and mechanical properties, as well as various models leading to the formation of the glassy states of matter from overcooled liquids. The models of agglomeration and growth are also applied to describe the formation of quasicrystals, fullerenes and, in biology, to describe virus assembly pathways.

  18. On relaxation nature of glass transition in amorphous materials

    Science.gov (United States)

    Sanditov, Damba S.; Ojovan, Michael I.

    2017-10-01

    A short review on relaxation theories of glass transition is presented. The main attention is paid to modern aspects of the glass transition equation qτg = C, suggested by Bartenev in 1951 (q - cooling rate of the melt, τg - structural relaxation time at the glass transition temperature Tg). This equation represents a criterion of structural relaxation at transition from liquid to glass at T = Tg (analogous to the condition of mechanical relaxation ωτ = 1, where the maximum of mechanical loss is observed). The empirical parameter С = δTg has the meaning of temperature range δTg that characterizes the liquid-glass transition. Different approaches of δTg calculation are reviewed. In the framework of the model of delocalized atoms a modified kinetic criterion of glass transition is proposed (q/Tg)τg = Cg, where Cg ≅ 7·10-3 is a practically universal dimensionless constant. It depends on fraction of fluctuation volume fg, which is frozen at the glass transition temperature Cg = fg/ln(1/fg). The value of fg is approximately constant fg ≅ 0.025. At Tg the process of atom delocalization, i.e. its displacement from the equilibrium position, is frozen. In silicate glasses atom delocalization is reduced to critical displacement of bridge oxygen atom in Si-O-Si bridge necessary to switch a valence bond according to Muller and Nemilov. An equation is derived for the temperature dependence of viscosity of glass-forming liquids in the wide temperature range, including the liquid-glass transition and the region of higher temperatures. Notion of (bridge) atom delocalization is developed, which is related to necessity of local low activation deformation of structural network for realization of elementary act of viscous flow - activated switch of a valence (bridge) bond. Without atom delocalization (;trigger mechanism;) a switch of the valence bond is impossible and, consequently, the viscous flow. Thus the freezing of atom delocalization process at low temperatures

  19. Frustration in Vicinity of Transition Point of Ising Spin Glasses

    Science.gov (United States)

    Miyazaki, Ryoji

    2013-09-01

    We conjecture the existence of a relationship between frustration and the transition point at zero temperature of Ising spin glasses. The relation reveals that, in several Ising spin glass models, the concentration of ferromagnetic bonds is close to the critical concentration at zero temperature when the output of a function about frustration is equal to unity. The function is the derivative of the average number of frustrated plaquettes with respect to the average number of antiferromagnetic bonds. This relation is conjectured in Ising spin glasses with binary couplings on two-dimensional lattices, hierarchical lattices, and three-body Ising spin glasses with binary couplings on two-dimensional lattices. In addition, the same argument in the Sherrington--Kirkpatrick model yields a point that is identical to the replica-symmetric solution of the transition point at zero temperature.

  20. Kinetics of Glass Transition and Crystallization in Carbon Nanotube Reinforced Mg-Cu-Gd Bulk Metallic Glass

    Institute of Scientific and Technical Information of China (English)

    2006-01-01

    Mg65Cu25Gd10 bulk metallic glass and its carbon nanotube reinforced composite were prepared. Differential scanning calorimeter (DSC) was used to investigate the kinetics of glass transition and crystallization processes. The influence of CNTs addition to the glass matrix on the glass transition and crystallization kinetics was studied. It is shown that the kinetic effect on glass transition and crystallization are preserved for both the monothetic glass and its glass composite.Adding CNTs in to the glass matrix reduces the influence of the heating rate on the crystallization process. In addition, the CNTs increase the energetic barrier for the glass transition. This results in the decrease of GFA. The mechanism of the GFA decrease was also discussed.

  1. Glass transition of repulsive charged rods (fd-viruses).

    Science.gov (United States)

    Kang, Kyongok

    2014-05-14

    It has recently been shown that suspensions of long and thin charged fibrous viruses (fd) form a glass at low ionic strengths. The corresponding thick electric double layers give rise to long-ranged repulsive electrostatic interactions, which lead to caging and structural arrest at concentrations far above the isotropic-nematic coexistence region. Structural arrest and freezing of the orientational texture are found to occur at the same concentration. In addition, various types of orientational textures are equilibrated below the glass transition concentration, ranging from a chiral-nematic texture with a large pitch (of about 100 μm), an X-pattern, and a tightly packed domain texture, consisting of helical domains with a relatively small pitch (of about 10 μm) and twisted boundaries. The dynamics of both particles as well as the texture are discussed, below and above the glass transition. Dynamic light scattering correlation functions exhibit two dynamical modes, where the slow mode is attributed to the elasticity of helical domains. On approach of the glass-transition concentration, the slow mode increases in amplitude, while as the amplitudes of the fast and slow mode become equal at the glass transition. Finally, interesting features of the "transient" behaviors of charged fd-rod glass are shown as the initial caging due to structural arrest, the propagation of flow originating from stress release, and the transition to the final metastable glass state. In addition to the intensity correlation function, power spectra are presented as a function of the waiting time, at the zero-frequency limit that may access to the thermal anomalities in a charged system.

  2. A NEURAL NETWORK STUDY ON GLASS TRANSITION TEMPERATURE OF POLYMERS

    Institute of Scientific and Technical Information of China (English)

    Lin-xi Zhanga; De-lu Zhao; You-xing Huang

    2002-01-01

    In this paper, an artificial neural network model is adopted to study the glass transition temperature of polymers. In our artificial neural networks, the input nodes are the characteristic ratio C∞, the average molecular weight M, between entanglement points and the molecular weight Mmon of repeating unit. The output node is the glass transition temperature Tg,and the number of the hidden layer is 6. We found that the artificial neural network simulations are accurate in predicting the outcome for polymers for which it is not trained. The maximum relative error for predicting of the glass transition temperature is 3.47%, and the overall average error is only 2.27%. Artificial neural networks may provide some new ideas to investigate other properties of the polymers.

  3. Glass transition and heavy oil dynamics at low temperature

    Energy Technology Data Exchange (ETDEWEB)

    Abivin, P.; Indo, K.; Cheng, Y.; Freed, D.; Taylor, S. D. [Schlumberger (Canada)], email: PAbivin@slb.com

    2011-07-01

    In the oil industry, the viscosity of crude oils is a key factor as it affects market value, field developments and the design of production strategies. In heavy oils, a glass transition occurs and previous work related this to oil's temperature-viscosity behavior. This study aimed at better characterizing heavy oil dynamics and the temperature dependency of viscosity. Experiments were conducted with differential scanning calorimetry and shear rate sweeps on heavy oils from Asia, South America and North America over a wide range of temperatures to measure their viscosities and characterize their glass transition. The glass transition was observed at around 210K and results showed that the Arrhenius model does not fit the experimental data at low temperatures but the WLF model does. This research provided a better understanding of heavy oil dynamics but further work is required to explain the viscosity-temperature behavior of heavy oils at low temperatures.

  4. Non-monotonic effect of confinement on the glass transition

    Science.gov (United States)

    Varnik, Fathollah; Franosch, Thomas

    2016-04-01

    The relaxation dynamics of glass forming liquids and their structure are influenced in the vicinity of confining walls. This effect has mostly been observed to be a monotonic function of the slit width. Recently, a qualitatively new behaviour has been uncovered by Mittal and coworkers, who reported that the single particle dynamics in a hard-sphere fluid confined in a planar slit varies in a non-monotonic way as the slit width is decreased from five to roughly two particle diametres (Mittal et al 2008 Phys. Rev. Lett. 100 145901). In view of the great potential of this effect for applications in those fields of science and industry, where liquids occur under strong confinement (e.g. nano-technology), the number of researchers studying various aspects and consequences of this non-monotonic behaviour has been rapidly growing. This review aims at providing an overview of the research activity in this newly emerging field. We first briefly discuss how competing mechanisms such as packing effects and short-range attraction may lead to a non-monotonic glass transition scenario in the bulk. We then analyse confinement effects on the dynamics of fluids using a thermodynamic route which relates the single particle dynamics to the excess entropy. Moreover, relating the diffusive dynamics to the Widom’s insertion probability, the oscillations of the local dynamics with density at moderate densities are fairly well described. At high densities belonging to the supercooled regime, however, this approach breaks down signaling the onset of strongly collective effects. Indeed, confinement introduces a new length scale which in the limit of high densities and small pore sizes competes with the short-range local order of the fluid. This gives rise to a non-monotonic dependence of the packing structure on confinement, with a corresponding effect on the dynamics of structural relaxation. This non-monotonic effect occurs also in the case of a cone-plate type channel, where the degree

  5. Fluorinated epoxy resins with high glass transition temperatures

    Science.gov (United States)

    Griffith, James R.

    1991-01-01

    Easily processed liquid resins of low dielectric constants and high glass transition temperatures are useful for the manufacture of certain composite electronic boards. That combination of properties is difficult to acquire when dielectric constants are below 2.5, glass transition temperatures are above 200 C and processability is of conventional practicality. A recently issued patent (US 4,981,941 of 1 Jan. 1991) teaches practical materials and is the culmination of 23 years of research and effort and 15 patents owned by the Navy in the field of fluorinated resins of several classes. In addition to high fluorine content, practical utility was emphasized.

  6. Review: Pressure-Induced Densification of Oxide Glasses at the Glass Transition

    Science.gov (United States)

    Kapoor, Saurabh; Wondraczek, Lothar; Smedskjaer, Morten M.

    2017-02-01

    Densification of oxide glasses at the glass transition offers a novel route to develop bulk glasses with tailored properties for emerging applications. Such densification can be achieved in the technologically relevant pressure regime of up to 1GPa. However, the present understanding of the composition-structure-property relationships governing these glasses is limited, with key questions, e.g., related to densification mechanism, remaining largely unanswered. Recent advances in structural characterization tools and high-pressure apparatuses have prompted new research efforts. Here, we review this recent progress and the insights gained in the understanding of the influence of isostatic compression at elevated temperature (so-called hot compression) on the composition-structure-property relationships of oxide glasses. We focus on compression at temperatures at or around the glass transition temperature (Tg), with relevant comparisons made to glasses prepared by pressure quenching and cold compression. We show that permanent densification at 1 GPa sets-in at temperatures above 0.7Tg and the degree of densification increases with increasing compression temperature and time, until attaining an approximately constant value for temperatures above Tg. For glasses compressed at the same temperature/pressure conditions, we demonstrate direct relations between the degree of volume densification and the pressure-induced change in micro-mechanical properties such as hardness, elastic moduli, and extent of the indentation size effect across a variety of glass families. Furthermore, we summarize the results on relaxation behavior of hot compressed glasses. All the pressure-induced changes in the structure and properties exhibit strong composition dependence. The experimental results highlight new opportunities for future investigation and identify research challenges that need to be overcome to advance the field.

  7. Structural, optical and glass transition studies on Nd{sup 3+}-doped lead bismuth borate glasses

    Energy Technology Data Exchange (ETDEWEB)

    Karthikeyan, B.; Mohan, S

    2003-07-01

    Nd{sup 3+}-doped lead bismuth borate (PbO-Bi{sub 2}O{sub 3}-B{sub 2}O{sub 3}) glasses were prepared with different concentrations of Nd{sup 3+}. The structural studies were done through FTIR spectral analysis. The glass transition studies were done through differential scanning calorimetry. The optical analysis was done by using Judd-Ofelt theory. The structural study reveals that the glass has [BiO{sub 3}], BO{sub 4}, BO{sub 3} and PbO{sub 4} units as the local structures.

  8. Glass transition in binary eutectic systems: best glass-forming composition.

    Science.gov (United States)

    Wang, Li-Min; Li, Zijing; Chen, Zeming; Zhao, Yue; Liu, Riping; Tian, Yongjun

    2010-09-23

    The glass transition and glass-forming ability in a binary eutectic system of methyl o-toluate (MOT) versus methyl p-toluate (MPT) are studied across the whole composition range. The phase diagram is constructed to explore the best glass-forming composition as the characteristic temperatures of the glass transition, crystallization, eutectic, and liquidus are determined. The best vitrification region is found to locate between the eutectic and the midpoint compositions of the eutectic line, indicating a remarkable deviation from the eutectic composition. The compilation of various simple binary eutectic systems covering inorganic, metallic, ionic, and molecular glass-forming liquids reproduces the rule. Kinetics and thermodynamics in binary systems are investigated to associate with the rule. The composition dependence of the structural relaxation time and the kinetic fragility are presented with dielectric measurements. It is found that whereas mixing of binary miscible liquids kinetically favors glass formation, thermodynamic contribution to the deviation of the best glass-forming composition from eutectics is implied.

  9. Liquid-Liquid Phase Transition and Glass Transition in a Monoatomic Model System

    Directory of Open Access Journals (Sweden)

    Nicolas Giovambattista

    2010-12-01

    Full Text Available We review our recent study on the polyamorphism of the liquid and glass states in a monatomic system, a two-scale spherical-symmetric Jagla model with both attractive and repulsive interactions. This potential with a parametrization for which crystallization can be avoided and both the glass transition and the liquid-liquid phase transition are clearly separated, displays water-like anomalies as well as polyamorphism in both liquid and glassy states, providing a unique opportunity to study the interplay between the liquid-liquid phase transition and the glass transition. Our study on a simple model may be useful in understanding recent studies of polyamorphism in metallic glasses.

  10. Thermal expansion accompanying the glass-liquid transition and crystallization

    Directory of Open Access Journals (Sweden)

    M. Q. Jiang

    2015-12-01

    Full Text Available We report the linear thermal expansion behaviors of a Zr-based (Vitreloy 1 bulk metallic glass in its as-cast, annealed and crystallized states. Accompanying the glass-liquid transition, the as-cast Vitreloy 1 shows a continuous decrease in the thermal expansivity, whereas the annealed glass shows a sudden increase. The crystallized Vitreloy 1 exhibits an almost unchanged thermal expansivity prior to its melting. Furthermore, it is demonstrated that the nucleation of crystalline phases can induce a significant thermal shrinkage of the supercooled liquid, but with the growth of these nuclei, the thermal expansion again dominates. These results are explained in the framework of the potential energy landscape, advocating that the configurational and vibrational contributions to the thermal expansion of the glass depend on both, structure and temperature.

  11. Electrical Resistance Measurement of Glass Transition and Crystallization Characteristics of Zr-Al-Cu-Ni Metallic Glasses

    Institute of Scientific and Technical Information of China (English)

    2002-01-01

    In this paper, glass transition and thermal stability of the Zr-Al-Cu-Ni metallic glasses were investigated by using electrical resistance measurement (ERM), DSC and X-ray diffraction techniques. The experimental results show that the ERM is capable of detecting the glass transition of the amorphous alloys and can help to distinguish the crystallization products of the Zr-Al-Cu-Ni metallic glasses owing to the difference of the electrical resistivity between the precipitation phases.

  12. Understanding the glass transition in GeSbTe materials

    Science.gov (United States)

    Martyna, Glenn

    2010-03-01

    Moore's law demands the continual reduction in size of the components of computers. One future direction for memory technology involves the use of phase change materials which can be switched by pulsed electrically heating from a conducting crystalline phase to an insulating amorphous phase. These materials are typically alloys of Germanium, Antimony and Tellurium (GST). In order to form multi-state bits, it is necessary to arrest the glass transition via varying annealing time such that differences in resistivity can be measured based. As might be expected, this process is hinder by ``creep'' of the glass towards higher resistance states after the quench is halted. In this lecture, simulation studies are employed to study the glass transition from the crystalline state and discern the mechanism for the gap opening. The nature of mid gaps states found from the simulated quenches gives insight into the mechanism of the creep and suggests ways in which the phenomena can be arrested.

  13. Polymer glass transitions switch electron transfer in individual molecules

    NARCIS (Netherlands)

    Siekierzycka, J.R.; Hippius, C.; Würthner, F.; Williams, R.M.; Brouwer, A.M.

    2010-01-01

    Essentially complete photoinduced electron transfer quenching of the fluorescence of a perylene−calixarene compound occurs in poly(methyl acrylate) and poly(vinyl acetate) above their glass transition temperatures (T-g), but the fluorescence is completely recovered upon cooling the polymer matrix to

  14. Predictions of Glass Transition Temperature for Hydrogen Bonding Biomaterials

    NARCIS (Netherlands)

    Sman, van der R.G.M.

    2013-01-01

    We show that the glass transition of a multitude of mixtures containing hydrogen bonding materials correlates strongly with the effective number of hydroxyl groups per molecule, which are available for intermolecular hydrogen bonding. This correlation is in compliance with the topological constraint

  15. Depression of Glass Transition Temperatures of Polymer Networks by Diluents

    NARCIS (Netherlands)

    Brinke, Gerrit ten; Karasz, Frank E.; Ellis, Thomas S.

    1983-01-01

    A classical thermodynamic theory is used to derive expressions for the depression of the glass transition temperature Tg of a polymer network by a diluent. The enhanced sensitivity of Tg in cross-linked systems to small amounts of diluent is explained. Predictions of the theory are in satisfactory a

  16. Inward Cationic Diffusion and Percolation Transition in Glass-Ceramics

    DEFF Research Database (Denmark)

    Smedsklaer, Morten Mattrup; Yue, Yuanzheng; Mørup, Steen

    2010-01-01

    of crystallization. Below the critical value, the diffusion extent decreases only slightly with the degree of crystallization. No cationic diffusion is observed in the fully crystalline materials. The critical value might be associated with a percolation transition from an interconnected to a disconnected glass...

  17. Glass-to-cryogenic-liquid transitions in aqueous solutions suggested by crack healing.

    Science.gov (United States)

    Kim, Chae Un; Tate, Mark W; Gruner, Sol M

    2015-09-22

    Observation of theorized glass-to-liquid transitions between low-density amorphous (LDA) and high-density amorphous (HDA) water states had been stymied by rapid crystallization below the homogeneous water nucleation temperature (∼235 K at 0.1 MPa). We report optical and X-ray observations suggestive of glass-to-liquid transitions in these states. Crack healing, indicative of liquid, occurs when LDA ice transforms to cubic ice at 160 K, and when HDA ice transforms to the LDA state at temperatures as low as 120 K. X-ray diffraction study of the HDA to LDA transition clearly shows the characteristics of a first-order transition. Study of the glass-to-liquid transitions in nanoconfined aqueous solutions shows them to be independent of the solute concentrations, suggesting that they represent an intrinsic property of water. These findings support theories that LDA and HDA ice are thermodynamically distinct and that they are continuously connected to two different liquid states of water.

  18. Polaronic Transport in Phosphate Glasses Containing Transition Metal Ions

    Science.gov (United States)

    Henderson, Mark

    The goal of this dissertation is to characterize the basic transport properties of phosphate glasses containing various amounts of TIs and to identify and explain any electronic phase transitions which may occur. The P2 O5-V2O5-WO3 (PVW) glass system will be analyzed to find the effect of TI concentration on conduction. In addition, the effect of the relative concentrations of network forming ions (SiO2 and P2O5) on transport will be studied in the P2O5-SiO2-Fe2O 3 (PSF) system. Also presented is a numerical study on a tight-binding model adapted for the purposes of modelling Gaussian traps, mimicking TI's, which are arranged in an extended network. The results of this project will contribute to the development of fundamental theories on the electronic transport in glasses containing mixtures of transition oxides as well as those containing multiple network formers without discernible phase separation. The present study on the PVW follows up on previous investigation into the effect on mixed transition ions in oxide glasses. Past research has focused on glasses containing transition metal ions from the 3d row. The inclusion of tungsten, a 5d transition metal, adds a layer of complexity through the mismatch of the energies of the orbitals contributing to localized states. The data have indicated that a transition reminiscent of a metal-insulator transition (MIT) occurs in this system as the concentration of tungsten increases. As opposed to some other MIT-like transitions found in phosphate glass systems, there seems to be no polaron to bipolaron conversion. Instead, the individual localization parameter for tungsten noticeably decreases dramatically at the transition point as well as the adiabaticity. Another distinctive feature of this project is the study of the PSF system, which contains two true network formers, phosphorous pentoxide (P2O 5) and silicon dioxide (SiO2). It is not usually possible to do a reliable investigation of the conduction properties of

  19. Molecular Dynamics Simulations of a Pressure-induced Glass Transition

    CERN Document Server

    Shumway, S L; Jonsson, H; Shumway, Shelly L.; Clarke, Andrew S.

    1994-01-01

    We simulate the compression of a two-component Lennard-Jones liquid at a variety of constant temperatures using a molecular dynamics algorithm in an isobaric-isothermal ensemble. The viscosity of the liquid increases with pressure, undergoing a broadened transition into a structurally arrested, amorphous state. This transition, like the more familiar one induced by cooling, is correlated with a significant increase in icosahedral ordering. In fact, the structure of the final state, as measured by an analysis of the bonding, is essentially the same in the glassy, frozen state whether produced by squeezing or by cooling under pressure. We have computed an effective hard-sphere packing fraction at the transition, defining the transition pressure or temperature by a cutoff in the diffusion constant, analogous to the traditional laboratory definition of the glass transition by an arbitrary, low cutoff in viscosity. The packing fraction at this transition point is not constant, but is consistently higher for runs c...

  20. The nature of the colloidal 'glass' transition.

    Science.gov (United States)

    Dawson, Kenneth A; Lawlor, A; DeGregorio, Paolo; McCullagh, Gavin D; Zaccarelli, Emanuela; Foffi, Giuseppe; Tartaglia, Piero

    2003-01-01

    The dynamically arrested state of matter is discussed in the context of athermal systems, such as the hard sphere colloidal arrest. We believe that the singular dynamical behaviour near arrest expressed, for example, in how the diffusion constant vanishes may be 'universal', in a sense to be discussed in the paper. Based on this we argue the merits of studying the problem with simple lattice models. This, by analogy with the the critical point of the Ising model, should lead us to clarify the questions, and begin the program of establishing the degree of universality to be expected. We deal only with 'ideal' athermal dynamical arrest transitions, such as those found for hard sphere systems. However, it is argued that dynamically available volume (DAV) is the relevant order parameter of the transition, and that universal mechanisms may be well expressed in terms of DAV. For simple lattice models we give examples of simple laws that emerge near the dynamical arrest, emphasising the idea of a near-ideal gas of 'holes', interacting to give the power law diffusion constant scaling near the arrest. We also seek to open the discussion of the possibility of an underlying weak coupling theory of the dynamical arrest transition, based on DAV.

  1. Structural relaxation and thermal conductivity of high-pressure formed, high-density di-n-butyl phthalate glass and pressure induced departures from equilibrium state

    Science.gov (United States)

    Johari, G. P.; Andersson, Ove

    2017-06-01

    We report a study of structural relaxation of high-density glasses of di-n-butyl phthalate (DBP) by measuring thermal conductivity, κ, under conditions of pressure and temperature (p,T) designed to modify both the vibrational and configurational states of a glass. Various high-density glassy states of DBP were formed by (i) cooling the liquid under a fixed high p and partially depressurizing the glass, (ii) isothermal annealing of the depressurized glass, and (iii) pressurizing the glass formed by cooling the liquid under low p. At a given low p, κ of the glass formed by cooling under high p is higher than that of the glass formed by cooling under low p, and the difference increases as glass formation p is increased. κ of the glass formed under 1 GPa is ˜20% higher at ambient p than κ of the glass formed at ambient p. On heating at low p, κ decreases until the glass to liquid transition range is reached. This is the opposite of the increase in κ observed when a glass formed under a certain p is heated under the same p. At a given high p, κ of the low-density glass formed by cooling at low p is lower than that of the high-density glass formed by cooling at that high p. On heating at high p, κ increases until the glass to liquid transition range is reached. The effects observed are due to a thermally assisted approach toward equilibrium at p different from the glass formation p. In all cases, the density, enthalpy, and entropy would change until the glasses become metastable liquids at a fixed p, thus qualitatively relating κ to variation in these properties.

  2. Glass transitions in the cellular Potts model

    Science.gov (United States)

    Chiang, M.; Marenduzzo, D.

    2016-10-01

    We study the dynamical transition between a fluid-like and a solid-like phase in a confluent cell monolayer, by using the cellular Potts model and computer simulations. We map out the phase diagram as a function of interfacial tension and of cell motility. While in the fluid phase there is normal diffusion, in the solid phase we observe sub-diffusion, very slow relaxation, and ageing, thereby strongly suggesting that this phase is glassy. Our results complement previous theoretical work within the vertex model and show that the cellular Potts model can account for the experimentally observed glassy dynamics of some biological tissues.

  3. PREFACE: Statistical Physics of Ageing Phenomena and the Glass Transition

    Science.gov (United States)

    Henkel, Malte; Pleimling, Michel; Sanctuary, Roland

    2006-06-01

    A summer school on `Ageing and the glass transition' was held at the University of Luxembourg on 18-24 September 2005. It brought together about 60 scientists actively studying the related fields of physical ageing and of the thermodynamics of glass-forming systems when undergoing a glass transition. The programme of the school can be found on the homepage ( http://www.theorie1.physik.uni-erlangen.de/sommerschule.html). The school contained both invited lectures and contributed talks and posters. This volume presents the works contributed to the summer school, while the invited lectures will be published elsewhere (M Henkel, M Pleimling and R Sanctuary (eds), Ageing and the glass transition, Springer Lecture Notes in Physics, Springer (Heidelberg 2006)). We have tried to encourage the exchange between theorists and experimentalists to which the topics treated in these proceedings bear witness. They range from experimental studies on the mechanical response of glasses, biopolymers, and granular materials to the effects of ageing on the long-time modification of the properties of glass-forming polymers, from simulational and analytical studies of theoretical models describing the non-equilibrium statistical mechanics of systems displaying the dynamical scaling typical of ageing phenomena and which are thought to capture essential aspects of glass-forming materials close to a glass transition to more mathematically oriented investigations on the symmetries of these systems. The `Grande Région' Sar-Lor-Lux is leading European efforts to overcome national and linguistic barriers, with the view of creating a common academic education. Physics has a standing internationalist tradition and the existing trinational integrated course in Physics SLLS (see the homepage http://www.uni-saarland.de/fak7/krueger/integ/sll/d/cursus.htm) is busily developing ways and means towards this goal, in particular through the delivery of multinational and multilingual university degrees in

  4. Instantaneous Normal Modes and the Protein Glass Transition

    Energy Technology Data Exchange (ETDEWEB)

    Schultz, Roland [University of Tennessee, Knoxville (UTK); Krishnan, Marimuthu [ORNL; Daidone, Isabella [University of Heidelberg; Smith, Jeremy C [ORNL

    2009-01-01

    In the instantaneous normal mode method, normal mode analysis is performed at instantaneous configurations of a condensed-phase system, leading to modes with negative eigenvalues. These negative modes provide a means of characterizing local anharmonicities of the potential energy surface. Here, we apply instantaneous normal mode to analyze temperature-dependent diffusive dynamics in molecular dynamics simulations of a small protein (a scorpion toxin). Those characteristics of the negative modes are determined that correlate with the dynamical (or glass) transition behavior of the protein, as manifested as an increase in the gradient with T of the average atomic mean-square displacement at 220 K. The number of negative eigenvalues shows no transition with temperature. Further, although filtering the negative modes to retain only those with eigenvectors corresponding to double-well potentials does reveal a transition in the hydration water, again, no transition in the protein is seen. However, additional filtering of the protein double-well modes, so as to retain only those that, on energy minimization, escape to different regions of configurational space, finally leads to clear protein dynamical transition behavior. Partial minimization of instantaneous configurations is also found to remove nondiffusive imaginary modes. In summary, examination of the form of negative instantaneous normal modes is shown to furnish a physical picture of local diffusive dynamics accompanying the protein glass transition.

  5. Structural behavior of Pd40Cu30Ni10P20 bulk metallic glass below and above the glass transition

    DEFF Research Database (Denmark)

    Mattern, N.; Hermann, H.; Roth, S.;

    2003-01-01

    The thermal behavior of the structure of Pd40Cu30Ni10P20 bulk metallic glass has been investigated in situ through the glass transition by means of high-temperature x-ray synchrotron diffraction. The dependence of the x-ray structure factor S(q) of the Pd40Cu30Ni10P20 glass on temperature follows...

  6. Predicting glass transition temperatures of polyarylethersulphones using QSPR methods.

    Directory of Open Access Journals (Sweden)

    Ian Hamerton

    Full Text Available The technique of Quantitative Structure Property Relationships has been applied to the glass transition temperatures of polyarylethersulphones. A general equation is reported that calculates the glass transition temperatures with acceptable accuracy (correlation coefficients of between 90-67%, indicating an error of 10-30% with regard to experimentally determined values for a series of 42 reported polyarylethersulphones. This method is quite simple in assumption and relies on a relatively small number of parameters associated with the structural unit of the polymer: the number of rotatable bonds, the dipole moment, the heat of formation, the HOMO eigenvalue, the molar mass and molar volume. For smaller subsets of the main group (based on families of derivatives containing different substituents the model can be simplified further to an equation that uses the volume of the substituents as the principal variable.

  7. Motility-driven glass and jamming transitions in biological tissues

    CERN Document Server

    Bi, Dapeng; Marchetti, M Cristina; Manning, M Lisa

    2015-01-01

    Cell motion inside dense tissues governs many biological processes, including embryonic development and cancer metastasis, and recent experiments suggest that these tissues exhibit collective glassy behavior. To make quantitative predictions about glass transitions in tissues, we study a self-propelled Voronoi (SPV) model that simultaneously captures polarized cell motility and multi-body cell-cell interactions in a confluent tissue, where there are no gaps between cells. We demonstrate that the model exhibits a jamming transition from a solid-like state to a fluid-like state that is controlled by three parameters: the single-cell motile speed, the persistence time of single-cell tracks, and a target shape index that characterizes the competition between cell-cell adhesion and cortical tension. In contrast to traditional particulate glasses, we are able to identify an experimentally accessible structural order parameter that specifies the entire jamming surface as a function of model parameters. We demonstrat...

  8. Multiple Glass Transitions and Freezing Events of Aqueous Citric Acid

    Science.gov (United States)

    2014-01-01

    Calorimetric and optical cryo-microscope measurements of 10–64 wt % citric acid (CA) solutions subjected to moderate (3 K/min) and slow (0.5 and 0.1 K/min) cooling/warming rates and also to quenching/moderate warming between 320 and 133 K are presented. Depending on solution concentration and cooling rate, the obtained thermograms show one freezing event and from one to three liquid–glass transitions upon cooling and from one to six liquid–glass and reverse glass–liquid transitions, one or two freezing events, and one melting event upon warming of frozen/glassy CA/H2O. The multiple freezing events and glass transitions pertain to the mother CA/H2O solution itself and two freeze-concentrated solution regions, FCS1 and FCS2, of different concentrations. The FCS1 and FCS2 (or FCS22) are formed during the freezing of CA/H2O upon cooling and/or during the freezing upon warming of partly glassy or entirely glassy mother CA/H2O. The formation of two FCS1 and FCS22 regions during the freezing upon warming to our best knowledge has never been reported before. Using an optical cryo-microscope, we are able to observe the formation of a continuous ice framework (IF) and its morphology and reciprocal distribution of IF/(FCS1 + FCS2). Our results provide a new look at the freezing and glass transition behavior of aqueous solutions and can be used for the optimization of lyophilization and freezing of foods and biopharmaceutical formulations, among many other applications where freezing plays a crucial role. PMID:25482069

  9. Beta relaxation of nonpolymeric liquids close to the glass transition

    DEFF Research Database (Denmark)

    Olsen, Niels Boye; Christensen, Tage Emil; Dyre, Jeppe

    2000-01-01

    Dielectric beta relaxation in a pyridine-toluene solution is studied close to the glass transition. Loss peak frequency and maximum loss both exhibit thermal hysteresis. An annealing-state-independent parameter involving loss and loss peak frequency is identified. This parameter has a simple Arrh...... Arrhenius temperature dependence. The same behavior is found for four other viscous liquids, indicating that the phenomenon is possibly general....

  10. Motility-Driven Glass and Jamming Transitions in Biological Tissues

    Science.gov (United States)

    Bi, Dapeng; Yang, Xingbo; Marchetti, M. Cristina; Manning, M. Lisa

    2016-04-01

    Cell motion inside dense tissues governs many biological processes, including embryonic development and cancer metastasis, and recent experiments suggest that these tissues exhibit collective glassy behavior. To make quantitative predictions about glass transitions in tissues, we study a self-propelled Voronoi model that simultaneously captures polarized cell motility and multibody cell-cell interactions in a confluent tissue, where there are no gaps between cells. We demonstrate that the model exhibits a jamming transition from a solidlike state to a fluidlike state that is controlled by three parameters: the single-cell motile speed, the persistence time of single-cell tracks, and a target shape index that characterizes the competition between cell-cell adhesion and cortical tension. In contrast to traditional particulate glasses, we are able to identify an experimentally accessible structural order parameter that specifies the entire jamming surface as a function of model parameters. We demonstrate that a continuum soft glassy rheology model precisely captures this transition in the limit of small persistence times and explain how it fails in the limit of large persistence times. These results provide a framework for understanding the collective solid-to-liquid transitions that have been observed in embryonic development and cancer progression, which may be associated with epithelial-to-mesenchymal transition in these tissues.

  11. Heat capacities and glass transitions of ion gels.

    Science.gov (United States)

    Yamamuro, Osamu; Someya, Takenori; Kofu, Maiko; Ueki, Takeshi; Ueno, Kazuhide; Watanabe, Masayoshi

    2012-09-06

    We have investigated thermodynamic properties of ion gels consisting of a PMMA [poly(methyl methacrylate)] network and EMITFSI [1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide] ionic liquid by means of an adiabatic calorimeter. The heat capacity data were measured in the temperature range between 5 and 375 K for 7 samples with x = 0 (pure PMMA), 0.10, 0.18, 0.27, 0.48, 0.65, and 1.0 (pure ionic liquid) where x is a mole fraction of EMITFSI. These data revealed that two broad but distinct glass transitions appeared in the low x region. The upper glass transition is mainly due to the freezing of the PMMA motion, while the lower one is due to the ionic liquid. The upper glass transition temperature T(g) drastically decreased with increasing x, reflecting a large plasticization effect observed in mechanical experiments. The x dependence of the T(g)s and the excess heat capacities gave new physical insight to the interaction between polymer and ionic liquid in ion gels.

  12. Simple solvable energy-landscape model that shows a thermodynamic phase transition and a glass transition.

    Science.gov (United States)

    Naumis, Gerardo G

    2012-06-01

    When a liquid melt is cooled, a glass or phase transition can be obtained depending on the cooling rate. Yet, this behavior has not been clearly captured in energy-landscape models. Here, a model is provided in which two key ingredients are considered in the landscape, metastable states and their multiplicity. Metastable states are considered as in two level system models. However, their multiplicity and topology allows a phase transition in the thermodynamic limit for slow cooling, while a transition to the glass is obtained for fast cooling. By solving the corresponding master equation, the minimal speed of cooling required to produce the glass is obtained as a function of the distribution of metastable states.

  13. Predicting bioactive glass properties from the molecular chemical composition: glass transition temperature.

    Science.gov (United States)

    O'Donnell, Matthew D

    2011-05-01

    The glass transition temperature (T(g)) of inorganic glasses is an important parameter than can be used to correlate with other glass properties, such as dissolution rate, which governs in vitro and in vivo bioactivity. Seven bioactive glass compositional series reported in the literature (77 in total) were analysed here with T(g) values obtained by a number of different methods: differential thermal analysis, differential scanning calorimetry and dilatometry. An iterative least-squares fitting method was used to correlate T(g) from thermal analysis of these compositions with the levels of individual oxide and fluoride components in the glasses. When all seven series were fitted a reasonable correlation was found between calculated and experimental values (R(2)=0.89). When the two compositional series that were designed in weight percentages (the remaining five were designed in molar percentage) were removed from the model an improved fit was achieved (R(2)=0.97). This study shows that T(g) for a wide range in compositions (e.g. SiO(2) content of 37.3-68.4 mol.%) can be predicted to reasonable accuracy enabling processing parameters to be predicted such as annealing, fibre-drawing and sintering temperatures.

  14. The glass transition and diffusion in simulated liquid TiO{sub 2}

    Energy Technology Data Exchange (ETDEWEB)

    Vo Van Hoang [Department of Physics, Institute of Technology, National University of HochiMinh City, 268 Ly Thuong Kiet Street, District 10, HochiMinh City (Viet Nam)

    2007-10-17

    The glass transition and diffusion in liquid TiO{sub 2} have been studied in a model containing 3000 atoms via molecular dynamics (MD) simulation. The density dependence of the glass transition temperature, T{sub g}, of liquid TiO{sub 2} has been found and is discussed. Diffusion of atomic species in 3.80 g cm{sup -3} TiO{sub 2} models has been investigated over a wide temperature range from 2100 to 7000 K. We found that the temperature dependence of the diffusion constant of atomic species follows an Arrhenius law at relatively low temperatures above the melting point, and at higher temperatures it deviates from an Arrhenius law. Differences between the structures of amorphous TiO{sub 2} models at three different densities in the range from 3.80 to 4.20 g cm{sup -3} have been found and are discussed. In addition, a transition from a low-density liquid (ldl) form to a high-density liquid (hdl) form was found and is discussed.

  15. Mathematical modeling of photoinitiated coating degradation: Effects of coating glass transition temperature and light stabilizers

    DEFF Research Database (Denmark)

    Kiil, Søren; G.de With, R.A.T.M.Van Benthem

    2013-01-01

    A mathematical model, describing coating degradation mechanisms of thermoset coatings exposed to ultraviolet radiation and humidity at constant temperature, was extended to simulate the behavior of a coating with a low glass transition temperature. The effects of adding light stabilizers (a UV...... absorber and a radical scavenger) to the coating were also explored. The extended model includes photoinitiated oxidation reactions, intrafilm oxygen permeability, water absorption and diffusion, reduction of crosslink density, absorption of ultraviolet radiation, a radical scavenger reaction......, and simulates the transient development of an oxidation zone. Simulations are in good agreement with experimental data for a fast degrading epoxy-amine coating with a glass transition temperature of −50°C. It was found that the degradation rate of the non-stabilized coating was influenced significantly...

  16. Amorphous to amorphous insulator-metal transition in GeSe3:Ag glasses

    Science.gov (United States)

    Prasai, Kiran; Chen, Gang; Drabold, D. A.

    2017-06-01

    We study an insulator-metal transition in a ternary chalcogenide glass (GeSe3)1 -xAgx for x =0.15 and 0.25. The conducting phase of the glass is obtained by using gap sculpting [Prasai et al., Sci. Rep. 5, 15522 (2015), 10.1038/srep15522] and it is observed that the metallic and insulating phases have nearly identical density functional energies but have a conductivity contrast of ˜108 . As such, we demonstrate an example of polyamorphism for which energetically close phases exhibit dramatically different optical properties. The transition from insulator to metal involves growth of an Ag-rich phase accompanied by a depletion of tetrahedrally bonded Ge (Se1/2)4 in the host network. The relative fraction of the amorphous Ag2Se phase and GeSe2 phase is shown to be a critical determinant of dc conductivity.

  17. Fuel Pellets from Wheat Straw: The Effect of Lignin Glass Transition and Surface Waxes on Pelletizing Properties

    DEFF Research Database (Denmark)

    Stelte, Wolfgang; Clemons, Craig; Holm, Jens K.;

    2012-01-01

    and a high concentration of hydrophobic waxes on its outer surface that may limit the pellet strength. The present work studies the impact of the lignin glass transition on the pelletizing properties of wheat straw. Furthermore, the effect of surface waxes on the pelletizing process and pellet strength...... are investigated by comparing wheat straw before and after organic solvent extraction. The lignin glass transition temperature for wheat straw and extracted wheat straw is determined by dynamic mechanical thermal analysis. At a moisture content of 8%, transitions are identified at 53°C and 63°C, respectively....... Pellets are pressed from wheat straw and straw where the waxes have been extracted from. Two pelletizing temperatures were chosen—one below and one above the glass transition temperature of lignin. The pellets compression strength, density, and fracture surface were compared to each other. Pellets pressed...

  18. First-principles computation of random-pinning glass transition, glass cooperative length scales, and numerical comparisons

    Science.gov (United States)

    Cammarota, Chiara; Seoane, Beatriz

    2016-11-01

    As a guideline for experimental tests of the ideal glass transition (random-pinning glass transition, RPGT) that shall be induced in a system by randomly pinning particles, we performed first-principle computations within the hypernetted chain approximation and numerical simulations of a hard-sphere model of a glass former. We obtain confirmation of the expected enhancement of glassy behavior under the procedure of random pinning. We present the analytical phase diagram as a function of c and of the packing fraction ϕ , showing a line of RPGT ending in a critical point. We also obtain microscopic results on cooperative length scales characterizing medium-range amorphous order in hard-sphere glasses and indirect quantitative information on a key thermodynamic quantity defined in proximity to ideal glass transitions, the amorphous surface tension. Finally, we present numerical results of pair correlation functions able to differentiate the liquid and the glass phases, as predicted by the analytic computations.

  19. Raman scattering boson peak and differential scanning calorimetry studies of the glass transition in tellurium-zinc oxide glasses

    Energy Technology Data Exchange (ETDEWEB)

    Stavrou, E; Tsiantos, C; Tsopouridou, R D; Kripotou, S; Kontos, A G; Raptis, C [Department of Physics, National Technical University of Athens, GR-15780 Athens (Greece); Capoen, B; Bouazaoui, M [Laboratoire de Physique des Lasers, Atomes et Molecules (CNRS, UMR 8523), Batiment P-5, Centre d' Etudes et de Recherches Lasers et Applications (CERLA-FR CNRS 2416), Universite de Sciences et Technologies de Lille, F-59655 Villeneuve d' Ascq Cedex (France); Turrell, S; Khatir, S, E-mail: craptis@central.ntua.g [Laboratoire de Spectrochimie Infrarouge et Raman (CNRS 8516), Batiment C-5, Centre d' Etudes et de Recherches Lasers et Applications (CERLA-FR CNRS 2416), Universite de Sciences et Technologies de Lille, F-59655 Villeneuve d' Ascq Cedex (France)

    2010-05-19

    Raman scattering and differential scanning calorimetry (DSC) measurements have been carried out on four mixed tellurium-zinc oxide (TeO{sub 2}){sub 1-x}(ZnO){sub x} (x = 0.1, 0.2, 0.3, 0.4) glasses under variable temperature, with particular attention being given to the respective glass transition region. From the DSC measurements, the glass transition temperature T{sub g} has been determined for each glass, showing a monotonous decrease of T{sub g} with increasing ZnO content. The Raman study is focused on the low-frequency band of the glasses, the so-called boson peak (BP), whose frequency undergoes an abrupt decrease at a temperature T{sub d} very close to the respective T{sub g} values obtained by DSC. These results show that the BP is highly sensitive to dynamical effects over the glass transition and provides a means for an equally reliable (to DSC) determination of T{sub g} in tellurite glasses and other network glasses. The discontinuous temperature dependence of the BP frequency at the glass transition, along with the absence of such a behaviour by the high-frequency Raman bands (due to local atomic vibrations), indicates that marked changes of the medium range order (MRO) occur at T{sub g} and confirms the correlation between the BP and the MRO of glasses.

  20. Dynamic thermal expansivity of liquids near the glass transition.

    Science.gov (United States)

    Niss, Kristine; Gundermann, Ditte; Christensen, Tage; Dyre, Jeppe C

    2012-04-01

    Based on previous works on polymers by Bauer et al. [Phys. Rev. E 61, 1755 (2000)], this paper describes a capacitative method for measuring the dynamical expansion coefficient of a viscous liquid. Data are presented for the glass-forming liquid tetramethyl tetraphenyl trisiloxane (DC704) in the ultraviscous regime. Compared to the method of Bauer et al., the dynamical range has been extended by making time-domain experiments and by making very small and fast temperature steps. The modeling of the experiment presented in this paper includes the situation in which the capacitor is not full because the liquid contracts when cooling from room temperature down to around the glass-transition temperature, which is relevant when measuring on a molecular liquid rather than a polymer.

  1. Single-particle dynamics near the glass transition of a metallic glass

    Science.gov (United States)

    Lü, Y. J.; Wang, W. H.

    2016-12-01

    The single-particle dynamics of the glass-forming C u50Z r50 alloy, from the supercooled liquid well above the glass-transition temperature, Tg to the glassy state, is studied by using the molecular dynamics simulations. When the liquid is cooled below 1.2 Tg , the dynamics heterogeneity characterized by the cage-jump motion becomes increasingly pronounced. The analyses based on the continuous time random walk method indicate that the liquid falls out of equilibrium in the present simulation time scale when it is cooled into the regime below 1.02 Tg . However, we find that the jump length and the jump rate do not display the non-equilibrium behaviors even in the glassy state below Tg, which allows us to study the intrinsic dynamic characteristics through Tg. The mean waiting time between two successive jumps has a rapid growth following the Vogel-Fulcher-Tammann law as the non-equilibrium regime is approached, in analogy with the temperature behaviors of transport properties for fragile supercooled liquids. In contrast, the jump rate maintains the Arrhenius decay and the jump length has even a weaker temperature dependence when the liquid is cooled into glassy state. We find that a pronounced enhancement of the spatial correlation of jumps occurs accompanied by the glass transition: the string-like cooperative jumps dominate the fast motion instead of the uncorrelated and individual jumps. Our work offers an insight into the equilibrium effect of the single-particle dynamics in glass transition.

  2. Affinity and its derivatives in the glass transition process

    Science.gov (United States)

    Garden, J.-L.; Guillou, H.; Richard, J.; Wondraczek, L.

    2012-07-01

    The thermodynamic treatment of the glass transition remains an issue of intense debate. When associated with the formalism of non-equilibrium thermodynamics, the lattice-hole theory of liquids can provide new insight in this direction, as has been shown by Schmelzer and Gutzow [J. Chem. Phys. 125, 184511 (2006)], 10.1063/1.2374894, by Möller et al. [J. Chem. Phys. 125, 094505 (2006)], 10.1063/1.2346673, and more recently by Tropin et al. [J. Non-Cryst. Solids 357, 1291 (2011), 10.1016/j.jnoncrysol.2010.11.111; Tropin et al., J. Non-Cryst. Solids 357, 1303 (2011)], 10.1016/j.jnoncrysol.2010.12.005. Here, we employ a similar approach. We include pressure as an additional variable, in order to account for the freezing-in of structural degrees of freedom upon pressure increase. Second, we demonstrate that important terms concerning first order derivatives of the affinity-driving-force with respect to temperature and pressure have been previously neglected. We show that these are of crucial importance in the approach. Macroscopic non-equilibrium thermodynamics is used to enlighten these contributions in the derivation of Cp,κT, and αp. The coefficients are calculated as a function of pressure and temperature following different theoretical protocols, revealing classical aspects of vitrification and structural recovery processes. Finally, we demonstrate that a simple minimalist model such as the lattice-hole theory of liquids, when being associated with rigorous use of macroscopic non-equilibrium thermodynamics, is able to account for the primary features of the glass transition phenomenology. Notwithstanding its simplicity and its limits, this approach can be used as a very pedagogical tool to provide a physical understanding on the underlying thermodynamics which governs the glass transition process.

  3. Pressure Dependence of the Glass Transition Temperature in the Fragile Glass Former Cumene

    Science.gov (United States)

    Raty, Jean-Yves; Baris Malcioglu, Osman; Bichara, Christophe

    2013-03-01

    The glass transition temperature, Tg, is one of the most important characteristics of glassy systems. While Tg has been measured for many systems at atmospheric pressure, direct measurement of the glass transition is difficult at high pressures due to small sample sizes and long time scales. Tg(P) measurements to date mostly involve extrapolations of high-pressure viscosity or relaxation data to η = 1013 P or t = 100 s, respectively. In this study we present direct measurement of Tg at pressures up to several GPa through a combination of pressure gradient tracking and observation of increases in the thermal expansion coefficient upon heating from the glass to the viscous liquid state. High pressures are attained through the use of a diamond anvil cell and precise temperatures are maintained via custom heating and cryogenic systems. By directly mapping this phase boundary, we can compare models for Tg(P). In addition, high-pressure analysis requiring knowledge of Tg at pressure will be greatly aided.

  4. Dynamic mechanical behavior of a Zr-based bulk metallic glass during glass transition and crystallization

    Institute of Scientific and Technical Information of China (English)

    CHAO Qi; WANG Qing; DONG Yuanda

    2009-01-01

    The dynamic mechanical behaviors of the Zr41Ti14Cu12.5Ni8Be22.5Fe2 bulk metallic glass (BMG) during continuous heating at a constant rate were investigated. The glass transition and crystallization of the Zr-based BMG were thus characterized by the measurements of storage modulus E and internal friction Q-1. It was found that the variations of these dynamic mechanical quantifies with temperature were interre-lated and were well in agreement with the DSC trace obtained at the same heating rate. The origin of the first peak in the internal friction curve was closely related to the dynamic glass transition and subsequent primary crystallization. Moreover, it can be well described by a physical model, which can characterize atomic mobility and mechanical response of disordered condense materials. In comparison with the DSC trace, the relative position of the first internal friction peak of the BMG was found to be dependent on its thermal stability against crys-tallization.

  5. QSPR Study on the Glass Transition Temperature of Polyacrylates

    Institute of Scientific and Technical Information of China (English)

    2007-01-01

    Structural parameters of 22 polyacrylic compounds were computed at two levels using Hartree-Fock and DFT methods. Based on the experimental data of glass transition temperature (Tg), four-parameter (energy of the lowest unoccupied molecular orbital (ELOMO), the highest positive charge (Qmax+), dipole moments (μ) and the next highest occupied molecular orbital (ENLOMO)) dependent equations were developed using structural parameters as theoretical descriptors. Especially, Tg dependent equation calculated at the HF/6-31G(d) level is more advantageous than others in view of their correlation and predictive abilities. This dependent equation was validated by variance inflation factors (VIF) and t-test methods.

  6. Molecular Dynamics Simulation of Glass Transition Behavior of Polyimide Ensemble

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    The effect of chromophores to the glass transition temperature of polyimide ensemble has been investigated by means of molecular dynamics simulation in conjunction with barrier analysis. Simulated Tg results indicated a good agreement with experimental value. This study showed the MD simulation could estimate the effect of chromophores to the Tg of polyimide ensemble conveniently and an estimation approach method had a surprising deviation of Tg from experiment. At the same time, a polyimide structure with higher barrier energy was designed and validated by MD simulation.

  7. Pressure Induced Liquid-to-Liquid Transition in Zr-based Supercooled Melts and Pressure Quenched Glasses

    Energy Technology Data Exchange (ETDEWEB)

    Dmowski, W.; Gierlotka, S.; Wang, Z.; Yokoyama, Y.; Palosz, B.; Egami, T.

    2017-07-26

    Through high-energy x-ray diffraction and atomic pair density function analysis we find that Zr-based metallic alloy, heated to the supercooled liquid state under hydrostatic pressure and then quenched to room temperature, exhibits a distinct glassy structure. The PDF indicates that the Zr-Zr distances in this glass are significantly reduced compared to those quenched without pressure. Annealing at the glass transition temperature at ambient pressure reverses structural changes and the initial glassy state is recovered. This result suggests that pressure causes a liquid-to-liquid phase transition in this metallic alloy supercooled melt. Such a pressure induced transition is known for covalent liquids, but has not been observed for metallic liquids. The High Pressure Quenched glasses are stable in ambient conditions after decompression.

  8. Glass transition temperatures of epoxy resins by pulsed nuclear magnetic resonance spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Rutenberg, A.C.; Dorsey, G.F.; Peck, C.G.

    1976-04-21

    Pulsed nuclear magnetic resonance spectroscopy has been used to measure the glass transition temperatures of cured epoxy resins. These measurements make it possible to monitor the cure and determine the glass transition temperature as a function of the curing conditions and the concentration of the components. Knowledge of the glass transition temperature of the cured epoxies allows screening of them for a number of uses, including adhesives and coatings operations.

  9. Effect of instantaneous and continuous quenches on the density of vibrational modes in model glasses

    Science.gov (United States)

    Lerner, Edan; Bouchbinder, Eran

    2017-08-01

    Computational studies of supercooled liquids often focus on various analyses of their "underlying inherent states"—the glassy configurations at zero temperature obtained by an infinitely fast (instantaneous) quench from equilibrium supercooled states. Similar protocols are also regularly employed in investigations of the unjamming transition at which the rigidity of decompressed soft-sphere packings is lost. Here we investigate the statistics and localization properties of low-frequency vibrational modes of glassy configurations obtained by such instantaneous quenches. We show that the density of vibrational modes grows as ωβ with β depending on the parent temperature T0 from which the glassy configurations were instantaneously quenched. For quenches from high temperature liquid states we find β ≈3 , whereas β appears to approach the previously observed value β =4 as T0 approaches the glass transition temperature. We discuss the consistency of our findings with the theoretical framework of the soft potential model, and contrast them with similar measurements performed on configurations obtained by continuous quenches at finite cooling rates. Our results suggest that any physical quench at rates sufficiently slower than the inverse vibrational time scale—including all physically realistic quenching rates of molecular or atomistic glasses—would result in a glass whose density of vibrational modes is universally characterized by β =4 .

  10. Structural influence of mixed transition metal ions on lithium bismuth borate glasses

    Science.gov (United States)

    Yadav, Arti; Dahiya, Manjeet S.; Hooda, A.; Chand, Prem; Khasa, S.

    2017-08-01

    Lithium bismuth borate glasses containing mixed transition metals having composition 7CoO·23Li2O·20Bi2O3·50B2O3 (CLBB), 7V2O5·23Li2O·20Bi2O3·50B2O3 (VLBB) and x(2CoO·V2O5)·(30 - x)Li2O·20Bi2O3·50B2O3 (x = 0.0 (LBB) and x = 2.0, 5.0, 7.0, 10.0 mol% (CVLBB1-4)) are synthesized via melt quench route. The synthesized compositions are investigated for their physical properties using density (D) and molar volume (Vm), thermal properties by analyzing DSC/TG thermo-graphs, structural properties using IR absorption spectra in the mid-IR range and optical properties using UV-Vis-NIR spectroscopy. The Electron Paramagnetic Resonance (EPR) spectra of vanadyl and cobalt ion have been analyzed to study compositional effects on spin-Hamiltonian parameters. The non linear variations in physical properties depict a strong structural influence of Co/V- oxides on the glassy matrix. The compositional variations in characteristic temperatures (glass transition temperature Tg, glass crystallization temperature Tp and glass melting temperature Tm) reveals that Tg for glass samples CLBB is relatively less than that of pure lithium bismuth borate (LBB) glass sample wherein Tg for sample VLBB is higher than that of LBB. The increase in Tg (as compared with LBB) with an enhanced substitution of mixed transition metal oxides (2CoO·V2O5) shows a progressive structure modification of bismuth borate matrix. These predictions are very well corroborated by corresponding compositional trends of Tp and Tm. FTIR studies reveal that Co2+& VO2+ ions lead to structural rearrangements through the conversion of three-coordinated boron into four coordinated boron and thereby reducing number of non-bridging oxygen atoms. Bismuth is found to exist in [BiO6] octahedral units only, whereas boroxol rings are not present in the glass network. The theoretical values of optical basicity (Λth) and corresponding oxide ion polarizability (αo2-) have also been calculated to investigate oxygen covalency of

  11. Transition and post-transition metal ions in borate glasses: Borate ligand speciation, cluster formation, and their effect on glass transition and mechanical properties

    Science.gov (United States)

    Möncke, D.; Kamitsos, E. I.; Palles, D.; Limbach, R.; Winterstein-Beckmann, A.; Honma, T.; Yao, Z.; Rouxel, T.; Wondraczek, L.

    2016-09-01

    A series of transition and post-transition metal ion (Mn, Cu, Zn, Pb, Bi) binary borate glasses was studied with special consideration of the cations impact on the borate structure, the cations cross-linking capacity, and more generally, structure-property correlations. Infrared (IR) and Raman spectroscopies were used for the structural characterization. These complementary techniques are sensitive to the short-range order as in the differentiation of tetrahedral and trigonal borate units or regarding the number of non-bridging oxygen ions per unit. Moreover, vibrational spectroscopy is also sensitive to the intermediate-range order and to the presence of superstructural units, such as rings and chains, or the combination of rings. In order to clarify band assignments for the various borate entities, examples are given from pure vitreous B2O3 to meta-, pyro-, ortho-, and even overmodified borate glass compositions. For binary metaborate glasses, the impact of the modifier cation on the borate speciation is shown. High field strength cations such as Zn2+ enhance the disproportionation of metaborate to polyborate and pyroborate units. Pb2+ and Bi3+ induce cluster formation, resulting in PbOn- and BiOn-pseudophases. Both lead and bismuth borate glasses show also a tendency to stabilize very large superstructural units in the form of diborate polyanions. Far-IR spectra reflect on the bonding states of modifier cations in glasses. The frequency of the measured cation-site vibration band was used to obtain the average force constant for the metal-oxygen bonding, FM-O. A linear correlation between glass transition temperature (Tg) and FM-O was shown for the metaborate glass series. The mechanical properties of the glasses also correlate with the force constant FM-O, though for cations of similar force constant the fraction of tetrahedral borate units (N4) strongly affects the thermal and mechanical properties. For paramagnetic Cu- and Mn-borate glasses, N4 was determined

  12. Assignment of the glass transition temperature using dielectric analysis: A review

    Energy Technology Data Exchange (ETDEWEB)

    Bidstrup, S.A. [Georgia Inst. of Technology, Atlanta, GA (United States). School of Chemical Engineering; Day, D.R. [Auburn International, Danvers, MA (United States)

    1994-09-01

    The use of dielectric analysis for the determination of the glass transition temperature for polymers is reviewed. Both a sharp increase in the permittivity and the dielectric loss peak have been correlated with the glass transition. Dielectric data for an epoxy resin and polyvinylchloride are presented and compared with data obtained by differential scanning calorimetry (DSC). The dielectric glass transition approaches the DSC glass transition as the frequency of the dielectric measurement is decreased. The effects of contact resistance and moisture on the dielectric measurement are also discussed.

  13. Kinetics of glass transition and crystallization in multicomponent bulk amorphous alloys

    Institute of Scientific and Technical Information of China (English)

    庄艳歆[1; 赵德乾[2; 张勇[3; 汪卫华[4; 潘明祥[5

    2000-01-01

    Differential scanning calorimeter (DSC) is used to investigate apparent activation energy of glass transition and crystallization of Zr-based bulk amorphous alloys by Kissinger equation under non-isothermal condition. It is shown that the glass transition behavior as well as crystallization reaction depends on the heating rate and has a characteristic of kinetic effects. After being isothermally annealed near glass transition temperature, the apparent activation energy of glass transition increases and the apparent activation energy of crystallization reaction decreases. However, the kinetic effects are independent of the pre-annealing.

  14. Evidence for a simple monatomic ideal glass former: the thermodynamic glass transition from a stable liquid phase.

    Science.gov (United States)

    Elenius, Måns; Oppelstrup, Tomas; Dzugutov, Mikhail

    2010-11-01

    Under cooling, a liquid can undergo a transition to the glassy state either as a result of a continuous slowing down or by a first-order polyamorphous phase transition. The second scenario has so far always been observed in a metastable liquid domain below the melting point where crystalline nucleation interfered with the glass formation. We report the first observation of the liquid-glass transition by a first-order polyamorphous phase transition from the equilibrium stable liquid phase. The observation was made in a molecular dynamics simulation of a one-component system with a model metallic pair potential. In this way, the model, demonstrating the thermodynamic glass transition from a stable liquid phase, may be regarded as a candidate for a simple monatomic ideal glass former. This observation is of conceptual importance in the context of continuing attempts to resolve the long-standing Kauzmann paradox. The possibility of a thermodynamic glass transition from an equilibrium melt in a metallic system also indicates a new strategy for the development of bulk metallic glass-forming alloys.

  15. On valence electron density, energy dissipation and plasticity of bulk metallic glasses

    Energy Technology Data Exchange (ETDEWEB)

    Pang, J.J.; Tan, M.J. [School of Mechanical and Aerospace Engineering, Nanyang Technological University, 639798 Singapore (Singapore); Liew, K.M., E-mail: kmliew@cityu.edu.hk [Department of Civil and Architectural Engineering, City University of Hong Kong, Kowloon (Hong Kong)

    2013-11-15

    Highlights: ► Relationship between valence electron density and plasticity of metallic glasses. ► Poisson's ratio increases as electron density decreases. ► Energy dissipation proposed to understand plasticity. ► Low electron density indicates small activation energy. -- Abstract: In conventional crystalline alloys, valence electron density (VED) is one of the most significant factors in determining their phase stability and mechanical properties. Extending the concept to metallic glasses (MGs), it is found, not totally surprisingly, that their mechanical properties are VED-dependent as in crystalline alloys. Interestingly, the whole VED region can be separated into two zones: Zone 1 consists of Mg-, Ca-, and RE-based (RE for rare earth) alloys; Zone 2 consists of the rest of MGs. In either zone, for each type of MGs, Poisson's ratio generally decreases as VED increases. From the energy dissipation viewpoint proposed recently, the amorphous plasticity is closely related to the activation energy for the operation of shear-transformation-zones (STZs). Smaller STZ activation energy suggests higher ductility because STZs with lower activation energy are able to convert deformation work more efficiently into configurational energy rather than heat, which yields mechanical softening and advances the growth of shear bands (SBs). Following this model, it is revealed that the activation energies for STZ operation and crystallization are certainly proportional to VED. Thus, it is understood that, in Zone 2, MGs have a smaller VED and hence lower activation energies which are favorable for ductility and Poisson's ratio. In Zone 1, MGs have the lowest VED but apparent brittleness because either of low glass transition temperature and poor resistance to oxidation or of a large fraction of covalent bonds.

  16. Glass Transitions in Monodisperse Cluster-Forming Ensembles: Vortex Matter in Type-1.5 Superconductors

    Science.gov (United States)

    Díaz-Méndez, Rogelio; Mezzacapo, Fabio; Lechner, Wolfgang; Cinti, Fabio; Babaev, Egor; Pupillo, Guido

    2017-02-01

    At low enough temperatures and high densities, the equilibrium configuration of an ensemble of ultrasoft particles is a self-assembled, ordered, cluster crystal. In the present Letter, we explore the out-of-equilibrium dynamics for a two-dimensional realization, which is relevant to superconducting materials with multiscale intervortex forces. We find that, for small temperatures following a quench, the suppression of the thermally activated particle hopping hinders the ordering. This results in a glass transition for a monodispersed ensemble, for which we derive a microscopic explanation in terms of an "effective polydispersity" induced by multiscale interactions. This demonstrates that a vortex glass can form in clean systems of thin films of "type-1.5" superconductors. An additional setup to study this physics can be layered superconducting systems, where the shape of the effective vortex-vortex interactions can be engineered.

  17. Breaking Through the Glass Ceiling: Recent Experimental Approaches to Probe the Properties of Supercooled Liquids near the Glass Transition.

    Energy Technology Data Exchange (ETDEWEB)

    Smith, R. Scott; Kay, Bruce D.

    2012-03-15

    Experimental measurements of the properties supercooled liquids at temperatures near their respective glass transition temperatures, Tg, are requisite for understanding the behavior of glasses and amorphous solids. Unfortunately, many supercooled molecular liquids rapidly crystallize at temperatures far above their Tg making such measurements difficult to nearly impossible. In this perspective we discuss some recent alternative approaches to obtain experimental data in the temperature regime near Tg. These new approaches may yield the additional experimental data necessary to test current theoretical models of the dynamical slowdown that occurs in supercooled liquids approaching the glass transition.

  18. Breaking Through the Glass Ceiling: Recent Experimental Approaches to Probe the Properties of Supercooled Liquids near the Glass Transition.

    Science.gov (United States)

    Smith, R Scott; Kay, Bruce D

    2012-03-15

    Experimental measurements of the properties of supercooled liquids at temperatures near their glass transition temperatures, Tg, are requisite for understanding the behavior of glasses and amorphous solids. Unfortunately, many supercooled molecular liquids rapidly crystallize at temperatures far above their Tg, making such measurements difficult to nearly impossible. In this Perspective, we discuss some recent alternative approaches to obtain experimental data in the temperature regime near Tg. These new approaches may yield the additional experimental data necessary to test current theoretical models of the dynamical slowdown that occurs in supercooled liquids approaching the glass transition.

  19. Glass transition, crystallization kinetics and pressure effect on crystallization of ZrNbCuNiBe bulk metallic glass

    DEFF Research Database (Denmark)

    Xing, P.F.; Zhuang, Yanxin; Wang, W.H.

    2002-01-01

    The glass transition behavior and crystallization kinetics of Zr48Nb8Cu14Ni12Be18 bulk metallic glass have been investigated by differential scanning calorimetry and x-ray powder diffraction (XRD). The activation energies of both glass transition and crystallization events have been obtained using...... effect on crystallization is studied by in situ high-pressure and high-temperature XRD using synchrotron radiation. Two crystallization temperatures, observed by in-situ XRD, behave differently with varying pressure. The onset crystallization temperature increases with pressure with a slope of 9.5 K...

  20. Effects of transition metal oxide doping on the structure of sodium metaphosphate glasses

    Energy Technology Data Exchange (ETDEWEB)

    Zotov, N.; Kirfel, A.; Beuneu, B.; Delaplane, R.; Hohlwein, D.; Reinauer, F.; Glaum, R

    2004-07-15

    Neutron diffraction measurements of transition metal-oxide-doped sodium metaphosphate glasses and melts show an anomalous increase of the first sharp diffraction peak both with increasing transition metal content and temperature due to progressive increase of the structural disorder.

  1. Spin-exchange interaction between transition metals and metalloids in soft-ferromagnetic metallic glasses

    Science.gov (United States)

    Das, Santanu; Choudhary, Kamal; Chernatynskiy, Aleksandr; Choi Yim, Haein; Bandyopadhyay, Asis K.; Mukherjee, Sundeep

    2016-06-01

    High-performance magnetic materials have immense industrial and scientific importance in wide-ranging electronic, electromechanical, and medical device technologies. Metallic glasses with a fully amorphous structure are particularly suited for advanced soft-magnetic applications. However, fundamental scientific understanding is lacking for the spin-exchange interaction between metal and metalloid atoms, which typically constitute a metallic glass. Using an integrated experimental and molecular dynamics approach, we demonstrate the mechanism of electron interaction between transition metals and metalloids. Spin-exchange interactions were investigated for a Fe-Co metallic glass system of composition [(Co1-x Fe x )0.75B0.2Si0.05]96Cr4. The saturation magnetization increased with higher Fe concentration, but the trend significantly deviated from simple rule of mixtures. Ab initio molecular dynamics simulation was used to identify the ferromagnetic/anti-ferromagnetic interaction between the transition metals and metalloids. The overlapping band-structure and density of states represent ‘Stoner type’ magnetization for the amorphous alloys in contrast to ‘Heisenberg type’ in crystalline iron. The enhancement of magnetization by increasing iron was attributed to the interaction between Fe 3d and B 2p bands, which was further validated by valence-band study.

  2. Influence of pulsing current on the glass transition and crystallizing kinetics of a Zr base bulk amorphous alloy

    Institute of Scientific and Technical Information of China (English)

    WU Wenfei; YAO Kefu; ZHAO Zhankui

    2004-01-01

    Based on the thermal analysis, the influence of pulsing current on the glass transition and crystallizing kinetics of Zr41.3Ti14.2Cu12.8Ni10.3Be21.4 bulk amorphous alloy has been studied. The obtained results show that after the Zr41.3Ti14.2Cu12.8Ni10.3Be21.4 bulk amorphous alloy was pretreated by high-density pulsing current at low temperature, its glass transition temperature Tg, the initial crystallizing temperature Tx and the corresponding exothermic peak of crystallization Tpi were reduced. But the temperature range of supercooled liquid ΔT=Tx-Tg is almost the same. The calculated results with Kissinger equation show that the activation energy of glass transition of the alloy pretreated is reduced significantly, while the activation energy of crystallization is basically unchanged. The influence of pulsing current on the glass transition and crystallization of the Zr41.3Ti14.2Cu12.8Ni10.3Be21.4 bulk amorphous alloy is believed to be related with the structure relaxation of the glass caused by the current.

  3. The glass transition process in humid biopolymers. DSC study

    Energy Technology Data Exchange (ETDEWEB)

    Grunina, N A; Belopolskaya, T V; Tsereteli, G I [V.A. Fock Research Institute for Physics of Saint-Petersburg State University, 198504, Petrodvorets (Russian Federation)

    2006-05-15

    Thermal properties of native and denatured biopolymers with quite different chemical and steric structure (globular and fibrillar proteins, DNA, starches) were studied by means of differential scanning calorimetry in a wide range of temperatures and concentrations of water. It was shown that both native and denatured humid biopolymers are glassy systems. The glass transition temperature of these systems strongly depends on percentage of water, with water being simultaneously an intrinsic element of systems' ordered structure and a plasticizer of its amorphous state. On the base of the absolute values of heat capacities for biopolymer-water systems as a whole, heat capacities for biopolymers themselves were calculated as functions on water concentration at fixed temperatures. The S-shaped change of heat capacity observed on diagrams of state both for native and denatured biopolymers is the manifestation of biopolymers' passing through the vitrification region, as it occurs for denatured samples at heating.

  4. The transition to the metallic state in low density hydrogen.

    Science.gov (United States)

    McMinis, Jeremy; Morales, Miguel A; Ceperley, David M; Kim, Jeongnim

    2015-11-21

    Solid atomic hydrogen is one of the simplest systems to undergo a metal-insulator transition. Near the transition, the electronic degrees of freedom become strongly correlated and their description provides a difficult challenge for theoretical methods. As a result, the order and density of the phase transition are still subject to debate. In this work, we use diffusion quantum Monte Carlo to benchmark the transition between paramagnetic and anti-ferromagnetic body centered cubic atomic hydrogen in its ground state. We locate the density of the transition by computing the equation of state for these two phases and identify the phase transition order by computing the band gap near the phase transition. These benchmark results show that the phase transition is continuous and occurs at a Wigner-Seitz radius of rs = 2.27(3) a0. We compare our results to previously reported density functional theory, Hedin's GW approximation, and dynamical mean field theory results.

  5. Modeling the nonlinear PMMA behavior near glass transition temperature: application to its thermoforming

    Science.gov (United States)

    Gilormini, P.; Chevalier, L.; Régnier, G.

    2011-01-01

    Using suitable constitutive equations, numerical simulation allows predicting the properties of transparencies that are thermoformed near their glass transition temperature. Such equations are presented, which describe the nonlinear viscoelastic behavior of poly(methyl methacrylate) at large deformations near glass transition. The simulation of the thermoforming of a transparency at constant and uniform temperature is performed and compared with experimental results.

  6. Effects of density difference of constituent elements on glass formation in TiCu-based bulk metallic glasses

    Institute of Scientific and Technical Information of China (English)

    Zhongyan Zhang; Zengbao Jiao; Jie Zhou; Yuan Wu; Hui Wang; Xiongjun Liu; Zhaoping Lun

    2013-01-01

    Glass formation is generally favored by a large atomic size mismatch among constituent elements, which usually leads to large density differences among them as well. During melting, elemental segregation occurs due to Stokes’ law and then inevitably affects glass formation. In this paper, such effects on glass-forming ability in a TiCu-based alloy system have been demonstrated. In the bulk glass-forming composition Ti43Cu42Hf14Si1, macroscopic segregation of Si was observed in the as-melted ingots and silicon was completely depleted in the as-cast rods. In another Ti33Cu47Ni8Zr11Si1 alloy, nevertheless, the effects of density differences among the constituent elements were less severe. It was also confirmed that using proper pre-alloys could be an effective way in alleviating the side effects of the elemental segregation.

  7. Direct investigations of deformation and yield induced structure transitions in polyamide 6 below glass transition temperature with WAXS and SAXS

    DEFF Research Database (Denmark)

    Guo, Huilong; Wang, Jiayi; Zhou, Chengbo;

    2015-01-01

    Deformation and yield induced structure transitions of polyamide 6 (PA6) were detected with the combination of the wide- and small-angle X-ray scattering (WAXS and SAXS) at 30 degrees C below glass transition temperature (T-g) of PA6. During deformation, gamma-alpha phase transition was found at ...

  8. Evaluation of Glass Density to Support the Estimation of Fissile Mass Loadings from Iron Concentrations in SB6 Glasses

    Energy Technology Data Exchange (ETDEWEB)

    Edwards, T.; Peeler, D.

    2010-12-15

    The Department of Energy - Savannah River (DOE-SR) previously provided direction to Savannah River Remediation (SRR) to maintain fissile concentration in glass below 897 g/m{sup 3}. In support of the guidance, the Savannah River National Laboratory (SRNL) provided a technical basis and a supporting Microsoft{reg_sign} Excel{reg_sign} spreadsheet for the evaluation of fissile loading in Sludge Batch 5 glass based on the Fe concentration in glass as determined by the measurements from the Slurry Mix Evaporator (SME) acceptability analysis. SRR has since requested that SRNL provide the necessary information to allow SRR to update the Excel spreadsheet so that it may be used to maintain fissile concentration in glass below 897 g/m{sup 3} during the processing of Sludge Batch 6 (SB6). One of the primary inputs into the fissile loading spreadsheet includes a bounding density for SB6-based glasses. Based on the measured density data of select SB6 variability study glasses, SRNL recommends that SRR utilize the 99/99 Upper Tolerance Limit (UTL) density value at 38% WL (2.823 g/cm{sup 3}) as a bounding density for SB6 glasses to assess the fissile concentration in this glass system. That is, the 2.823 g/cm{sup 3} is recommended as a key (and fixed) input into the fissile concentration spreadsheet for SB6 processing. It should be noted that no changes are needed to the underlying structure of the Excel based spreadsheet to support fissile assessments for SB6. However, SRR should update the other key inputs to the spreadsheet that are based on fissile and Fe concentrations reported from the SB6 Waste Acceptance Product Specification (WAPS) sample. The purpose of this technical report is to present the density measurements that were determined for the SB6 variability study glasses and to conduct a statistical evaluation of these measurements to provide a bounding density value that may be used as input to the Excel{reg_sign} spreadsheet to be employed by SRR to maintain the

  9. Glass fiber addition strengthens low-density ablative compositions

    Science.gov (United States)

    Chandler, H. H.

    1974-01-01

    Approximately 15% of E-glass fibers was added to compositions under test and greatly improved char stability. Use of these fibers also reduced thermal strains which, in turn, minimized char shrinkage and associated cracks, subsurface voids, and disbonds. Increased strength allows honeycomb core reinforcement to be replaced by equivalent amount of glass fibers.

  10. Glass transition and crystallization process of hard magnetic bulk Nd60Al10Fe20Co10 metallic glass

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    Glass transition and crystallization process of bulk Nd60Al10Fe20Co10 metallic glass were investigated by means of dynamic mechanical thermal analysis (DMTA), differential scanning calorimetry (DSC), X-ray diffraction (XRD) and scanning electronic microscopy (SEM). It is shown that the glass transition and onset crystallization temperature determined by DMTA at a heating rate of 0.167 K/s are 480 and 588 K respectively. The crystallization process of the metallic glass is concluded as follows: amorphous α→α′+metastable FeNdAl novel phase →α′+primary δ phase→primary δ phase+eutectic δ phase Nd3Al phase+Nd3Co phase. The appearance of hard magnetism in this alloy is ascribed to the presence of amorphous phase with highly relaxed structure. The hard magnetism disappeared after the eutectic crystallization of amorphous phase.

  11. Mobility restrictions and glass transition behaviour of an epoxy resin under confinement.

    Science.gov (United States)

    Djemour, A; Sanctuary, R; Baller, J

    2015-04-07

    Confinement can have a big influence on the dynamics of glass formers in the vicinity of the glass transition. Already 40 to 50 K above the glass transition temperature, thermal equilibration of glass formers can be strongly influenced by the confining substrate. We investigate the linear thermal expansion and the specific heat capacity cp of an epoxy resin (diglycidyl ether of bisphenol A, DGEBA) in a temperature interval of 120 K around the glass transition temperature. The epoxy resin is filled into controlled pore glasses with pore diameters between 4 and 111 nm. Since DGEBA can form H-bonds with silica surfaces, we also investigate the influence of surface silanization of the porous substrates. In untreated substrates a core/shell structure of the epoxy resin can be identified. The glass transition behaviours of the bulk phase and that of the shell phase are different. In silanized substrates, the shell phase disappears. At a temperature well above the glass transition, a second transition is found for the bulk phase - both in the linear expansion data as well as in the specific heat capacity. The cp data do not allow excluding the glass transition of a third phase as being the cause for this transition, whereas the linear expansion data do so. The additional transition temperature is interpreted as a separation between two regimes: above this temperature, macroscopic flow of the bulk phase inside the porous structure is possible to balance the mismatch of thermal expansion coefficients between DGEBA and the substrate. Below the transition temperature, this degree of freedom is hindered by geometrical constraints of the porous substrates. Moreover, this second transition could also be found in the linear expansion data of the shell phase.

  12. The glass transition temperature and microstructure of polyurethane/epoxy resin interpenetrating polymer networks nanocomposites

    Institute of Scientific and Technical Information of China (English)

    JIA Qingming; ZHENG Maosheng; SHEN Renjie; CHEN Hongxiang

    2006-01-01

    Nanocomposites with various contents of organophilic montmorillonite (oMMT) have been prepared by adding oMMT to interpenetrating polymer networks (IPNs) of polyurethane and epoxy resin (PU/EP) which had been prepared by a sequential polymeric technique. DSC experiment indicates a novel phenomenon that the glass transition temperature (Tg) of the nanocomposites increases with the oMMT content up to 3 %, then decreases with further increasing oMMT content. In order to explain this phenomenon, crosslink density, hydrogen bonding in the hard segments, crystallization of the nanocomposites and the exfoliation degree of oMMT in the nanocomposites have been investigated by swelling method, FT-IR, XRD, SEM and TEM, respectively. The results indicate that the crosslink density and the hydrogen bonding index of the nanocomposites increase, but the crystallization degree of the nanocomposites decreases with increasing oMMT content. In addition, oMMT improves the network structure of PU/EP.

  13. Analysis of early medieval glass beads - Glass in the transition period

    Science.gov (United States)

    Šmit, Žiga; Knific, Timotej; Jezeršek, David; Istenič, Janka

    2012-05-01

    Glass beads from graves excavated in Slovenia and dated archaeologically to the 7th-10th century AD were analysed by the combined PIXE-PIGE method. The results indicate two groups of glass; natron glass made in the Roman tradition and glass made with alkalis from the ash of halophytic plants, which gradually replaced natron glass after c. 800 AD. The alkalis used in the second group of glass seem to be in close relation to a variant of the Venetian white glass that appeared several centuries later. The origin of this glass may be traced to glass production in Mesopotamia and around the Aral Sea. All the mosaic beads with eye decoration, as well as most of the drawn-segmented and drawn-cut beads analysed, are of plant-ash glass, which confirms their supposed oriental origin.

  14. Analysis of early medieval glass beads - Glass in the transition period

    Energy Technology Data Exchange (ETDEWEB)

    Smit, Ziga, E-mail: ziga.smit@ijs.si [Faculty of Mathematics and Physics, University of Ljubljana, Jadranska 19, SI-1000 Ljubljana (Slovenia); Jozef Stefan Institute, Jamova 39, P.O.B. 3000, SI-1001 Ljubljana (Slovenia); Knific, Timotej [National Museum of Slovenia, Presernova 20, SI-1000 Ljubljana (Slovenia); Jezersek, David [Jozef Stefan Institute, Jamova 39, P.O.B. 3000, SI-1001 Ljubljana (Slovenia); Istenic, Janka [National Museum of Slovenia, Presernova 20, SI-1000 Ljubljana (Slovenia)

    2012-05-01

    Glass beads from graves excavated in Slovenia and dated archaeologically to the 7th-10th century AD were analysed by the combined PIXE-PIGE method. The results indicate two groups of glass; natron glass made in the Roman tradition and glass made with alkalis from the ash of halophytic plants, which gradually replaced natron glass after c. 800 AD. The alkalis used in the second group of glass seem to be in close relation to a variant of the Venetian white glass that appeared several centuries later. The origin of this glass may be traced to glass production in Mesopotamia and around the Aral Sea. All the mosaic beads with eye decoration, as well as most of the drawn-segmented and drawn-cut beads analysed, are of plant-ash glass, which confirms their supposed oriental origin.

  15. Effect of UV exposure on photochromic glasses doped with transition metal oxides

    Science.gov (United States)

    El-Zaiat, S. Y.; Medhat, M.; Omar, Mona F.; Shirif, Marwa A.

    2016-07-01

    Silver halide photochromic glasses doped with one of the transition metal oxides, (Ti O2) , (CoO) ,(Cr2 O3) are prepared using the melt quench technique. Glass samples are exposed to a UV source for 20 min. Spectral reflectance and transmittance at normal incidence of the prepared glasses are recorded before and after UV exposure with a double beam spectrophotometer in the spectral range 200-2500 nm. Dispersion parameters such as: single oscillator energy, dispersion energy and Abbe's number are deduced and compared. Absorption dispersion parameters, like optical energy gap for direct and indirect transitions, Urbach energy and steepness parameter, are deduced for the different glass prepared. Reflection loss, molar refractivity and electronic polarizability are deduced and compared. The effect of UV light exposure of these glasses on transmittance, reflectance, the linear and the predicted nonlinear optical parameters are investigated and discussed for the three transition metals. Nonlinear parameters increase in the three glass samples after UV exposure.

  16. Predict the glass transition temperature of glycerol-water binary cryoprotectant by molecular dynamic simulation.

    Science.gov (United States)

    Li, Dai-Xi; Liu, Bao-Lin; Liu, Yi-shu; Chen, Cheng-lung

    2008-04-01

    Vitrification is proposed to be the best way for the cryopreservation of organs. The glass transition temperature (T(g)) of vitrification solutions is a critical parameter of fundamental importance for cryopreservation by vitrification. The instruments that can detect the thermodynamic, mechanical and dielectric changes of a substance may be used to determine the glass transition temperature. T(g) is usually measured by using differential scanning calorimetry (DSC). In this study, the T(g) of the glycerol-aqueous solution (60%, wt/%) was determined by isothermal-isobaric molecular dynamic simulation (NPT-MD). The software package Discover in Material Studio with the Polymer Consortium Force Field (PCFF) was used for the simulation. The state parameters of heat capacity at constant pressure (C(p)), density (rho), amorphous cell volume (V(cell)) and specific volume (V(specific)) and radial distribution function (rdf) were obtained by NPT-MD in the temperature range of 90-270K. These parameters showed a discontinuity at a specific temperature in the plot of state parameter versus temperature. The temperature at the discontinuity is taken as the simulated T(g) value for glycerol-water binary solution. The T(g) values determined by simulation method were compared with the values in the literatures. The simulation values of T(g) (160.06-167.51K) agree well with the DSC results (163.60-167.10K) and the DMA results (159.00K). We drew the conclusion that molecular dynamic simulation (MDS) is a potential method for investigating the glass transition temperature (T(g)) of glycerol-water binary cryoprotectants and may be used for other vitrification solutions.

  17. Conformational Fluctuations of Polymers in a Melt Associated with Glass Transition

    Science.gov (United States)

    Iwaoka, Nobuyuki; Takano, Hiroshi

    2017-03-01

    The conformational fluctuations of a glassy short polymer melt are studied by coarse-grained molecular dynamics simulations and principal component analysis (PCA). The distribution of PCA eigenvalues, which measure static fluctuations of the polymers, shows a clear difference between above and below the conventional glass transition temperature Tg. The approximate conformational entropy of the polymers also indicates a transition near Tg. This is evidence that the static properties of polymers in the melt signal the glass transition.

  18. Replica symmetry breaking transition of the weakly anisotropic Heisenberg spin glass in magnetic fields.

    Science.gov (United States)

    Imagawa, Daisuke; Kawamura, Hikaru

    2004-02-20

    The spin and the chirality orderings of the three-dimensional Heisenberg spin glass with the weak random anisotropy are studied under applied magnetic fields by equilibrium Monte Carlo simulations. A replica symmetry breaking transition occurs in the chiral sector accompanied by the simultaneous spin-glass order. The ordering behavior differs significantly from that of the Ising spin glass, despite the similarity in the global symmetry. Our observation is consistent with the spin-chirality decoupling-recoupling scenario of a spin-glass transition.

  19. The Gardner Transition: A new approach for understanding low-temperature glasses

    Science.gov (United States)

    Charbonneau, Patrick

    Recent theoretical advances in the mean-field theory of glasses predict the existence deep in the glass phase of a novel phase transition, a so-called Gardner transition. This transition signals the emergence of a complex free energy landscape composed of a marginally stable hierarchy of sub-basins within a broad glass metabasin. It is thus the onset of marked changes in thermal and transport properties of glasses, and ultimately leads to the unusual critical behavior at jamming. The Gardner transition itself is immediately related to a diverging (i) characteristic relaxation time, (ii) caging susceptibility and (iii) correlation length of the caging heterogeneity as well as aging, even in well-thermalized glasses. We have detected some of these signatures both in a mean-field model and in standard hard-sphere glass formers. We find the results to quantitatively agree with theory in the former and qualitatively so in the latter, which suggest that the transition should be detectable in a wide array of numerical and experimental systems. Interestingly, although the Gardner transitions is primarily associated with structural glass formers, we also find features of the transition in crystals of polydisperse particles once the landscape becomes rough.

  20. The Calorimetric Glass Transition of Polystyrene Ultrathin Films

    Science.gov (United States)

    Gao, Siyang; Koh, Yung; Simon, Sindee; Texas Tech University Team

    2013-03-01

    The glass transition temperature (Tg) for nanoconfined materials have been widely studied since the early 1990s. For supported polystyrene ultrathin films, Tg differs from bulk value. Recent work has attributed nanoconstrained Tg effects to artifact. In this study, we attempted to resolve this controversy and measure Tg for single polystyrene ultrathin films using Flash DSC. Films have been prepared in two ways: spincast films placed on a layer of inert oil or grease and films directly spincast on the back of the calorimetric chip. For the films on oil or on grease, the 160 nm thick films show no Tg depression. On the other hand, thinner films on oil and on grease show a Tg depression which decreases with increasing cooling rate. The depression reverts to the bulk values over the course of a day at 160 °C due to dewetting and thickening. For directly spincast films, no Tg depression is observed, consistent with results from other nanocalorimetry work. Our results are consistent with literature results that Tg decreases with decreasing substrate surface energy, and they also demonstrate that the Tg depression observed is not due to degradation or to plasticization effects.

  1. Interparticle interactions mediated superspin glass to superferromagnetic transition in Ni-bacterial cellulose aerogel nanocomposites

    Science.gov (United States)

    Thiruvengadam, V.; Vitta, Satish

    2016-06-01

    The interparticle interactions in the magnetic nanocomposites play a dominant role in controlling phase transitions: superparamagnetic to superspin glass and to superferromagnetic. These interactions can be tuned by controlling the size and number density of nanoparticles. The aerogel composites, 0.3Ni-BC and 0.7Ni-BC, consisting of Ni nanoparticles distributed in the bacterial cellulose have been used as a model system to study these interactions. Contrary to conventional approach, size of Ni-nanoparticles is not controlled and allowed to form naturally in bacterial cellulose template. The uncontrolled growth of Ni results in the formation of nanoparticles with 3 different size distributions - 100 nm particles in voids formed by reticulate structure. At room temperature, the composites exhibit a weakly ferromagnetic behaviour with a coercivity of 40 Oe, which increases to 160 Oe at 10 K. The transition from weakly ferromagnetic state to superferromagnetic state at low temperatures is mediated by the superspin glass state at intermediate temperatures via the interparticle interactions aided by nanoparticles present along the length of fibres. A temperature dependent microstructural model has been developed to understand the magnetic behaviour of nanocomposite aerogels.

  2. Glass heat capacity and its abrupt change in glass transition region

    DEFF Research Database (Denmark)

    Yue, Yuanzheng; Smedskjær, Morten Mattrup; Mauro, John C.

    substitution) or glass systems of different bonding types (covalent, metallic and ionic bonds). In addition, we discuss how chemical bond is associated with glass Cp (at T ... cover a large range of glass formers from metallic to non-metallic glasses. To conduct this study we convert the units of all the Cp data from J/mol K and J/g K to J/g-atom K. This study will provide insight into the correlations among chemical bonding, microstructure structure, liquid fragility, glass...

  3. The Effects of Electron Radiation on the Glass Transition Temperature of a Polyetherimide.

    Science.gov (United States)

    Kern, Kristen Tulloch

    The effects of electron radiation on a polyetherimide (PEI), Ultem^{cdot}, were investigated. In particular, the changes in the glass transition temperature (T_{g} ) with absorbed radiation dose were studied. The polymer was exposed to mono-energetic beams of 100-keV electrons and 1.0-MeV electrons for doses up to 100 megagray (MGy). Dosimetry for the exposures was based on Monte -Carlo simulations of the transfer of energy from an energetic electron to the polymer and on comparison to Nylon standards. Dynamic mechanical analysis was used to determine the T _{g} for non-exposed PEI and the changes in T_{g} resulting from irradiation. The T_{g} did not change significantly for doses up to and including 75 MGy, while a significant increase in T_ {g} occurred for a dose of 100 MGy. The cross-link and chain scission densities in the irradiated PEI were determined using infrared spectroscopy. The cross -link density increased with dose for all doses investigated. The chain scission density increased with dose for doses up to 75 MGy, but was lower for a dose of 100 MGy than for a dose of 75 MGy. Radical population kinetics, based in part on data from an electron paramagnetic resonance study, were correlated with the cross-link density and chain scission density to investigate the mechanism for the observed density variations with dose. The radical population simulations suggest that chain scissioning occurs less readily when the average radical separation during the exposure is less than three molecular radii. Finally, a model for the combined effects of cross-linking and chain scissioning is proposed which combines a statistical-mechanical model for the change in T_{g} with cross-link density and a free-volume model for the change in T _{g} with chain scission density.

  4. Predicting Glass Transition Temperature of Polyethylene/Graphene Nanocomposites by Molecular Dynamic Simulation

    Institute of Scientific and Technical Information of China (English)

    SHENG Yan-zhen; YANG Hua; LI Jun-yin; SUN Miao

    2013-01-01

    The glass transition temperature of polyethylene/graphene nanocomposites was investigated by molecular dynamic simulation.The specific volumes of three systems(polyethylene,polyethylene with a small graphene sheet and two small graphene sheets) were examined as a function of temperature.We found that the glass transition temperature decreases with increasing graphene.Then the van der Waals energy changes obviously with increasing graphene and the torsion energy also plays an important role in the glass transition of polymer.The radial distribution functions of the inter-molecular carbon atoms suggest the interaction between PE and graphene weakens with increasing graphene.These indicate that graphene can prompt the motion of chain segments of polymer and decrease the glass transition temperature (Tg) of polymer.

  5. Resolution of conflicting views on thermodynamics of glass transition: A unified model

    Indian Academy of Sciences (India)

    K T Jacob; Sagar Prabhudev; R M Mallya

    2010-10-01

    Classical description of thermodynamic properties during glass transition has been questioned by the entropy-loss model. The uncompensated loss of entropy at the glass transition temperature and zero residual entropy is at the heart of the controversy. Both the models are critically reviewed. A unified model is presented which incorporates features of both entropy loss and residual entropy. It implies two different types of contributions to the entropy of the supercooled liquid, one of which vanishes at the transition and the other which contributes to residual entropy. Entropy gain during spontaneous relaxation of glass, and the nature of heat capacity ‘hysteresis’ during cooling and heating through the glass transition range support the proposed model. Experiments are outlined for differentiating between the models.

  6. Relationship between Compostion,Density and Refractive Index for Heavy Metal Fluoride Glasses

    Institute of Scientific and Technical Information of China (English)

    ShaukatS.F; HobsonP.R.; 等

    2001-01-01

    The density and the refractive index for various compositions of heavy metal fluoride(HMF) glasses,used to make low-loss optical wave-guides,have been measured by standard archimedes method and by using as Pulfrich refrctometer respectively.The density as a function of composition is calculated considering the effective volume of the ions contained in the glass to be invariant.The refractive index as a function of composition is also calcuated.based on the Lorenz-Lorentz equation,by computing the electronic polarizability of HMF glasses.All calculated results are in good agreement with the observed data.

  7. Transition matrices and orbitals from reduced density matrix theory

    Energy Technology Data Exchange (ETDEWEB)

    Etienne, Thibaud [Université de Lorraine – Nancy, Théorie-Modélisation-Simulation, SRSMC, Boulevard des Aiguillettes 54506, Vandoeuvre-lès-Nancy (France); CNRS, Théorie-Modélisation-Simulation, SRSMC, Boulevard des Aiguillettes 54506, Vandoeuvre-lès-Nancy (France); Unité de Chimie Physique Théorique et Structurale, Université de Namur, Rue de Bruxelles 61, 5000 Namur (Belgium)

    2015-06-28

    In this contribution, we report two different methodologies for characterizing the electronic structure reorganization occurring when a chromophore undergoes an electronic transition. For the first method, we start by setting the theoretical background necessary to the reinterpretation through simple tensor analysis of (i) the transition density matrix and (ii) the natural transition orbitals in the scope of reduced density matrix theory. This novel interpretation is made more clear thanks to a short compendium of the one-particle reduced density matrix theory in a Fock space. The formalism is further applied to two different classes of excited states calculation methods, both requiring a single-determinant reference, that express an excited state as a hole-particle mono-excited configurations expansion, to which particle-hole correlation is coupled (time-dependent Hartree-Fock/time-dependent density functional theory) or not (configuration interaction single/Tamm-Dancoff approximation). For the second methodology presented in this paper, we introduce a novel and complementary concept related to electronic transitions with the canonical transition density matrix and the canonical transition orbitals. Their expression actually reflects the electronic cloud polarisation in the orbital space with a decomposition based on the actual contribution of one-particle excitations from occupied canonical orbitals to virtual ones. This approach validates our novel interpretation of the transition density matrix elements in terms of the Euclidean norm of elementary transition vectors in a linear tensor space. A proper use of these new concepts leads to the conclusion that despite the different principles underlying their construction, they provide two equivalent excited states topological analyses. This connexion is evidenced through simple illustrations of (in)organic dyes electronic transitions analysis.

  8. Transition matrices and orbitals from reduced density matrix theory

    Science.gov (United States)

    Etienne, Thibaud

    2015-06-01

    In this contribution, we report two different methodologies for characterizing the electronic structure reorganization occurring when a chromophore undergoes an electronic transition. For the first method, we start by setting the theoretical background necessary to the reinterpretation through simple tensor analysis of (i) the transition density matrix and (ii) the natural transition orbitals in the scope of reduced density matrix theory. This novel interpretation is made more clear thanks to a short compendium of the one-particle reduced density matrix theory in a Fock space. The formalism is further applied to two different classes of excited states calculation methods, both requiring a single-determinant reference, that express an excited state as a hole-particle mono-excited configurations expansion, to which particle-hole correlation is coupled (time-dependent Hartree-Fock/time-dependent density functional theory) or not (configuration interaction single/Tamm-Dancoff approximation). For the second methodology presented in this paper, we introduce a novel and complementary concept related to electronic transitions with the canonical transition density matrix and the canonical transition orbitals. Their expression actually reflects the electronic cloud polarisation in the orbital space with a decomposition based on the actual contribution of one-particle excitations from occupied canonical orbitals to virtual ones. This approach validates our novel interpretation of the transition density matrix elements in terms of the Euclidean norm of elementary transition vectors in a linear tensor space. A proper use of these new concepts leads to the conclusion that despite the different principles underlying their construction, they provide two equivalent excited states topological analyses. This connexion is evidenced through simple illustrations of (in)organic dyes electronic transitions analysis.

  9. Transition matrices and orbitals from reduced density matrix theory.

    Science.gov (United States)

    Etienne, Thibaud

    2015-06-28

    In this contribution, we report two different methodologies for characterizing the electronic structure reorganization occurring when a chromophore undergoes an electronic transition. For the first method, we start by setting the theoretical background necessary to the reinterpretation through simple tensor analysis of (i) the transition density matrix and (ii) the natural transition orbitals in the scope of reduced density matrix theory. This novel interpretation is made more clear thanks to a short compendium of the one-particle reduced density matrix theory in a Fock space. The formalism is further applied to two different classes of excited states calculation methods, both requiring a single-determinant reference, that express an excited state as a hole-particle mono-excited configurations expansion, to which particle-hole correlation is coupled (time-dependent Hartree-Fock/time-dependent density functional theory) or not (configuration interaction single/Tamm-Dancoff approximation). For the second methodology presented in this paper, we introduce a novel and complementary concept related to electronic transitions with the canonical transition density matrix and the canonical transition orbitals. Their expression actually reflects the electronic cloud polarisation in the orbital space with a decomposition based on the actual contribution of one-particle excitations from occupied canonical orbitals to virtual ones. This approach validates our novel interpretation of the transition density matrix elements in terms of the Euclidean norm of elementary transition vectors in a linear tensor space. A proper use of these new concepts leads to the conclusion that despite the different principles underlying their construction, they provide two equivalent excited states topological analyses. This connexion is evidenced through simple illustrations of (in)organic dyes electronic transitions analysis.

  10. Critical test of the mode-coupling theory of the glass transition.

    Science.gov (United States)

    Berthier, Ludovic; Tarjus, Gilles

    2010-09-01

    In its common implementation, the mode-coupling theory of the glass transition predicts the time evolution of the intermediate scattering functions in viscous liquids on the sole basis of the structural information encoded in two-point density correlations. We provide a critical test of this property and show that the theory fails to describe the strong differences of dynamical behavior seen in two model liquids characterized by very similar pair-correlation functions. Because we use "exact" static information provided by numerical simulations, our results are a direct indication that some important information about the dynamics of viscous liquids is not captured by pair correlations and is thus not described by the mode-coupling theory, even in the temperature regime where the theory is usually applied.

  11. Structure, ionic conductivity and mobile carrier density in fast ionic conducting chalcogenide glasses

    Energy Technology Data Exchange (ETDEWEB)

    Yao, Wenlong [Iowa State Univ., Ames, IA (United States)

    2006-01-01

    This thesis consists of six sections. The first section gives the basic research background on the ionic conduction mechanism in glass, polarization in the glass, and the method of determining the mobile carrier density in glass. The proposed work is also included in this section. The second section is a paper that characterizes the structure of MI + M2S + (0.1 Ga2S3 + 0.9 GeS2) (M = Li, Na, K and Cs) glasses using Raman and IR spectroscopy. Since the ionic radius plays an important role in determining the ionic conductivity in glasses, the glass forming range for the addition of different alkalis into the basic glass forming system 0.1 Ga2S3 + 0.9 GeS2 was studied. The study found that the change of the alkali radius for the same nominal composition causes significant structure change to the glasses. The third section is a paper that investigates the ionic conductivity of MI + M2S + (0.1Ga2S3 + 0.9 GeS2) (M = Li, Na, K and Cs) glasses system. Corresponding to the compositional changes in these fast ionic conducting glasses, the ionic conductivity shows changes due to the induced structural changes. The ionic radius effect on the ionic conductivity in these glasses was investigated. The fourth section is a paper that examines the mobile carrier density based upon the measurements of space charge polarization. For the first time, the charge carrier number density in fast ionic conducting chalcogenide glasses was determined. The experimental impedance data were fitted using equivalent circuits and the obtained parameters were used to determine the mobile carrier density. The influence of mobile carrier density and mobility on the ionic conductivity was separated. The fifth section is a paper that studies the structures of low-alkali-content Na2S + B2S3 (x ≤ 0.2) glasses by neutron and synchrotron x-ray diffraction

  12. Effect of the metal-insulator transition on the spin-glass interaction

    Science.gov (United States)

    Hauser, J. J.; Felder, R. J.; Blitzer, L. D.

    1986-03-01

    The effect of the metal-insulator transition on the spin-glass interaction was studied by measuring the magnetic properties of (MnSi)O X as a function of oxygen content X. As X varies from 0 to 3.6 one changes from a metallic to an insulating spin-glass. The transition at X ≲ 1 is marked by a sharp decrease in the susceptibility and a change of the Curie-Weiss temperature (θ) from ferromagnetic to antiferromagnetic.

  13. Direct evidence of entropy driven fluid-like - glass-like transition in microgel suspensions

    Science.gov (United States)

    Guo, Yun Xia; Liu, Ying Dan; Liu, Riping; Tian, Yongjun; Chen, Ke; Wang, Li-Min

    2017-02-01

    The phase transitions in poly (N-isopropylacrylamide) (PNIPAM) microgel suspensions are studied using rheological and calorimetric measurements at various concentrations. Two transitions are resolved, one being the hydrophilic-hydrophobic transition imposed by the gain/release of H2O molecules in PNIPAM particles via H-bond interactions, the other the fluid-like - glass-like transition of the hydrated microgels. The relaxation behaviors in the frozen glass-like states are observed by monitoring the shear modulus upon aging. Nevertheless, no enthalpic signature is detected in the relaxation process, suggesting entropy-driven relaxation dynamics.

  14. The transition to the metallic state in low density hydrogen

    Energy Technology Data Exchange (ETDEWEB)

    McMinis, Jeremy; Morales, Miguel A. [Lawrence Livermore National Laboratory, Livermore, California 94550 (United States); Ceperley, David M. [Department of Physics, University of Illinois, Urbana, Illinois 61801 (United States); Kim, Jeongnim [Oak Ridge National Laboratory, Oak Ridge, Tennessee 37831 (United States)

    2015-11-21

    Solid atomic hydrogen is one of the simplest systems to undergo a metal-insulator transition. Near the transition, the electronic degrees of freedom become strongly correlated and their description provides a difficult challenge for theoretical methods. As a result, the order and density of the phase transition are still subject to debate. In this work, we use diffusion quantum Monte Carlo to benchmark the transition between paramagnetic and anti-ferromagnetic body centered cubic atomic hydrogen in its ground state. We locate the density of the transition by computing the equation of state for these two phases and identify the phase transition order by computing the band gap near the phase transition. These benchmark results show that the phase transition is continuous and occurs at a Wigner-Seitz radius of r{sub s} = 2.27(3) a{sub 0}. We compare our results to previously reported density functional theory, Hedin’s GW approximation, and dynamical mean field theory results.

  15. Effects of phase transition induced density fluctuations on pulsar dynamics

    Directory of Open Access Journals (Sweden)

    Partha Bagchi

    2015-07-01

    Full Text Available We show that density fluctuations during phase transitions in pulsar cores may have non-trivial effects on pulsar timings, and may also possibly account for glitches and anti-glitches. These density fluctuations invariably lead to non-zero off-diagonal components of the moment of inertia, leading to transient wobbling of star. Thus, accurate measurements of pulsar timing and intensity modulations (from wobbling may be used to identify the specific pattern of density fluctuations, hence the particular phase transition, occurring inside the pulsar core. Changes in quadrupole moment from rapidly evolving density fluctuations during the transition, with very short time scales, may provide a new source for gravitational waves.

  16. Nuclear shape transitions, level density, and underlying interactions

    CERN Document Server

    Karampagia, S

    2016-01-01

    The configuration interaction approach to nuclear structure uses the effective Hamiltonian in a finite orbital space. The various parts of this Hamiltonian and their interplay are responsible for specific features of physics including the shape of the mean field and level density. This interrelation is not sufficiently understood. We intend to study phase transitions between spherical and deformed shapes driven by different parts of the nuclear Hamiltonian and to establish the presence of the collective enhancement of the nuclear level density by varying the shell-model matrix elements. Varying the interaction matrix elements we define, for nuclei in the sd and pf shells, the sectors with spherical and deformed shapes. Using the moments method that does not require the full diagonalization we relate the shape transitions with the corresponding level density. Enhancement of the level density in the low-energy part of the spectrum is observed in clear correlation with a deformation phase transition induced main...

  17. Effect of Heating Rate on Glass Foaming: Transition to Bulk Foam

    Energy Technology Data Exchange (ETDEWEB)

    Hrma, Pavel R.

    2009-02-15

    Foaming of glass is an undesirable side effect of glass fining. According to a recent experimental study, the gas-phase volume in the melt heated at a constant rate dramatically increased with an increased rate of heating. This observation indicates that an increased rate of heating (a natural consequence of the increased processing rate experienced as a result of transition to oxy-fuel firing) may exert a substantial influence on glass foaming in advanced glass-melting furnaces. This paper attributes this effect to the change of mode of foam formation in response to an increased rate of heating.

  18. Quantum spin-glass transition in the two-dimensional electron gas

    Indian Academy of Sciences (India)

    Subir Sachdev

    2002-02-01

    We discuss the possibility of spin-glass order in the vicinity of the unexpected metallic state of the two-dimensional electron gas in zero applied magnetic field. An average ferromagnetic moment may also be present, and the spin-glass order then resides in the plane orthogonal to the ferromagnetic moment. We argue that a quantum transition involving the destruction of the spin-glass order in an applied in-plane magnetic field offers a natural explanation of some features of recent magnetoconductance measurements. We present a quantum field theory for such a transition and compute its mean field properties.

  19. Numerical detection of the Gardner transition in a mean-field glass former

    Science.gov (United States)

    Charbonneau, Patrick; Jin, Yuliang; Parisi, Giorgio; Rainone, Corrado; Seoane, Beatriz; Zamponi, Francesco

    2015-07-01

    Recent theoretical advances predict the existence, deep into the glass phase, of a novel phase transition, the so-called Gardner transition. This transition is associated with the emergence of a complex free energy landscape composed of many marginally stable sub-basins within a glass metabasin. In this study, we explore several methods to detect numerically the Gardner transition in a simple structural glass former, the infinite-range Mari-Kurchan model. The transition point is robustly located from three independent approaches: (i) the divergence of the characteristic relaxation time, (ii) the divergence of the caging susceptibility, and (iii) the abnormal tail in the probability distribution function of cage order parameters. We show that the numerical results are fully consistent with the theoretical expectation. The methods we propose may also be generalized to more realistic numerical models as well as to experimental systems.

  20. Irreversible transitions in the exchange-striction model of spin-glass state

    Science.gov (United States)

    Valkov, V. I.; Golovchan, A. V.

    2014-08-01

    Based on the assumption of a negative volume dependence of random exchange integrals, it is possible to switch to a compressible Sherrington-Kirkpatrick spin-glass model. Within the proposed model, temperature-pressure phase diagrams were calculated and pressure- and magnetic-field-induced first-order phase transitions from the initial paramagnetic and spin-glass states to the ferromagnetic state were predicted. It was shown that the application of pressure in the spin-glass state not only increases and shifts magnetic susceptibility, but also reduces the critical magnetic fields of irreversible induced phase transitions from the spin-glass to the ferromagnetic state. The obtained results are used to describe the spin-glass state in (Sm1-xGdx)0.55Sr0.45MnO3.

  1. Dependence of the width of the glass transition interval on cooling and heating rates

    Science.gov (United States)

    Schmelzer, Jürn W. P.; Tropin, Timur V.

    2013-01-01

    In a preceding paper [J. W. P. Schmelzer, J. Chem. Phys. 136, 074512 (2012), 10.1063/1.3685510], a general kinetic criterion of glass formation has been advanced allowing one to determine theoretically the dependence of the glass transition temperature on cooling and heating rates (or similarly on the rate of change of any appropriate control parameter determining the transition of a stable or metastable equilibrium system into a frozen-in, non-equilibrium state of the system, a glass). In the present paper, this criterion is employed in order to develop analytical expressions for the dependence of the upper and lower boundaries and of the width of the glass transition interval on the rate of change of the external control parameters. It is shown, in addition, that the width of the glass transition range is strongly correlated with the entropy production at the glass transition temperature. The analytical results are supplemented by numerical computations. Analytical results and numerical computations as well as existing experimental data are shown to be in good agreement.

  2. Insight into Structural Phase Transitions from Density Functional Theory

    Science.gov (United States)

    Ruzsinszky, Adrienn

    2014-03-01

    Structural phase transitions caused by high pressure or temperature are very relevant in materials science. The high pressure transitions are essential to understand the interior of planets. Pressure or temperature induced phase transitions can be relevant to understand other phase transitions in strongly correlated systems or molecular crystals.Phase transitions are important also from the aspect of method development. Lower level density functionals, LSDA and GGAs all fail to predict the lattice parameters of different polymorphs and the phase transition parameters at the same time. At this time only nonlocal density functionals like HSE and RPA have been proved to resolve the geometry-energy dilemma to some extent in structural phase transitions. In this talk I will report new results from the MGGA_MS family of meta-GGAs and give an insight why this type of meta-GGAs can give a systematic improvement of the geometry and phase transition parameters together. I will also present results from the RPA and show a possible way to improve beyond RPA.

  3. Electron Momentum Density and Phase Transition in ZnS

    Directory of Open Access Journals (Sweden)

    N. Munjal

    2013-01-01

    Full Text Available The electron momentum density distribution and phase transition in ZnS are reported in this paper. The calculations are performed on the basis of density functional theory (DFT based on the linear combination of atomic orbitals (LCAO method. To compare the theoretical Compton profile, the measurement on polycrystalline ZnS has been made using a Compton spectrometer employing 59.54 keV gamma rays. The spherically averaged theoretical Compton profile is in agreement with the measurement. On the basis of equal valence-electron-density Compton profiles, it is found that ZnS is less covalent as compared to ZnSe. The present study suggests zincblende (ZB to rocksalt (RS phase transition at 13.7 GPa. The calculated transition pressure is found in good agreement with the previous investigations.

  4. Testing the paradigms of the glass transition in colloids via dynamic simulation

    Science.gov (United States)

    Wang, Jialun; Peng, Xiaoguang; Li, Qi; McKenna, Gregory; Zia, Roseanna

    2016-11-01

    Upon cooling, molecular glass-formers undergo a glass transition during which viscosity appears to diverge, and the material transitions from a liquid to an amorphous solid. However, the new state is not an equilibrium phase: material properties such as enthalpy continue to evolve in time. Rather, the material evolves toward an "intransient" state, as measured by the Kovacs signature experiments, e.g. the intrinsic isotherm, which reveals a paradoxical dependence of transition time on quench depth, and suggests that whether the glass transition occurs at the beginning or end of this transition is an open question. Colloidal glass formers provide a natural way to model such behavior, owing to the disparity in time scales that allow tracking of particle dynamics. We interrogate these ideas via dynamic simulation of a hard-sphere colloidal glassy state induced by jumps in volume fraction. We explore three methods to model the jump: evaporation, aspiration, and particle-size jumps. During and following each jump, the positions, velocities, and particle-phase stress are tracked and utilized to characterize relaxation time scales and structural changes. Analogs for the intrinsic isotherms are developed. The results provide insight into the existence of an "ideal" glass transition.

  5. Spin glass transition in canonical AuFe alloys: A numerical study

    Science.gov (United States)

    Zhang, Kai-Cheng; Li, Yong-Feng; Liu, Gui-Bin; Zhu, Yan

    2012-05-01

    Although spin glass transitions have long been observed in diluted magnetic alloys, e.g. AuFe and CuMn alloys, previous numerical studies are not completely consistent with the experiment results. The abnormal critical exponents of the alloys remain still puzzling. By employing parallel tempering algorithm with finite-size scaling analysis, we investigated the phase transitions in canonical AuFe alloys. Our results strongly support that spin glass transitions occur at finite temperatures in the alloys. The calculated critical exponents agree well with those obtained from experiments.

  6. Kinetics of the glass transition of fragile soft colloidal suspensions

    Science.gov (United States)

    Saha, Debasish; Joshi, Yogesh M.; Bandyopadhyay, Ranjini

    2015-12-01

    Microscopic relaxation time scales are estimated from the autocorrelation functions obtained by dynamic light scattering experiments for Laponite suspensions with different concentrations (CL), added salt concentrations (CS), and temperatures (T). It has been shown in an earlier work [D. Saha, Y. M. Joshi, and R. Bandyopadhyay, Soft Matter 10, 3292 (2014)] that the evolutions of relaxation time scales of colloidal glasses can be compared with molecular glass formers by mapping the waiting time (tw) of the former with the inverse of thermodynamic temperature (1/T) of the latter. In this work, the fragility parameter D, which signifies the deviation from Arrhenius behavior, is obtained from fits to the time evolutions of the structural relaxation time scales. For the Laponite suspensions studied in this work, D is seen to be independent of CL and CS but is weakly dependent on T. Interestingly, the behavior of D corroborates the behavior of fragility in molecular glass formers with respect to equivalent variables. Furthermore, the stretching exponent β, which quantifies the width w of the spectrum of structural relaxation time scales, is seen to depend on tw. A hypothetical Kauzmann time tk, analogous to the Kauzmann temperature for molecular glasses, is defined as the time scale at which w diverges. Corresponding to the Vogel temperature defined for molecular glasses, a hypothetical Vogel time tα ∞ is also defined as the time at which the structural relaxation time diverges. Interestingly, a correlation is observed between tk and tα ∞ , which is remarkably similar to that known for fragile molecular glass formers. A coupling model that accounts for the tw-dependence of the stretching exponent is used to analyse and explain the observed correlation between tk and tα ∞ .

  7. Dynamic thermal expansivity of liquids near the glass transition

    DEFF Research Database (Denmark)

    Niss, Kristine; Gundermann, Ditte; Christensen, Tage Emil;

    2012-01-01

    Based on previous works on polymers by Bauer et al. [ Phys. Rev. E 61 1755 (2000)], this paper describes a capacitative method for measuring the dynamical expansion coefficient of a viscous liquid. Data are presented for the glass-forming liquid tetramethyl tetraphenyl trisiloxane (DC704) in the ......Based on previous works on polymers by Bauer et al. [ Phys. Rev. E 61 1755 (2000)], this paper describes a capacitative method for measuring the dynamical expansion coefficient of a viscous liquid. Data are presented for the glass-forming liquid tetramethyl tetraphenyl trisiloxane (DC704...

  8. Measuring the Densities of Aqueous Glasses at Cryogenic Temperatures.

    Science.gov (United States)

    Shen, Chen; Julius, Ethan F; Tyree, Timothy J; Dan, Ritwik; Moreau, David W; Thorne, Robert

    2017-06-28

    We demonstrate a method for determining the vitreous phase cryogenic temperature densities of aqueous mixtures, and other samples that require rapid cooling, to prepare the desired cryogenic temperature phase. Microliter to picoliter size drops are cooled by projection into a liquid nitrogen-argon (N2-Ar) mixture. The cryogenic temperature phase of the drop is evaluated using a visual assay that correlates with X-ray diffraction measurements. The density of the liquid N2-Ar mixture is adjusted by adding N2 or Ar until the drop becomes neutrally buoyant. The density of this mixture and thus of the drop is determined using a test mass and Archimedes principle. With appropriate care in drop preparation, management of gas above the liquid cryogen mixture to minimize icing, and regular mixing of the cryogenic mixture to prevent density stratification and phase separation, densities accurate to <0.5% of drops as small as 50 pL can readily be determined. Measurements on aqueous cryoprotectant mixtures provide insight into cryoprotectant action, and provide quantitative data to facilitate thermal contraction matching in biological cryopreservation.

  9. Thermodynamic signature of the dynamic glass transition in hard spheres

    NARCIS (Netherlands)

    Hermes, M|info:eu-repo/dai/nl/304829854; Dijkstra, M.|info:eu-repo/dai/nl/123538807

    2010-01-01

    We use extensive event-driven molecular dynamics simulations to study the thermodynamic, structural and dynamic properties of hard-sphere glasses. We determine the equation of state of the metastable fluid branch for hard spheres with a size polydispersity of 10%. Our results show a clear jump in

  10. Local order evolution of liquid Cu during glass transition under different pressures: A molecular dynamics study

    Energy Technology Data Exchange (ETDEWEB)

    Li, Y.D., E-mail: ydli@ustc.edu [School of Physics and Material Science, Anhui University, Hefei 230039 (China); Lu, Q.L. [School of Physics and Material Science, Anhui University, Hefei 230039 (China); Wang, C.C., E-mail: ccwang@ahu.edu.cn [School of Physics and Material Science, Anhui University, Hefei 230039 (China); Huang, S.G. [School of Physics and Material Science, Anhui University, Hefei 230039 (China); Liu, C.S. [Key Laboratory of Materials Physics, Institute of Solid State Physics, Chinese Academy of Sciences, P. O. Box 1129, Hefei 230031 (China)

    2013-01-01

    Based on the second-moment approximation of tight-binding scheme, constant-pressure molecular dynamics simulations are performed for liquid Cu during the glass transition under different pressures. By means of pair analysis technique and bond orientational order analysis we find that the dominant bond pairs are those related to fcc and hcp crystalline order not those representing icosahedral short-range order (ISRO) when the systems enter into glass transition region. Although these two kinds of bond pairs compete with each other, the system tends towards a mixture of crystalline bond pairs during glass formation. The effect on various bond pairs brought about by higher pressure is much less for liquids than for glasses. The experimental observation of a shoulder on the second peak of the structure factor for supercooled liquids might not merely attribute to ISRO, since supercooled liquid Cu exhibits such a shoulder, but does not display an enhanced icosahedral symmetry.

  11. Glass Transitions, Semiconductor-Metal Transitions, and Fragilities in Ge -V -Te (V =As , Sb) Liquid Alloys: The Difference One Element Can Make

    Science.gov (United States)

    Wei, Shuai; Coleman, Garrett J.; Lucas, Pierre; Angell, C. Austen

    2017-03-01

    Glass-transition temperatures (Tg ) and liquid fragilities are measured along a line of constant Ge content in the system Ge-As-Te, and contrasted with the lack of glass-forming ability in the twin system Ge-Sb-Te at the same Ge content. The one composition established as free of crystal contamination in the latter system shows a behavior opposite to that of a more covalent system. The comparison of Tg vs bond density in the three systems Ge-As-chalcogen differing in chalcogen, i.e., S, Se, or Te, shows that as the chalcogen becomes more metallic, i.e., in the order S ambient pressure) melting point.

  12. Aluminosilicate melts and glasses at 1 to 3 GPa: Temperature and pressure effects on recovered structural and density changes

    Science.gov (United States)

    Bista, S; Stebbins, Jonathan; Hankins, William B.; Sisson, Thomas W.

    2015-01-01

    In the pressure range in the Earth’s mantle where many basaltic magmas are generated (1 to 3 GPa) (Stolper et al. 1981), increases in the coordination numbers of the network-forming cations in aluminosilicate melts have generally been considered to be minor, although effects on silicon and particularly on aluminum coordination in non-bridging oxygen-rich glasses from the higher, 5 to 12 GPa range, are now well known. Most high-precision measurements of network cation coordination in such samples have been made by spectroscopy (notably 27Al and 29Si NMR) on glasses quenched from high-temperature, high-pressure melts synthesized in solid-media apparatuses and decompressed to room temperature and 1 bar pressure. There are several effects that could lead to the underestimation of the extent of actual structural (and density) changes in high-pressure/temperature melts from such data. For non-bridging oxygen-rich sodium and calcium aluminosilicate compositions in the 1 to 3 GPa range, we show here that glasses annealed near to their glass transition temperatures systematically record higher recovered increases in aluminum coordination and in density than samples quenched from high-temperature melts. In the piston-cylinder apparatus used, rates of cooling through the glass transition are measured as very similar for both higher and lower initial temperatures, indicating that fictive temperature effects are not the likely explanation of these differences. Instead, transient decreases in melt pressure during thermal quenching, which may be especially large for high initial run temperatures, of as much as 0.5 to 1 GPa, may be responsible. As a result, the equilibrium proportion of high-coordinated Al in this pressure range may be 50 to 90% greater than previously estimated, reaching mean coordination numbers (e.g., 4.5) that are probably high enough to significantly affect melt properties. New data on jadeite (NaAlSi2O6) glass confirm that aluminum coordination increase

  13. Series multilayer internal electrodes for high energy density glass-ceramic capacitors

    Institute of Scientific and Technical Information of China (English)

    LUO Jun; DU Jun; TANG Qun; MAO ChangHui

    2009-01-01

    The glass-ceramic dielectrics and internal electrode structures are investigated for improving the general energy storage density of capacitors.Calculation indicates that glass-ceramics acquired from glass matrix annealing at 850℃ for 3 hours can be approximately up to 17 J/cm3 in energy storage density.They are appropriately chosen as the dielectrics for preparing high energy storage density capacitors (HESDCs).A series multilayer structure of internal electrode is developed for the HESDCs,in which each layer is a combination of gold film and silver paste.This electrode structure promises the capacitor immune from the residual porosity defects inevitably brought by electrode paste sintering process,and specifically improves the electrical breakdown strength of the capacitor.Based on this new electrode structure,the energy storage densities of capacitors are increased by more than one order of magnitude compared with those traditional ones with only single layer of internal electrode.Thus,HESDCs based on the optimized glass-ceramic dielectrics can potentially achieve 7.5 J/cm3 in energy storage density,even taking into consideration the enlargement of total capacitor volumes while encapsulating practicable capacitors from dielectrics media.

  14. First-order phase transitions in spin-glass models with multiple paramagnetic solutions

    Energy Technology Data Exchange (ETDEWEB)

    Lozza, H.F. [Departamento de Fisica, FCEyN, Universidad de Buenos Aires, Pab. I, Ciudad Universitaria - (1428) Buenos Aires (Argentina)]. E-mail: homero@df.uba.ar

    2004-12-31

    The paramagnetic and the one-step replica-symmetry-breaking spin-glass solutions of a p-spin-glass model in the presence of a transverse field are studied in the neighborhood of the phase transition curve. Two qualitatively different regions are found in the phase diagram. For a transition temperature higher than a certain value Tc, the thermodynamic transition is of second order, otherwise it is of first order with latent heat. The temperature Tc is joined to a point in the phase diagram where a transition between two paramagnetic solutions happens. A discussion about the order of the thermodynamic-phase transition in the quantum random orthogonal model is presented.

  15. First-order phase transitions in spin-glass models with multiple paramagnetic solutions

    Science.gov (United States)

    Lozza, H. F.

    2004-12-01

    The paramagnetic and the one-step replica-symmetry-breaking spin-glass solutions of a p-spin-glass model in the presence of a transverse field are studied in the neighborhood of the phase transition curve. Two qualitatively different regions are found in the phase diagram. For a transition temperature higher than a certain value Tc, the thermodynamic transition is of second order, otherwise it is of first order with latent heat. The temperature Tc is joined to a point in the phase diagram where a transition between two paramagnetic solutions happens. A discussion about the order of the thermodynamic-phase transition in the quantum random orthogonal model is presented.

  16. POLYMER CHAIN DIFFUSION AT A TEMPERATURE BELOW ITS BULK GLASS TRANSITION TEMPERATURE

    Institute of Scientific and Technical Information of China (English)

    Tisato Kajiyama; Daisuke Kawaguchi; Keiji Tanaka

    2003-01-01

    In this study, it was examined whether the dynamics of polymer chains at a surface is different from that in the bulk, and if so, to what extent they differ in terms of surface glass transition temperature and diffusion coefficient. Obtained results clearly indicate that surface chains can travel for a relatively large distance in comparison with the characteristic length scale of usual segmental motion even at a temperature below its bulk glass transition temperature, Tbg. This is consistent with our previous results that the surface glass transition temperature is much lower than the corresponding Tbg.Also, it was experimentally revealed that there was a gradient of molecular motion in the surface region.

  17. Resolving glass transition in Te-based phase-change materials by modulated differential scanning calorimetry

    Science.gov (United States)

    Chen, Yimin; Mu, Sen; Wang, Guoxiang; Shen, Xiang; Wang, Junqiang; Dai, Shixun; Xu, Tiefeng; Nie, Qiuhua; Wang, Rongping

    2017-10-01

    Glass transitions of Te-based phase-change materials (PCMs) were studied by modulated differential scanning calorimetry. It was found that both Ge2Sb2Te5 and GeTe are marginal glass formers with ΔT (= T x ‑ T g) less than 2.1 °C when the heating rate is below 3 °C min‑1. The fragilities of Ge2Sb2Te5 and GeTe can be estimated as 46.0 and 39.7, respectively, around the glass transition temperature, implying that a fragile-to-strong transition would be presented in such Te-based PCMs. The above results provide direct experimental evidence to support the investigation of crystallization kinetics in supercooled liquid PCMs.

  18. Continuous Structural Transition in Glass-Forming Molten Titanate BaTi 2 O 5

    Energy Technology Data Exchange (ETDEWEB)

    Alderman, O. L. G.; Benmore, C. J.; Tamalonis, A.; Sendelbach, S.; Heald, S.; Weber, R.

    2016-12-01

    The structure of the model titanate glass former BaTi2O5 has been studied over a wide temperature (T) range in the molten, supercooled, and glassy states under conditions of aerodynamic levitation. Both high-energy X-ray diffraction and Ti K-edge X-ray absorption spectroscopy reveal a continuous structural transition involving reduction of the cation-oxygen (and oxygen-cation) average coordination numbers and bond lengths with increasing T. Ti-0 coordination in the moderately supercooled and equilibrium melt follows a linear trend n(Tio) = 5.4(1)- [3.5(7) x 10(-4)]T [K] (1300 <= T <= 1830 K, T-g = 960 K, T-m = 1660 K). Comparison to the melt-quenched glass implies an increase in partial derivative n(Tio)/partial derivative T at lower T, as T-g is approached from above. Both Ba-0 coordination and bond length also decrease at higher T, and the role of Ba addition is to reduce n(Tio) below its value in pure molten TiO2, which is related to the presence of density maxima in molten BaO-TiO2. Density measurements made by imaging of the levitated melt yielded rho(T) = 4.82(55)- 0.0004(3)T in units of K and g cm(-3). While BaTi2O5 glass likely consists of a fully connected Ti-0 network, free of nonbridging oxygen (NBO) [OTi1 and with at least 13(4)% [OTi3] triclusters, the 1835(40) K equilibrium melt contains at least 10(4)% NBO along with 90(4)% bridging oxygen [OTi2]. The results highlight the fact that glasses can be considered as structural analogues of melts only for those melts deeply supercooled into the glass transition region. The results imply possible fictive T dependence of titanate glass structure, suggesting applications as, e.g., laser written waveguides with large refractive indices and refractive index contrasts. The temperature-dependent structure further implies a super-Arrhenian melt viscosity with consequences for glass manufacture, titanate-rich slags produced in iron smelting, TiO2-bearing magmas, and by analogy silicate melts at high pressures, as

  19. Structural relaxation time and cooling rate of a melt in the glass transition region

    Science.gov (United States)

    Sanditov, D. S.; Sydykov, B. S.

    2015-03-01

    The nature of the parameter involved in the Bartenev equation qτg = C relating the cooling rate of a glass-forming melt to its structural relaxation time in the glass transition region is discussed on the basis of the Volkenshtein-Ptitsyn theory using a number of known relationships. It is established that parameter C for amorphous substances with the same fragility is linearly temperature dependent. This parameter is shown to equal the narrow temperature range δ T g characterizing the liquid-glass transition region (by Nemilov); i.e., C = δ T g. It is concluded that δ T g for most glassy systems is only ˜0.7% of the glass transition temperature T g. The narrowness of temperature range δ T g is explained by the small fluctuation volume fraction f g "frozen" at the glass transition temperature. The concept of a close relationship between constant C and the structural order at T g (i.e., the characteristic of the inner state of a nonequilibrium "frozen" amorphous system) is developed.

  20. Glass Transition Temperature of Water: from Simulations of Diffusion and Excess Entropy

    Institute of Scientific and Technical Information of China (English)

    LIU Jia; WANG Shu-Ying; ZHENG Cai-Ping; XIN Li-Juan; WANG Dan; SUN Min-Hua

    2007-01-01

    We report a computer simulation study of the glass transition of water with SP2 potential. The temperature dependences of the diffusion coefficient and the excess entropy on cooling process are calculated. It is found that both the diffusion coefficient and the excess entropy show a break point at 160K. Our results support the viewpoint that the glass transition temperature is 160K. According to the calculated viscosity, we obtain a fragility index of water to be 326, which is much larger than the value accepted before.

  1. Glass transition behavior of ternary disaccharide-ethylene glycol-water solutions

    Science.gov (United States)

    Yu, Tongxu; Zhao, Lishan; Wang, Qiang; Cao, Zexian

    2017-06-01

    Glass transition behavior of ternary disaccharide-ethylene glycol-water solutions, in reference to that of the binary combinations, has been investigated towards a better understanding of their cryoprotective ability. In water-deficient solutions, the disaccharides, including trehalose, sucrose and maltose, can associate with more than 100 ethylene glycol molecules to form amorphous complex, one order of magnitude larger than the corresponding hydration numbers. In water-rich solutions, a second glass transition emerges with increasing molar fraction of ethylene glycol, indicating the possible synergy of disaccharides and ethylene glycol in vitrification of the ternary aqueous solution.

  2. Density-temperature scaling of the fragility in a model glass-former

    DEFF Research Database (Denmark)

    Schrøder, Thomas; Sengupta, Shiladitya; Sastry, Srikanth

    2013-01-01

    Dynamical quantities e.g. diffusivity and relaxation time for some glass-formers may depend on density and temperature through a specific combination, rather than independently, allowing the representation of data over ranges of density and temperature as a function of a single scaling variable...... of the activation free energy in the Adam-Gibbs relation, is consistent with the exponent values obtained by other means....

  3. Thermal and fragility aspects of microwave synthesized glasses containing transition metal ions and heavy metal ions

    Science.gov (United States)

    Renuka, C.; Viswanatha, R.; Reddy, C. Narayana

    2017-02-01

    A simple, clean and energy efficient microwave heating route is used to prepare glasses in the systems xMnO-33(0.09PbCl2:0.91PbO)-(67-x) NaPO3 and xPbCl2-33PbO-(67-x) NaPO3 where 0.1 ≤ x ≤ 4 (mol%). Thermal data extracted from differential scanning calorimetry (DSC) thermograms are used to study the composition dependence of glass transition temperature (Tg), heat capacity, thermal stability and fragility. The decrease in glass transition temperature with modifier oxide (Na2O + MnO) content can be ascribed to network degradation and the volume increasing effect caused by PbCl2. The change in heat capacity of MnPb glass being greater than that of PbNP glass, suggests that MnPb glasses are more covalent than PbNP glasses. DSC thermograms taken at different heating rates (φ) reveal the dependence of Tg on φ, and the thermal stability of the glass increases due to MnO addition. Fragility aspects have also been studied by calculating the fragility functions ( {{Δ {{C}}_{{p}} }/{{{C}_{{pl}} }}{{and}}{[ {{NBO}} ]}/{{{V}_{{m}}3 {{T}}_{{g}} }}} ). Results obtained from both the fragility functions compare well and reveal the dependence of fragility functions on modifier content and PbCl2 mol%. Further, the decrease in Tg and Hv are suggested to be due to the increase in the number of non-bridging oxygens, which results in the lowering of stiffness and rigidity of the glass network. Analysis of the infrared spectra confirms that the glassy matrix is composed of P-O-P, P-O-Pb, P=O and P-O- bonding.

  4. Analyses of kinetic glass transition in short-range attractive colloids based on time-convolutionless mode-coupling theory

    Science.gov (United States)

    Narumi, Takayuki; Tokuyama, Michio

    2017-03-01

    For short-range attractive colloids, the phase diagram of the kinetic glass transition is studied by time-convolutionless mode-coupling theory (TMCT). Using numerical calculations, TMCT is shown to recover all the remarkable features predicted by the mode-coupling theory for attractive colloids: the glass-liquid-glass reentrant, the glass-glass transition, and the higher-order singularities. It is also demonstrated through the comparisons with the results of molecular dynamics for the binary attractive colloids that TMCT improves the critical values of the volume fraction. In addition, a schematic model of three control parameters is investigated analytically. It is thus confirmed that TMCT can describe the glass-glass transition and higher-order singularities even in such a schematic model.

  5. Topological deconfinement transition in QCD at finite isospin density

    Science.gov (United States)

    Kashiwa, Kouji; Ohnishi, Akira

    2017-09-01

    The confinement-deconfinement transition is discussed from topological viewpoints. The topological change of the system is achieved by introducing the dimensionless imaginary chemical potential (θ). Then, the non-trivial free-energy degeneracy becomes the signal of the deconfinement transition and it can be visualized by using the map of the thermodynamic quantities to the circle S1 along θ. To understand this "topological" deconfinement transition at finite real quark chemical potential (μR), we consider the isospin chemical potential (μiso) in the effective model of QCD. The phase diagram at finite μiso is identical with that at finite μR outside of the pion-condensed phase at least in the large-Nc limit via the well-known orbifold equivalence. In the present effective model, the topological deconfinement transition does not show a significant dependence on μiso and then we can expect that this tendency also appears at small μR. Also, the chiral transition and the topological deconfinement transition seems to be weakly correlated. If we will access lattice QCD data for the temperature dependence of the quark number density at finite μiso with θ = π / 3, our surmise can be judged.

  6. Sub-Tg features of glasses formed by cooling glycerol under pressure - Additional incompatibility of vibrational with configurational states in the depressurized, high density glass

    Science.gov (United States)

    Andersson, Ove; Johari, G. P.

    2016-11-01

    The vibrational state of a glass is naturally incompatible with its configurational state, which makes the glass structurally unstable. When a glass is kept at constant temperature, both the vibrational and configurational states of a glass change with time until it becomes metastable (equilibrium) liquid and the two states become compatible. The process, known as structural relaxation, occurs at a progressively higher rate during heating, and the properties of a glass change accordingly. We add to this incompatibility by depressurizing a glass that had been formed by cooling a liquid under a high pressure, p, and then investigate the effects of the added incompatibility by studying thermal conductivity, κ , and the heat capacity per unit volume ρ Cp of the depressurized glass. We use glycerol for the purpose and study first the changes in the features of κ and of ρ Cp during glass formation on cooling under a set of different p. We then partially depressurize the glass and study the effect of the p-induced instability on the features of κ and ρ Cp as the glass is isobarically heated to the liquid state. At a given low p, the glass configuration that was formed by cooling at high-p had a higher κ than the glass configuration that was formed by cooling at a low p. The difference is more when the glass is formed at a higher p and/or is depressurized to a lower p. On heating at a low p, its κ decreases before its glass-liquid transition range is reached. The effect is the opposite of the increase in κ observed on heating a glass at the same p under which it was formed. It is caused by thermally assisted loss of the added incompatibility of configurational and vibrational states of a high-p formed glass kept at low p. If a glass formed under a low-p is pressurized and then heated under high p, it would show the opposite effect, i.e., its κ would first increase to its high p value before its glass-to-liquid transition range.

  7. Spin-glass transition in Heisenberg spin system with ± J random bonds

    Science.gov (United States)

    Ghazali, A.; Lallemand, P.; Diep, H. T.

    1986-02-01

    We investigate by Monte Carlo simulations the simple cubic lattice with Heisenberg spins interacting via short range ± J random bonds for different antiferromagnetic bond concentrations x. We find that for x<0.25, a transition of the para-ferromagnetic type occurs. For 0.25⪅ x⩽0.5, the existence of a remanant magnetization and of a rounded peak of the specific heat together with other data support a paramagnetic-spin-glass transition at finite temperature.

  8. Water sorption and glass transition temperatures in red raspberry (Rubus idaeus)

    Energy Technology Data Exchange (ETDEWEB)

    Syamaladevi, Roopesh M. [Biological Systems Engineering Department, Washington State University, PO Box 646120, Pullman, WA 99164-6120 (United States); Sablani, Shyam S., E-mail: ssablani@wsu.edu [Biological Systems Engineering Department, Washington State University, PO Box 646120, Pullman, WA 99164-6120 (United States); Tang, Juming [Biological Systems Engineering Department, Washington State University, PO Box 646120, Pullman, WA 99164-6120 (United States); Powers, Joseph; Swanson, Barry G. [School of Food Science, Washington State University, PO Box 6463760, Pullman, WA 99164-6376 (United States)

    2010-05-20

    Water sorption isotherms and glass transition temperatures of raspberries were determined to understand interactions between water and biopolymers. Water adsorption and desorption isotherms of raspberries were determined with an isopiestic method. Thermal transitions of raspberries equilibrated at selected water concentrations using adsorption and desorption were determined by differential scanning calorimetry (DSC). The sorption isotherm data were modeled by BET and GAB equations, while the plasticizing influence of water on glass transition was modeled by the Gordon-Taylor equation. Equilibrium water concentrations varied at equivalent water activities during adsorption and desorption indicating occurrence of hysteresis and irreversibility of thermodynamic processes. The monolayer water concentrations of 0.099 and 0.108 kg water/kg dry raspberry solids obtained by BET and GAB models during desorption were larger than those during adsorption (0.059 and 0.074 kg water/kg dry raspberry solids). The glass transition temperature of raspberries decreased with increasing water concentrations. The Gordon-Taylor parameters T{sub gs} and k obtained for raspberries during adsorption were 42.6 {sup o}C and 4.73 and during desorption were 44.9 {sup o}C and 5.03, respectively. The characteristic glass transition temperature of the maximally freeze concentrated solution T{sup '}{sub g} was -63.1 {+-} 5 {sup o}C and the onset of ice crystal melting temperature T{sup '}{sub m} was -32.3 {+-} 0.4 {sup o}C. Although the water activity differed significantly at equivalent water concentrations obtained using absorption or desorption, the glass transition temperatures of raspberries were dependent on the concentration of water present not the method of equilibration.

  9. Asymptotic Expansions of Transition Densities for Hybrid Jump-Diffusions

    Institute of Scientific and Technical Information of China (English)

    Yuan-jin Liu; G.Yin

    2004-01-01

    A class of hybrid jump diffusions modulated by a Markov chain is considered in this work.The motivation stems from insurance risk models,and emerging applications in production planning and wireless communications.The models are hybrid in that they involve both continuous dynamics and discrete events.Under suitable conditions,asymptotic expansions of the transition densities for the underlying processes are developed.The formal expansions are validated and the error bounds obtained.

  10. Thermal Rounding of the Charge Density Wave Depinning Transition

    OpenAIRE

    Middleton, A. Alan

    1992-01-01

    The rounding of the charge density wave depinning transition by thermal noise is examined. Hops by localized modes over small barriers trigger ``avalanches'', resulting in a creep velocity much larger than that expected from comparing thermal energies with typical barriers. For a field equal to the $T=0$ depinning field, the creep velocity is predicted to have a {\\em power-law} dependence on the temperature $T$; numerical computations confirm this result. The predicted order of magnitude of t...

  11. Density shift and broadening of transition lines in antiprotonic helium

    Science.gov (United States)

    Bakalov; Jeziorski; Korona; Szalewicz; Tchoukova

    2000-03-13

    The density shift and broadening of the transition lines of antiprotonic helium have been evaluated in the impact approximation using an interatomic potential calculated ab initio with the symmetry-adapted perturbation theory. The results help to remove an uncertainty of up to 10 ppm in the laser spectroscopy data on antiprotonic helium and are of importance in experimental tests of bound state QED and CPT invariance.

  12. Density functional theory studies of transition metal nanoparticles in catalysis

    DEFF Research Database (Denmark)

    Greeley, Jeffrey Philip; Rankin, Rees; Zeng, Zhenhua

    2013-01-01

    Periodic Density Functional Theory calculations are capable of providing powerful insights into the structural, energetics, and electronic phenomena that underlie heterogeneous catalysis on transition metal nanoparticles. Such calculations are now routinely applied to single crystal metal surfaces...... and to subnanometer metal clusters. Descriptions of catalysis on truly nanosized structures, however, are generally not as well developed. In this talk, I will illustrate different approaches to analyzing nanocatalytic phenomena with DFT calculations. I will describe case studies from heterogeneous catalysis...

  13. Glass Transition Temperature Depression at the Percolation Threshold in Carbon Nanotube-Epoxy Resin and Polypyrrole-Epoxy Resin Composites

    OpenAIRE

    Barrau, Sophie; Demont, Philippe; Maraval, Céline; Bernès, Alain; Lacabanne, Colette

    2005-01-01

    The glass transition temperatures of conducting composites, obtained by blending carbon nanotubes (CNTs) or polypyrrole (PPy) particles with epoxy resin, were investigated by using both differential scanning calorimetry (DSC) and dynamical mechanical thermal analysis (DMTA). For both composites, dc and ac conductivity measurements revealed an electrical percolation threshold at which the glass transition temperature and mechanical modulus of the composites pass through a minimum.

  14. Thermalization calorimetry: A simple method for investigating glass transition and crystallization of supercooled liquids

    Directory of Open Access Journals (Sweden)

    Bo Jakobsen

    2016-05-01

    Full Text Available We present a simple method for fast and cheap thermal analysis on supercooled glass-forming liquids. This “Thermalization Calorimetry” technique is based on monitoring the temperature and its rate of change during heating or cooling of a sample for which the thermal power input comes from heat conduction through an insulating material, i.e., is proportional to the temperature difference between sample and surroundings. The monitored signal reflects the sample’s specific heat and is sensitive to exo- and endothermic processes. The technique is useful for studying supercooled liquids and their crystallization, e.g., for locating the glass transition and melting point(s, as well as for investigating the stability against crystallization and estimating the relative change in specific heat between the solid and liquid phases at the glass transition.

  15. Glass transition in driven granular fluids: A mode-coupling approach

    Science.gov (United States)

    Kranz, W. T.; Sperl, M.; Zippelius, A.

    2013-02-01

    We consider the stationary state of a fluid comprised of inelastic hard spheres or disks under the influence of a random, momentum-conserving external force. Starting from the microscopic description of the dynamics, we derive a nonlinear equation of motion for the coherent scattering function in two and three space dimensions. A glass transition is observed for all coefficients of restitution, ɛ, at a critical packing fraction φc(ɛ) below random close packing. The divergence of timescales at the glass transition implies a dependence on compression rate upon further increase of the density—similar to the cooling-rate dependence of a thermal glass. The critical dynamics for coherent motion as well as tagged particle dynamics is analyzed and shown to be nonuniversal with exponents depending on space dimension and degree of dissipation.

  16. Material properties and glass transition temperatures of different thermoplastic starches after extrusion processing

    NARCIS (Netherlands)

    Janssen, Léon P.B.M.; Karman, Andre P.; Graaf, Robbert A. de

    2003-01-01

    Four different starch sources, namely waxy maize, wheat, potato and pea starch were extruded with the plasticizer glycerol, the latter in concentrations of 15, 20 and 25% (w/w). The glass transition temperatures of the resulting thermoplastic products were measured by Dynamic Mechanical Thermal Anal

  17. Exploring the Origin of Fragile-to-Strong Transition in Some Glass-Forming Liquids

    DEFF Research Database (Denmark)

    Yue, Yuanzheng; Hu, L. N.

    2014-01-01

    The slow dynamics of glass-forming liquids is a complex subject of the condensed matter science. But the fragile-to-strong transition, which was observed not long ago [Ito, et al, Nature 1999], makes this subject even more complex since it is extremely challenging to directly probe the structural...

  18. Practical Considerations for Determination of Glass Transition Temperature of a Maximally Freeze Concentrated Solution.

    Science.gov (United States)

    Pansare, Swapnil K; Patel, Sajal Manubhai

    2016-08-01

    Glass transition temperature is a unique thermal characteristic of amorphous systems and is associated with changes in physical properties such as heat capacity, viscosity, electrical resistance, and molecular mobility. Glass transition temperature for amorphous solids is referred as (T g), whereas for maximally freeze concentrated solution, the notation is (T g'). This article is focused on the factors affecting determination of T g' for application to lyophilization process design and frozen storage stability. Also, this review provides a perspective on use of various types of solutes in protein formulation and their effect on T g'. Although various analytical techniques are used for determination of T g' based on the changes in physical properties associated with glass transition, the differential scanning calorimetry (DSC) is the most commonly used technique. In this article, an overview of DSC technique is provided along with brief discussion on the alternate analytical techniques for T g' determination. Additionally, challenges associated with T g' determination, using DSC for protein formulations, are discussed. The purpose of this review is to provide a practical industry perspective on determination of T g' for protein formulations as it relates to design and development of lyophilization process and/or for frozen storage; however, a comprehensive review of glass transition temperature (T g, T g'), in general, is outside the scope of this work.

  19. CORRELATION OF THE GLASS TRANSITION TEMPERATURE OF PLASTICIZED PVC USING A LATTICE FLUID MODEL

    Science.gov (United States)

    A model has been developed to describe the composition dependence of the glass transition temperature (Tg) of polyvinyl chloride (PVC) + plasticizer mixtures. The model is based on Sanchez-Lacombe equation of state and the Gibbs-Di Marzio criterion, which states that th...

  20. Cooperative length scale of Aroclor near its dynamic glass transition

    Energy Technology Data Exchange (ETDEWEB)

    Rizos, A.K. [Univ. of Crete, Heraklion (Greece); Ngai, K.L. [Naval Research Lab., Washington, DC (United States)

    1997-12-31

    Photon correlation spectroscopy in the depolarized mode has been used to monitor the reorientational dynamics of Aroclor (A1248) (polychlorinated biphenyls) that contain in solutions various amounts of low and high molecular weight (M{sub W}) polymers. For the high M{sub W} polymer/A1248 solutions the authors observe a very small dependence of the stretched exponential parameter {beta} on temperature. In contrast, the low M{sub W} polymer/A1248 solutions display a pronounced temperature dependence of {beta}. These preliminary experiments allow them to use the effect of modification of the solvent dynamics by added polymer to estimate the length scale of cooperative motion in glass forming systems from the size of the polymer chain.

  1. Glass transition and degree of conversion of a light-cured orthodontic composite

    Directory of Open Access Journals (Sweden)

    Michela M. D. S. Sostena

    2009-12-01

    Full Text Available OBJECTIVE: This study evaluated the glass transition temperature (Tg and degree of conversion (DC of a light-cured (Fill Magic versus a chemically cured (Concise orthodontic composite. MATERIAL AND METHODS: Anelastic relaxation spectroscopy was used for the first time to determine the Tg of a dental composite, while the DC was evaluated by infrared spectroscopy. The light-cured composite specimens were irradiated with a commercial LED light-curing unit using different exposure times (40, 90 and 120 s. RESULTS: Fill Magic presented lower Tg than Concise (35-84ºC versus 135ºC, but reached a higher DC. CONCLUSIONS: The results of this study suggest that Fill Magic has lower Tg than Concise due to its higher organic phase content, and that when this light-cured composite is used to bond orthodontic brackets, a minimum energy density of 7.8 J/cm² is necessary to reach adequate conversion level and obtain satisfactory adhesion.

  2. Physical stability of drugs after storage above and below the glass transition temperature: Relationship to glass-forming ability.

    Science.gov (United States)

    Alhalaweh, Amjad; Alzghoul, Ahmad; Mahlin, Denny; Bergström, Christel A S

    2015-11-10

    Amorphous materials are inherently unstable and tend to crystallize upon storage. In this study, we investigated the extent to which the physical stability and inherent crystallization tendency of drugs are related to their glass-forming ability (GFA), the glass transition temperature (Tg) and thermodynamic factors. Differential scanning calorimetry was used to produce the amorphous state of 52 drugs [18 compounds crystallized upon heating (Class II) and 34 remained in the amorphous state (Class III)] and to perform in situ storage for the amorphous material for 12h at temperatures 20°C above or below the Tg. A computational model based on the support vector machine (SVM) algorithm was developed to predict the structure-property relationships. All drugs maintained their Class when stored at 20°C below the Tg. Fourteen of the Class II compounds crystallized when stored above the Tg whereas all except one of the Class III compounds remained amorphous. These results were only related to the glass-forming ability and no relationship to e.g. thermodynamic factors was found. The experimental data were used for computational modeling and a classification model was developed that correctly predicted the physical stability above the Tg. The use of a large dataset revealed that molecular features related to aromaticity and π-π interactions reduce the inherent physical stability of amorphous drugs.

  3. Density Functional Theory for Phase-Ordering Transitions

    Energy Technology Data Exchange (ETDEWEB)

    Wu, Jianzhong [Univ. of California, Riverside, CA (United States)

    2016-03-30

    Colloids display astonishing structural and dynamic properties that can be dramatically altered by modest changes in the solution condition or an external field. This complex behavior stems from a subtle balance of colloidal forces and intriguing mesoscopic and macroscopic phase transitions that are sensitive to the processing conditions and the dispersing environment. Whereas the knowledge on the microscopic structure and phase behavior of colloidal systems at equilibrium is now well-advanced, quantitative predictions of the dynamic properties and the kinetics of phase-ordering transitions in colloids are not always realized. Many important mesoscopic and off-equilibrium colloidal states remain poorly understood. The proposed research aims to develop a new, unifying approach to describe colloidal dynamics and the kinetics of phase-ordering transitions based on accomplishments from previous work for the equilibrium properties of both uniform and inhomogeneous systems and on novel concepts from the state-of-the-art dynamic density functional theory. In addition to theoretical developments, computational research is designed to address a number of fundamental questions on phase-ordering transitions in colloids, in particular those pertinent to a competition of the dynamic pathways leading to various mesoscopic structures, off-equilibrium states, and crystalline phases. By providing a generic theoretical framework to describe equilibrium, metastable as well as non-ergodic phase transitions concurrent with the colloidal self-assembly processes, accomplishments from this work will have major impacts on both fundamental research and technological applications.

  4. Impact-Induced Glass Transition in Elastomeric Coatings

    Science.gov (United States)

    Roland, C. M.

    2013-03-01

    When an elastomer layer is applied to the front surface of steel, the resistance to penetration by hard projectiles increases significantly. It is not obvious why a soft polymer should affect this property of metals, and most rubbers do not. However, we have found that a few are very effective; the requirement is that the polymer undergo a viscoelastic phase transition upon impact. This means that the frequency of its segmental dynamics correspond to the impact frequency. The latter is estimated as the ratio of the projectile velocity to the coating thickness, and is on the order of 105 s-1 for the experiments herein. Our data and a non-linear dynamics finite-element analysis offer support for this resonance condition as a primary mechanism underlying the penetration-resistance of elastomer-coated metal substrates. The impact-induced phase transition causes large energy absorption, decreasing the kinetic energy of the impacting projectile. However, this energy absorption only accounts for about half the enhanced stopping power of the elastomer/steel bilayer. An additional mechanism is lateral spreading of the impact force, resulting from the transient hardening of the elastomeric during its transition to the glassy state - the modulus of the rubber increases 1000-fold over a time period of microseconds. The penetration-resistance is a very nonlinear function of the coating thickness. Moreover, tests on various metals show that hardness is the principal substrate parameter controlling the contribution of the coating. This work was supported by the Office of Naval Research.

  5. Locating Malleable Bulk Metallic Glasses in Zr-Ti-Cu-Al Alloys with Calorimetric Glass Transition Temperature as an Indicator

    Institute of Scientific and Technical Information of China (English)

    2012-01-01

    We defined the plastic deformability under constrained loading conditions as malleability for bulk metallic glass (BMG) materials. Quaternary Zr-Ti-Cu-Al alloys in the Zr-rich composition range are selected to investigate the compositional dependence of malleability assessed by bending testing and glass transition temperature (Tg ). As indicated, increasing the Al or Cu concentration in the alloys leads to the rise of T g . The Zr(61)Ti2Cu(25)Al(12) (ZT1) and Zr(61.6)Ti(4.4)Cu(24)Al(10) (ZT3) alloys exhibit an optimal combination of lower T g and higher glass-forming ability. The malleable BMGs such as ZT1 manifests two characters during deformation, the stable propagation of a single shear band indicated by large shear offsets and easy proliferation of shear bands. With increasing the T g of BMG, the yield strength σy,Young's modulus and shear modulus simultaneously increase as well, while the Poisson s ratio decreases. The σy of ZT1 BMG is about 1680 MPa in compression and 1600 MPa in tension. In tensile loading, no any visible plasticity appears even when the strain rate increases up to the order of magnitude of 10(-1)s(-1). In consistent with the T g , malleability of Zr-Ti-Cu-Al BMGs manifests significant compositional dependence. The malleable BMG is associated with lower Tg , as well as lower shear modulus or higher Poisson s ratio, which can be understood on the basis of the correlation of Tg with shear energy barrier in metallic glass. Thus, the calorimetric Tg can be used as an indicator to screen malleable BMG-forming composition, with advantage of experimental accessibility.

  6. On the nature of the liquid-to-glass transition equation

    Science.gov (United States)

    Sanditov, D. S.

    2016-09-01

    Within the model of delocalized atoms, it is shown that the parameter δ T g , which enters the glasstransition equation qτ g = δ T g and characterizes the temperature interval in which the structure of a liquid is frozen, is determined by the fluctuation volume fraction {f_g} = {( {{{Δ {V_e}} / V _{T = {T_g}}} frozen at the glass-transition temperature T g and the temperature T g itself. The parameter δ T g is estimated by data on f g and T g . The results obtained are in agreement with the values of δ T g calculated by the Williams-Landel-Ferry (WLF) equation, as well as with the product qτ g —the left-hand side of the glass-transition equation ( q is the cooling rate of the melt, and τ g is the structural relaxation time at the glass-transition temperature). Glasses of the same class with f g ≈ const exhibit a linear correlation between δ T g and T g . It is established that the currently used methods of Bartenev and Nemilov for calculating δ T g yield overestimated values, which is associated with the assumption, made during deriving the calculation formulas, that the activation energy of the glass-transition process is constant. A generalized Bartenev equation is derived for the dependence of the glass-transition temperature on the cooling rate of the melt with regard to the temperature dependence of the activation energy of the glasstransition process. A modified version of the kinetic glass-transition criterion is proposed. A conception is developed that the fluctuation volume fraction f = Δ V e / V can be interpreted as an internal structural parameter analogous to the parameter ξ in the Mandelstam-Leontovich theory, and a conjecture is put forward that the delocalization of an active atom—its critical displacement from the equilibrium position—can be considered as one of possible variants of excitation of a particle in the Vol'kenshtein-Ptitsyn theory. The experimental data used in the study refer to a constant cooling rate of q = 0.05 K

  7. Detection of a Transiting Low-Density Super-Earth

    CERN Document Server

    Henry, Gregory W; Marcy, Geoffrey W; Fischer, Debra A; Johnson, John Asher

    2011-01-01

    We present evidence for photometric transits of the low-mass planet HD 97658b across the disk of its host star, an early K dwarf. This planet was previously discovered in radial velocities (RVs) from Keck/HIRES as part of the Eta-Earth Survey. Using photometry from the Automated Photometric Telescopes at Fairborn Observatory, we detected four separate planetary egress events at times predicted from the RV orbit. We measured a transit depth of 1470 +/- 260 ppm, a result that should be confirmed and refined with space-based photometry. We also collected additional Keck-HIRES RV measurements that refined the transit ephemeris and planet mass. With an orbital period of 9.4957 +/- 0.0022 days, HD 97658b is a close-in planet that had been classified as a `super-Earth' based on its mass of 6.4 +/- 0.7 Mearth. However, the planet radius of 2.93 +/- 0.28 Rearth implies a density of 1.40 g/cc and suggests `sub-Neptune' status. The low density can be explained by an extended atmosphere of volatiles such as hydrogen, hel...

  8. Enhancement of glass-forming ability of Fe-based bulk metallic glasses with high saturation magnetic flux density

    Directory of Open Access Journals (Sweden)

    Mingxiao Zhang

    2012-06-01

    Full Text Available The effects of substituting Fe with Ni on thermal properties, glass-forming ability (GFA and magnetic properties of Fe76-xNixMo3.5P10C4B4Si2.5 (x = 0−30 at.% alloys were investigated in detail. The breadth of the supercooled liquid region was found to gradually increase from 42 to 55 K with increasing Ni content to 30 at.%. When x = 5 at.%, the alloy composition approached a eutectic point, resulting in an increase in GFA. As a result, FeNiMoPCBSi bulk metallic glasses with critical diameters up to 5.5 mm were successfully synthesized by copper mold casting. These glassy alloys exhibit a high saturation magnetic flux density of 0.75−1.21 T and excellent soft magnetic properties, i.e., low coercive force of 1.1−2.0 A/m, and high effective permeability of 14400−19700 at 1 kHz under a field of 1 A/m. The reasons for the high stability of the supercooled liquid, and the high GFA as well as excellent soft magnetic properties are discussed in this article.

  9. Direct Measurement of the Pressure Dependence of the Glass Transition Temperature: A Comparison of Methods

    Science.gov (United States)

    Oliver, William, III; Ransom, Timothy; Cooper, James, III

    2013-03-01

    Two methods for the direct measurement of the pressure dependence of the glass-transition temperature Tg are presented and compared. These methods involve the use of the diamond anvil cell (DAC), and hence, enable the ability to measure Tg(P) to record high pressures of several GPa. Such studies are increasingly relevant as new methods have pushed other high-pressure experimental investigations of glass-forming systems into the same pressure regime. Both methods use careful ruby fluorescence measurements in the DAC as temperature is increased from the glass (TTg) . Method 1 observes the disappearance of pressure gradients as the viscous liquid region is entered, whereas method 2 involves observation of slope changes in the P-T curve during temperature ramps. Such slope changes are associated with the significant change in the volume expansion coefficient between the highly viscous, metastable, supercooled liquid state and the solid glassy state. In most cases, the two methods yield good agreement in the Tg(P) curve. Data will be presented for more than one glass-forming system, including the intermediate strength glass-forming system glycerol and the fragile glass former salol. We acknowledge support from the NSF under DMR-0552944

  10. Connection between slow and fast dynamics of molecular liquids around the glass transition

    DEFF Research Database (Denmark)

    Niss, Kristine; Dalle-Ferrier, Cecile; Frick, Bernhard

    2010-01-01

    The mean-square displacement (MSD) was measured by neutron scattering at various temperatures and pressures for a number of molecular glass-forming liquids. The MSD is invariant along the glass-transition line at the pressure studied, thus establishing an “intrinsic” Lindemann criterion for any...... given liquid. A one-to-one connection between the MSD’s temperature dependence and the liquid’s fragility is found when the MSD is evaluated on a time scale of ∼4 ns, but does not hold when the MSD is evaluated at shorter times. The findings are discussed in terms of the elastic model and the role...

  11. Insights into phase transitions and entanglement from density functional theory

    Science.gov (United States)

    Wei, Bo-Bo

    2016-11-01

    Density functional theory (DFT) has met great success in solid state physics, quantum chemistry and in computational material sciences. In this work we show that DFT could shed light on phase transitions and entanglement at finite temperatures. Specifically, we show that the equilibrium state of an interacting quantum many-body system which is in thermal equilibrium with a heat bath at a fixed temperature is a universal functional of the first derivatives of the free energy with respect to temperature and other control parameters respectively. This insight from DFT enables us to express the average value of any physical observable and any entanglement measure as a universal functional of the first derivatives of the free energy with respect to temperature and other control parameters. Since phase transitions are marked by the nonanalytic behavior of free energy with respect to control parameters, the physical quantities and entanglement measures may present nonanalytic behavior at critical point inherited from their dependence on the first derivative of free energy. We use two solvable models to demonstrate these ideas. These results give new insights for phase transitions and provide new profound connections between entanglement and phase transitions in interacting quantum many-body physics.

  12. Density changes in shear bands of a metallic glass determined by correlative analytical transmission electron microscopy

    Energy Technology Data Exchange (ETDEWEB)

    Rösner, Harald, E-mail: rosner@uni-muenster.de [Institut für Materialphysik, Westfälische Wilhelms-Universität Münster, Wilhelm-Klemm-Strasse 10, D-48149 Münster (Germany); Peterlechner, Martin [Institut für Materialphysik, Westfälische Wilhelms-Universität Münster, Wilhelm-Klemm-Strasse 10, D-48149 Münster (Germany); Kübel, Christian [Karlsruhe Institute of Technology (KIT), Institute of Nanotechnology (INT), Hermann-von-Helmholtz-Platz 1, D-76344 Eggenstein-Leopoldshafen (Germany); Karlsruhe Nano Micro Facility (KNMF), Karlsruhe Institute of Technology (KIT), D-76344 Eggenstein-Leopoldshafen (Germany); Schmidt, Vitalij [Institut für Materialphysik, Westfälische Wilhelms-Universität Münster, Wilhelm-Klemm-Strasse 10, D-48149 Münster (Germany); Wilde, Gerhard [Institut für Materialphysik, Westfälische Wilhelms-Universität Münster, Wilhelm-Klemm-Strasse 10, D-48149 Münster (Germany); Institute of Nanochemistry and Nanobiology, School of Environmental and Chemical Engineering, Shanghai University, Shanghai 200444 (China)

    2014-07-01

    Density changes between sheared zones and their surrounding amorphous matrix as a result of plastic deformation in a cold-rolled metallic glass (melt-spun Al{sub 88}Y{sub 7}Fe{sub 5}) were determined using high-angle annular dark-field (HAADF) detector intensities supplemented by electron-energy loss spectroscopy (EELS), energy-dispersive X-ray (EDX) and nano-beam diffraction analyses. Sheared zones or shear bands were observed as regions of bright or dark contrast arising from a higher or lower density relative to the matrix. Moreover, abrupt contrast changes from bright to dark and vice versa were found within individual shear bands. We associate the decrease in density mainly with an enhanced free volume in the shear bands and the increase in density with concomitant changes of the mass. This interpretation is further supported by changes in the zero loss and Plasmon signal originating from such sites. The limits of this new approach are discussed. - Highlights: • We describe a novel approach for measuring densities in shear bands of metallic glasses. • The linear relation of the dark-field intensity I/I{sub 0} and the mass thickness ρt was used. • Individual shear bands showed abrupt contrast changes from bright to dark and vice versa. • Density changes ranging from about −10% to +6% were found for such shear bands. • Mixtures of amorphous/medium range ordered domains were found within the shear bands.

  13. Probing heterogeneous dynamics from spatial density correlation in glass-forming liquids

    Science.gov (United States)

    Li, Yan-Wei; Zhu, You-Liang; Sun, Zhao-Yan

    2016-12-01

    We numerically investigate the connection between spatial density correlation and dynamical heterogeneity in glass-forming liquids. We demonstrate that the cluster size defined by the spatial aggregation of densely packed particles (DPPs) can better capture the difference between the dynamics of the Lennard-Jones glass model and the Weeks-Chandler-Andersen truncation model than the commonly used pair correlation functions. More interestingly, we compare the mobility of DPPs and loosely packed particles, and we find that high local density correlates well with slow dynamics in systems with relatively hard repulsive interactions but links to mobile ones in the system with soft repulsive interactions at one relaxation time scale. Our results show clear evidence that the above model dependence behavior stems from the hopping motion of DPPs at the end of the caging stage due to the compressive nature of soft repulsive spheres, which activates the dynamics of DPPs in the α relaxation stage.

  14. Quantum yield in blue-emitting anthracene derivatives: vibronic coupling density and transition dipole moment density.

    Science.gov (United States)

    Uejima, Motoyuki; Sato, Tohru; Yokoyama, Daisuke; Tanaka, Kazuyoshi; Park, Jong-Wook

    2014-07-21

    A theoretical design principle for enhancement of the quantum yield of light-emitting molecules is desired. For the establishment of the principle, we focused on the S1 states of blue-emitting anthracene derivatives: 2-methyl-9,10-di(2'-naphthyl)anthracene (MADN), 4,9,10-bis(3',5'-diphenylphenyl)anthracene (MAM), 9-(3',5'-diphenylphenyl)-10-(3'',5''-diphenylbiphenyl-4''-yl) anthracene (MAT), and 9,10-bis(3''',5'''-diphenylbiphenyl-4'-yl) anthracene (TAT) [Kim et al., J. Mater. Chem., 2008, 18, 3376]. The vibronic coupling constants and transition dipole moments were calculated and analyzed by using the concepts of vibronic coupling density (VCD) and transition dipole moment density (TDMD), respectively. It is found that the driving force of the internal conversions and vibrational relaxations originate mainly from the anthracenylene group. On the other hand, fluorescence enhancement results from the large torsional distortion of the side groups in the S1 state. The torsional distortion is caused by the diagonal vibronic coupling for the lowest-frequency mode in the Franck-Condon (FC) S1 state, which originates from a small portion of the electron density difference on the side groups. These findings lead to the following design principles for anthracene derivatives with a high quantum yield: (1) reduction in the electron density difference and overlap density between the S0 and S1 states in the anthracenylene group to suppress vibrational relaxation and radiationless transitions, respectively; (2) increase in the overlap density in the side group to enhance the fluorescence.

  15. Anomalous Crystallization as a Signature of the Fragile-to-Strong Transition in Metallic Glass-Forming Liquids

    DEFF Research Database (Denmark)

    Yang, X.N.; Zhou, C.; Sun, Q.J.;

    2014-01-01

    We study the fragile-to-strong (F−S) transition of metallic glass-forming liquids (MGFLs) by measuring the thermal response during annealing and dynamic heating of La55Al25Ni5Cu15 glass ribbons fabricated at different cooling rates. We find that the glasses fabricated in the intermediate regime...... of cooling rates (15−25 m/s) exhibit an anomalous crystallization behavior upon reheating as compared to the glasses formed at other cooling rates. This anomalous crystallization behavior implies the existence of a thermodynamic F−S transition, could be used as an alternative method for detecting the F...

  16. Electron star birth: a continuous phase transition at nonzero density.

    Science.gov (United States)

    Hartnoll, Sean A; Petrov, Pavel

    2011-03-25

    We show that charged black holes in anti-de Sitter spacetime can undergo a third-order phase transition at a critical temperature in the presence of charged fermions. In the low temperature phase, a fraction of the charge is carried by a fermion fluid located a finite distance from the black hole. In the zero temperature limit, the black hole is no longer present and all charge is sourced by the fermions. The solutions exhibit the low temperature entropy density scaling s~T(2/z) anticipated from the emergent IR criticality of recently discussed electron stars.

  17. Chiral Phase Transition at Finite Isospin Density in Linear Sigma Model

    Institute of Scientific and Technical Information of China (English)

    SHU Song; LI Jia-Rong

    2005-01-01

    Using the linear sigma model, we have introduced the pion isospin chemical potential. The chiral phase transition is studied at finite temperatures and finite isospin densities. We have studied the μ - T phase diagram for the chiral phase transition and found the transition cannot happen below a certain low temperature because of the BoseEinstein condensation in this system. Above that temperature, the chiral phase transition is studied by the isotherms of pressure versus density. We indicate that the transition, in the chiral limit, is a first-order transition from a low-density phase to a high-density phase like a gas-liquid phase transition.

  18. Kepler-7b: A Transiting Planet with Unusually Low Density

    CERN Document Server

    Latham, David W; Koch, David G; Brown, Timothy M; Buchhave, Lars A; Basri, Gibor; Batalha, Natalie M; Caldwell, Douglas A; Cochran, William D; Dunham, Edward W; Furesz, Gabor; Gautier, Thomas N; Geary, John C; Gilliland, Ronald L; Howell, Steve B; Jenkins, Jon M; Lissauer, Jack J; Marcy, Geoffrey W; Monet, David G; Rowe, Jason F; Sasselov, Dimitar D

    2010-01-01

    We report the discovery and confirmation of Kepler-7b, a transiting planet with unusually low density. The mass is less than half that of Jupiter, Mp = 0.43 Mj, but the radius is fifty percent larger, Rp = 1.48 Rj. The resulting density, 0.17 g/cc, is the second lowest reported so far for an extrasolar planet. The orbital period is fairly long, P = 4.886 days, and the host star is not much hotter than the Sun, Teff = 6000 K. However, it is more massive and considerably larger than the sun, Mstar = 1.35 Msun and Rstar = 1.84 Rsun, and must be near the end of its life on the Main Sequence.

  19. Doping influence by some transition elements on the irradiation effects in nuclear waste glasses; Influence du dopage par certains elements de transition sur les effets d'irradiation dans des verres d'interet nucleaire

    Energy Technology Data Exchange (ETDEWEB)

    Florent, Olivier

    2006-06-15

    High-level waste glasses are submitted to auto-irradiation. Modelling it using external irradiations on simple glasses revealed defects production and non negligible structural changes. This thesis aims at determining the impact of a more complex composition on these effects, especially the influence of adding polyvalent transition metals. Silicate, soda-lime and alumino-borosilicate glasses are doped with different iron, chromium and manganese concentrations then {beta} irradiated at different doses up to 10{sup 9} Gy. Non doped glasses show an increase of their density and polymerisation coupled with a molecular oxygen and point defects production. Adding 0.16 mol% Fe decreases the amount of defects by 85 % and all irradiation effects. A Fe{sup 3+} reduction is also observed by EPR, optical absorption and indirectly by Raman spectroscopy. A higher than 0.32 mol% Fe concentration causes complete blockage of the evolution of polymerisation, density and defect production. The same results are obtained on chromium or manganese doped glasses. An original in situ optical absorption device shows the quick decrease of Fe{sup 3+} amount to a 25 % lower level during irradiation. Stopping irradiation causes a lower decrease of 65 %, suggesting a dynamic (h{sup 0}/e-) consuming equilibrium. He{sup +} and Kr{sup 3+} ions and {gamma} irradiated glasses tend to confirm these phenomena for all kind of irradiation with electronic excitations. (author)

  20. Anomalous crystallization as a signature of the fragile-to-strong transition in metallic glass-forming liquids.

    Science.gov (United States)

    Yang, Xiunan; Zhou, Chao; Sun, Qijing; Hu, Lina; Mauro, John C; Wang, Chunzhen; Yue, Yuanzheng

    2014-08-28

    We study the fragile-to-strong (F-S) transition of metallic glass-forming liquids (MGFLs) by measuring the thermal response during annealing and dynamic heating of La55Al25Ni5Cu15 glass ribbons fabricated at different cooling rates. We find that the glasses fabricated in the intermediate regime of cooling rates (15-25 m/s) exhibit an anomalous crystallization behavior upon reheating as compared to the glasses formed at other cooling rates. This anomalous crystallization behavior implies the existence of a thermodynamic F-S transition, could be used as an alternative method for detecting the F-S transition in MGFLs, and sheds light on the structure origin of the F-S transition. This work also contributes to obtaining a general thermodynamic picture of the F-S transition in supercooled liquids.

  1. Pressure effect of glass transition temperature in Zr46.8Ti8.2Cu7.5Ni10Be27.5 bulk metallic glass

    DEFF Research Database (Denmark)

    Jiang, Jianzhong; Roseker, W.; Sikorski, M.

    2004-01-01

    Pressure effects on glass transition temperature and supercooled liquid region of a Zr46.8Ti8.2Cu7.5Ni10Be27.5 bulk glass have been investigated by performing in situ high-temperature and high-pressure x-ray powder diffraction measurements using synchrotron radiation. The glass transition...... was detected from the change of the slope of peak position as a function of temperature. It is found that the glass transition temperature increases with pressure by 4.4 K/GPa for the Zr46.8Ti8.2Cu7.5Ni10Be27.5 bulk glass, and the supercooled liquid range decreases with pressure by 2.9 K/GPa in a pressure...... range of 0-2.2 GPa. This method opens a possibility to study the pressure effect of glass transition process in glassy systems under high pressures (>1 GPa). (C) 2004 American Institute of Physics....

  2. EFFECTS OF TRITIUM GAS EXPOSURE ON THE GLASS TRANSITION TEMPERATURE OF EPDM ELASTOMER AND ON THE CONDUCTIVITY OF POLYANILINE

    Energy Technology Data Exchange (ETDEWEB)

    Clark, E; Marie Kane, M

    2008-12-12

    Four formulations of EPDM (ethylene-propylene diene monomer) elastomer were exposed to tritium gas initially at one atmosphere and ambient temperature for between three and four months in closed containers. Material properties that were characterized include density, volume, mass, appearance, flexibility, and dynamic mechanical properties. The glass transition temperature was determined by analysis of the dynamic mechanical property data per ASTM standards. EPDM samples released significant amounts of gas when exposed to tritium, and the glass transition temperature increased by about 3 C. during the exposure. Effects of ultraviolet and gamma irradiation on the surface electrical conductivity of two types of polyaniline films are also documented as complementary results to planned tritium exposures. Future work will determine the effects of tritium gas exposure on the electrical conductivity of polyaniline films, to demonstrate whether such films can be used as a sensor to detect tritium. Surface conductivity was significantly reduced by irradiation with both gamma rays and ultraviolet light. The results of the gamma and UV experiments will be correlated with the tritium exposure results.

  3. Incommensurate Chirality Density Wave Transition in a Hybrid Molecular Framework

    Science.gov (United States)

    Hill, Joshua A.; Christensen, Kirsten E.; Goodwin, Andrew L.

    2017-09-01

    Using single-crystal x-ray diffraction we characterize the 235 K incommensurate phase transition in the hybrid molecular framework tetraethylammonium silver(I) dicyanoargentate, [NEt4]Ag3(CN )4 . We demonstrate the transition to involve spontaneous resolution of chiral [NEt4]+ conformations, giving rise to a state in which molecular chirality is incommensurately modulated throughout the crystal lattice. We refer to this state as an incommensurate chirality density wave (XDW) phase, which represents a fundamentally new type of chiral symmetry breaking in the solid state. Drawing on parallels to the incommensurate ferroelectric transition of NaNO2 , we suggest the XDW state arises through coupling between acoustic (shear) and molecular rotoinversion modes. Such coupling is symmetry forbidden at the Brillouin zone center but symmetry allowed for small but finite modulation vectors q =[0 ,0 ,qz]* . The importance of long-wavelength chirality modulations in the physics of this hybrid framework may have implications for the generation of mesoscale chiral textures, as required for advanced photonic materials.

  4. Understanding ductile-to-brittle transition of metallic glasses from shear transformation zone dilatation

    Directory of Open Access Journals (Sweden)

    M.Q. Jiang

    2015-08-01

    Full Text Available A theoretical model that takes into account the free-volume aided cooperative shearing of shear transformation zones (STZs is developed to quantitatively understand the ductile-to-brittle transition (DBT of metallic glasses. The STZ dilatational strain is defined as the ratio of STZ-activated free volume to STZ volume itself. The model demonstrates that the STZ dilatational strain will increase drastically and exceed the characteristic shear strain of STZ as temperature decreases below a critical value. This critical temperature is in good agreement with the experimentally measured DBT temperature. Our results suggest that the DBT of metallic glasses is underpinned by the transition of atomic-cluster motions from STZ-type rearrangements to dilatational processes (termed tension transformation zones (TTZs.

  5. Terahertz spectral change associated with glass transition of poly-ε-caprolactone

    Energy Technology Data Exchange (ETDEWEB)

    Komatsu, Marina, E-mail: mkomatsu@toki.waseda.jp [Department of Electrical Engineering and Bioscience, Waseda University, Shinjuku, Tokyo 169-8555 (Japan); Mizuno, Maya; Fukunaga, Kaori [Applied Electromagnetic Research Institute, National Institute of Information and Communications Technology, Koganei, Tokyo 184-8795 (Japan); Saito, Shingo [Advanced ICT Research Institute, National Institute of Information and Communications Technology, Koganei, Tokyo 184-8795 (Japan); Ohki, Yoshimichi, E-mail: yohki@waseda.jp [Department of Electrical Engineering and Bioscience, Waseda University, Shinjuku, Tokyo 169-8555 (Japan); Research Institute for Materials Science and Technology, Waseda University, Shinjuku, Tokyo 169-8555 (Japan)

    2015-04-07

    We measured absorption spectra of unidirectionally stretched poly-ε-caprolactone (PCL) film in a range from 0.3 to 3.6 THz at temperatures from 10 to 300 K. Several absorption peaks were observed, when the electric field of THz waves was set in directions parallel and perpendicular to the stretching direction. The absorption bandwidths became significantly broad at around 200 K and above at least in two specific peaks. This temperature is close to the glass transition temperature of PCL. Further, it is shown by quantum chemical calculations that all the peaks obtained experimentally originate in skeletal vibrations of PCL. Therefore, it has become clear that a specific feature appears in the THz absorption spectrum of PCL associated with its glass transition.

  6. Electronic and ionic conductivity studies on microwave synthesized glasses containing transition metal ions

    Directory of Open Access Journals (Sweden)

    Basareddy Sujatha

    2017-01-01

    Full Text Available Glasses in the system xV2O5·20Li2O·(80 − x [0.6B2O3:0.4ZnO] (where 10 ≤ x ≤ 50 have been prepared by a simple microwave method. Microwave synthesis of materials offers advantages of efficient transformation of energy throughout the volume in an effectively short time. Conductivity in these glasses was controlled by the concentration of transition metal ion (TMI. The dc conductivity follows Arrhenius law and the activation energies determined by regression analysis varies with the content of V2O5 in a non-linear passion. This non-linearity is due to different conduction mechanisms operating in the investigated glasses. Impedance and electron paramagnetic resonance (EPR spectroscopic studies were performed to elucidate the nature of conduction mechanism. Cole–cole plots of the investigated glasses consist of (i single semicircle with a low frequency spur, (ii two depressed semicircles and (iii single semicircle without spur, which suggests the operation of two conduction mechanisms. EPR spectra reveal the existence of electronic conduction between aliovalent vanadium sites. Further, in highly modified (10V2O5 mol% glasses Li+ ion migration dominates.

  7. Study of the avalanche to streamer transition in the glass RPC exited by UV light

    CERN Document Server

    Ammosov, V; Kulemzin, A; Semak, A A; Sviridov, Yu; Zaetz, V G; Sviridov, Yu.

    2002-01-01

    A small glass RPC filled with Ar/Isob./Freon mixture has been exposed to a UV laser light. Avalanche and streamer regimes of discharge were reached in a fixed region of the RPC exited by the UV. A dependence of avalanche to streamer transition process on the laser beam intensity and on the applied high voltage was studied. Two types of the streamer signal have been observed. Using a CCD TV camera, pictures on multi-streamer propagation over RPC were obtained.

  8. Molecular dynamics simulations on specific heat capacity and glass transition tempera-ture of liquid silver

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    The embedded-atom method is adopted to simulate the specific heat capacity of liquid silver. The relationship between the specific heat capacity and the temperature above and below melting point is derived. The results show that there exists an anormaly of the specific heat capacity of liquid silver near 950 K. Simulated pair distribution functions show that the liquid-to-glass transition takes place at this temperature.

  9. Hard sphere-like glass transition in eye lens α-crystallin solutions.

    Science.gov (United States)

    Foffi, Giuseppe; Savin, Gabriela; Bucciarelli, Saskia; Dorsaz, Nicolas; Thurston, George M; Stradner, Anna; Schurtenberger, Peter

    2014-11-25

    We study the equilibrium liquid structure and dynamics of dilute and concentrated bovine eye lens α-crystallin solutions, using small-angle X-ray scattering, static and dynamic light scattering, viscometry, molecular dynamics simulations, and mode-coupling theory. We find that a polydisperse Percus-Yevick hard-sphere liquid-structure model accurately reproduces both static light scattering data and small-angle X-ray scattering liquid structure data from α-crystallin solutions over an extended range of protein concentrations up to 290 mg/mL or 49% vol fraction and up to ca. 330 mg/mL for static light scattering. The measured dynamic light scattering and viscosity properties are also consistent with those of hard-sphere colloids and show power laws characteristic of an approach toward a glass transition at α-crystallin volume fractions near 58%. Dynamic light scattering at a volume fraction beyond the glass transition indicates formation of an arrested state. We further perform event-driven molecular dynamics simulations of polydisperse hard-sphere systems and use mode-coupling theory to compare the measured dynamic power laws with those of hard-sphere models. The static and dynamic data, simulations, and analysis show that aqueous eye lens α-crystallin solutions exhibit a glass transition at high concentrations that is similar to those found in hard-sphere colloidal systems. The α-crystallin glass transition could have implications for the molecular basis of presbyopia and the kinetics of molecular change during cataractogenesis.

  10. Retrogradation of Waxy Rice Starch Gel in the Vicinity of the Glass Transition Temperature

    OpenAIRE

    2013-01-01

    The retrogradation rate of waxy rice starch gel was investigated during storage at temperatures in the vicinity of the glass transition temperature of a maximally concentrated system (T g ′), as it was hypothesized that such temperatures might cause different effects on retrogradation. The T g ′ value of fully gelatinized waxy rice starch gel with 50% water content and the enthalpy of melting retrograded amylopectin in the gels were investigated using differential scanning calorimetry. Starch...

  11. Glasses

    DEFF Research Database (Denmark)

    Dyre, Jeppe

    2004-01-01

    The temperature dependence of the viscosity of most glassforming liquids is known to depart significantly from the classical Arrhenius behaviour of simple fluids. The discovery of an unexpected correlation between the extent of this departure and the Poisson ratio of the resulting glass could lead...... to new understanding of glass ageing and viscous liquid dynamics....

  12. Glasses

    DEFF Research Database (Denmark)

    Dyre, Jeppe

    2004-01-01

    The temperature dependence of the viscosity of most glassforming liquids is known to depart significantly from the classical Arrhenius behaviour of simple fluids. The discovery of an unexpected correlation between the extent of this departure and the Poisson ratio of the resulting glass could lead...... to new understanding of glass ageing and viscous liquid dynamics....

  13. Liquid -to-glass transition in bulk glass-forming Cu55-xZr45Agx alloys using molecular dynamic simulations

    Directory of Open Access Journals (Sweden)

    Celtek M.

    2011-05-01

    Full Text Available We report results from molecular dynamics (MD studies concerning the microscopic structure of the ternary, bulk metallic glass-forming Cu55-x Zr45Agx (x=0,10,20 alloys using tight-binding potentials. Understanding of the nature of Glass Forming Ability (GFA of studied alloys, GFA parameters, glass transition temperature (T-g, melting temperature (T-m, reduced glass transition temperature (T-g/T-m, the supercooled liquid region and other parameters were simulated and compared with experiments. The computed pair distribution functions reproduce well experimental x-ray data of Inoue and co-workers. Structure analysis of the Cu-Zr-Ag alloy based on MD simulation will be also presented

  14. Viscoelastic processes in non-ergodic states (percolation and glass transitions) of attractive micellar systems

    Science.gov (United States)

    Mallamace, F.; Broccio, M.; Tartaglia, P.; Chen, W. R.; Faraone, A.; Chen, S. H.

    2003-12-01

    We report a set of viscoelastic measurements in aqueous solutions of a copolymer micellar system with attractive interactions, a system characterized by a percolation line (PT), and a structural arrest (SA) in the particle diffusion motions of a kinetic glass transition (KGT). We observe, in both transitions, dramatic variations in both the elastic (or storage G‧( ω)) and loss components ( G″( ω)) of the shear moduli. At the PT, rheological data are characterized by a scaling behavior, whereas at the SA G‧ and G″ develop a plateau and a marked minimum, respectively. These behaviors are described in the frame of percolation models and mode coupling theory (MCT).

  15. Cubic to tetragonal phase transition of Tm3+ doped nanocrystals in oxyfluoride glass ceramics

    Directory of Open Access Journals (Sweden)

    Yiming Li

    2016-02-01

    Full Text Available Tm3+ ions doped β-PbF2 nanocrystals in oxyfluoride glass ceramics with different doping concentrations and thermal temperatures are prepared by a traditional melt-quenching and thermal treatment method to investigate the structure and the phase transition of Tm3+ doped nanocrystals. The structures are characterized by X-ray diffraction Rietveld analysis and confirmed with numerical simulation. The phase transitions are proved further by the emission spectra. Both of the doping concentration and thermal temperature can induce an Oh to D4h site symmetry distortion and a cubic to tetragonal phase transition. The luminescence of Tm3+ doped nanocrystals at 800 nm was modulated by the phase transition of the surrounding crystal field.

  16. Cubic to tetragonal phase transition of Tm{sup 3+} doped nanocrystals in oxyfluoride glass ceramics

    Energy Technology Data Exchange (ETDEWEB)

    Li, Yiming; Fu, Yuting; Shi, Yahui; Zhang, Xiaoyu; Yu, Hua, E-mail: zhaolj@nankai.edu.cn, E-mail: yuhua@nankai.edu.cn [The Key Laboratory of Weak-Light Nonlinear Photonics, Ministry of Education, School of Physics, Nankai University, Tianjin 300071 (China); Zhao, Lijuan, E-mail: zhaolj@nankai.edu.cn, E-mail: yuhua@nankai.edu.cn [The Key Laboratory of Weak-Light Nonlinear Photonics, Ministry of Education, School of Physics, Nankai University, Tianjin 300071 (China); Applied Physics School of TEDA, Nankai University, Tianjin 300457 (China)

    2016-02-15

    Tm{sup 3+} ions doped β-PbF{sub 2} nanocrystals in oxyfluoride glass ceramics with different doping concentrations and thermal temperatures are prepared by a traditional melt-quenching and thermal treatment method to investigate the structure and the phase transition of Tm{sup 3+} doped nanocrystals. The structures are characterized by X-ray diffraction Rietveld analysis and confirmed with numerical simulation. The phase transitions are proved further by the emission spectra. Both of the doping concentration and thermal temperature can induce an O{sub h} to D{sub 4h} site symmetry distortion and a cubic to tetragonal phase transition. The luminescence of Tm{sup 3+} doped nanocrystals at 800 nm was modulated by the phase transition of the surrounding crystal field.

  17. Effect of chain end group on surface glass transition temperature of thin polymer film

    Science.gov (United States)

    Jiang, Xiqun; Yang, Chang Zheng; Tanaka, Keiji; Takahara, Atsushi; Kajiyama, Tisato

    2001-04-01

    Surface glass transition behaviors of proton end capped poly(2-vinylpyridine) (P2VP-H) and perfluoroalkyl end capped poly(2-vinylpyridine) (P2VP-C 2C 8F) thin films were investigated based on temperature-dependent lateral force microscopic (TDLFM) measurement. It is found that the species of chain end groups have significant influence on the surface glass transition temperature of the thin polymer film. For both samples, it is revealed that the surface glass transition temperatures decrease significantly in comparison to the bulk ones, and the magnitude order of reduction in surface Tg for P2VP-C 2C 8F is larger than that for P2VP-H. The apparent activation energy of surface α-relaxation calculated from the Arrhenius plot is ca. 292±40 and 212±40 kJ/mol for P2VP-H and P2VP-C 2C 8F, respectively, and is much smaller than the bulk one. The depression of the surface Tg for thin polymer films is explained by the excess free volume induced by the enrichment of chain end groups at the surface.

  18. Reversibility and hysteresis of the sharp yielding transition of a colloidal glass under oscillatory shear.

    Science.gov (United States)

    Dang, M T; Denisov, D; Struth, B; Zaccone, A; Schall, P

    2016-04-01

    The mechanical response of glasses remains challenging to understand. Recent results indicate that the oscillatory rheology of soft glasses is accompanied by a sharp non-equilibrium transition in the microscopic dynamics. Here, we use simultaneous x-ray scattering and rheology to investigate the reversibility and hysteresis of the sharp symmetry change from anisotropic solid to isotropic liquid dynamics observed in the oscillatory shear of colloidal glasses (D. Denisov, M.T. Dang, B. Struth, A. Zaccone, P. Schall, Sci. Rep. 5 14359 (2015)). We use strain sweeps with increasing and decreasing strain amplitude to show that, in analogy with equilibrium transitions, this sharp symmetry change is reversible and exhibits systematic frequency-dependent hysteresis. Using the non-affine response formalism of amorphous solids, we show that these hysteresis effects arise from frequency-dependent non-affine structural cage rearrangements at large strain. These results consolidate the first-order-like nature of the oscillatory shear transition and quantify related hysteresis effects both via measurements and theoretical modelling.

  19. Dynamic Heterogeneity in Highly Cross-linked Epoxy in the Vicinity of Glass Transition

    Science.gov (United States)

    Lin, Po-Han; Khare, Rajesh

    2010-03-01

    Cross-linked epoxy has been widely used in aerospace and electronics industries. The highly cross-linked nature of these systems leads to different chain dynamics as compared to the linear polymeric systems. In this work, we have used molecular dynamics (MD) simulations to study the dynamic heterogeneity in cross-linked epoxy near the glass transition temperature. Well-relaxed atomistic models of cross-linked epoxy were first created by employing the simulated annealing polymerization approach. The specific epoxy system studied consisted of diglycidyl ether of bisphenol-A (DGEBA) as the epoxy monomer and trimethylene glycol di-p-aminobenzoate (TMAB) as the cross-linker. The glass transition temperature of these model structures was determined from MD simulation by monitoring their volume-temperature behaviour in a stepwise cooling run. The chain dynamics of these systems were characterized by their local translational and orientational mobility. Furthermore, dynamic heterogeneity was studied by analyzing the spatial distribution of the mobile and immobile atoms in the system near the glass transition temperature.

  20. Energy boost in laser wakefield accelerators using sharp density transitions

    CERN Document Server

    Döpp, A; Thaury, C; Lifschitz, A; Phuoc, K Ta; Malka, V

    2015-01-01

    The energy gain in laser wakefield accelerators is limited by dephasing between the driving laser pulse and the highly relativistic electrons in its wake. Since this phase depends on both the driver and the cavity length, the effects of dephasing can be mitigated with appropriate tailoring of the plasma density along propagation. Preceding studies have discussed the prospects of continuous phase-locking in the linear wakefield regime. However, most experiments are performed in the highly non-linear regime and rely on self-guiding of the laser pulse. Due to the complexity of the driver evolution in this regime it is much more difficult to achieve phase locking. As an alternative we study the scenario of rapid rephasing in sharp density transitions, as was recently demonstrated experimentally. Starting from a phenomenological model we deduce expressions for the electron energy gain in such density profiles. The results are in accordance with particle-in-cell simulations and we present gain estimations for singl...

  1. Kinetics of Ge20Se80–As ( = 0, 5, 10, 15 and 20) in glass transition region

    Indian Academy of Sciences (India)

    Kedar Singh; N S Saxena

    2003-08-01

    The results of differential scanning calorimetric (DSC) measurements on Ge20Se80–As ( = 0, 5, 10, 15 and 20) system with the specific aim of investigating the effect of heating rate and composition on glass transition temperature have been discussed. The results indicate that the glass transition temperature () is dependent both on the heating rate and composition. The glass transition activation energy () and heat absorbed in glass transition region () are higher for Ge20Se65As15 as compared to the values of other compositions of arsenic. An effort has also been made to develop an empirical model for the composition dependence of . A good agreement has been observed between the experimental values and the results of model calculation.

  2. Thermodynamic aspects of the glass transition phenomenon. II. Molecular liquids with variable interactions

    Science.gov (United States)

    Alba-Simionesco, C.; Fan, J.; Angell, C. A.

    1999-03-01

    As a contribution to the understanding of the thermodynamics of the glass transition phenomenon a series of molecules having the same steric character, but differing in the strength and nature of intermolecular interactions, has been investigated. The series is based on systematic changes of substituents on disubstituted benzene ring compounds, the simplest example of which is meta-xylene. Meta-isomers are chosen in each instance because of their greater tendency to supercool. In particular, m-fluoroaniline cannot be crystallized at ambient pressure. The principal measurements performed were of heat capacity and enthalpy change, using the technique of differential scanning calorimetry, and these have been examined in the light of literature data on the liquid viscosities and some recent data for dielectric relaxation. As the strength of hydrogen-bonding interactions between the ring substituents on adjacent molecules increases, the glass transition temperature Tg increases by almost 100 degrees from the lowest value in the series, 122.5 K, for m-fluorotoluene. Empirical rules involving Tb/Tm and Tg/Tm are found wanting. The important thermodynamic characteristic of the glass transition, viz., the change in heat capacity at the glass transition, ΔCp, remains approximately constant until the -OH substituent is introduced, whereupon a new element appears. This is a specific component of ΔCp which appears at temperatures above an initially small jump at Tg. It is well accounted for by the addition of a two-state H-bond breaking component (with the usual H⋯-OH bond energy) to the total excess heat capacity. The liquid ground state (or Kauzmann) temperature TK assessed from thermodynamic data acquired in this study, falls 20%-30% below the glass transition temperature. From the limited transport data available, these liquids appear to be quite fragile in character implying that the phenyl group influence dominates the hydrogen bond factor which has often seemed

  3. Single-frequency dielectric relaxation used to characterize the glass transition time of polydextrose

    Science.gov (United States)

    Buehler, Martin G.; Campbell, Zachary J.; Carter, Brady P.

    2017-02-01

    Dielectric relaxation methods are applicable to powdery materials such as carbohydrates. These materials have relaxations that occur in the milli-Hz range while samples are held at fixed temperatures and fixed water activities, a w, (relativity humidity). Under proper conditions these materials undergo physical changes where the initially glassy powder transitions to an amorphous equilibrium state at the glass transition temperature, T g. Determining this transition involves characterizing the boundary curve (T g versus a w) which determines T g and a w conditions where materials are stable with long-shelf life or unstable with very a short shelf-life. This paper serves to illustrate multiple methodologies which can be used to characterize glass transition from frequency-spectra. Three methodologies are described: peak-broadening, peak-shift, and single-frequency. The new single frequency method not only provides results that identical to those of the peak-shift method but increases the data acquisition speeds by a factor of 5. This method is illustrated on polydextrose, a common sugar substitute. The information gathered can then be used to construct the boundary curve which is used to characterize the shelf-life of a material at various conditions.

  4. Slow dynamics and glass transition in simulated free-standing polymer films: a possible relation between global and local glass transition temperatures

    Energy Technology Data Exchange (ETDEWEB)

    Peter, S [Institut Charles Sadron, 6 rue Boussingault, 67083 Strasbourg Cedex (France); Meyer, H [Institut Charles Sadron, 6 rue Boussingault, 67083 Strasbourg Cedex (France); Baschnagel, J [Institut Charles Sadron, 6 rue Boussingault, 67083 Strasbourg Cedex (France); Seemann, R [Max Planck Institute for Dynamics and Self-Organization, D-37018 Goettingen (Germany)

    2007-05-23

    We employ molecular dynamics simulations to explore the influence that the surface of a free-standing polymer film exerts on its structural relaxation when the film is cooled toward the glass transition. Our simulations are concerned with the features of a coarse-grained bead-spring model in a temperature regime above the critical temperature T{sub c} of mode-coupling theory. We find that the film dynamics is spatially heterogeneous. Monomers at the free surface relax much faster than they would in the bulk at the same temperature T. The fast relaxation of the surface layer continuously turns into bulk-like relaxation with increasing distance y from the surface. This crossover remains smooth for all T, but its range grows on cooling. We show that it is possible to associate a gradient in critical temperatures T{sub c}(y) with the gradient in the relaxation dynamics. This finding is in qualitative agreement with experimental results on supported polystyrene (PS) films (Ellison and Torkelson 2003 Nat. Mater. 2 695). Furthermore we show that the y dependence of T{sub c}(y) can be expressed in terms of the depression of T{sub c}(h)-the global T{sub c} for a film of thickness h-if we assume that T{sub c}(h) is the arithmetic mean of T{sub c}(y) and parameterize the depression of T{sub c}(h) by T{sub c}(h) = T{sub c}/(1+h{sub 0}/h), a formula suggested by Herminghaus et al (2001 Eur. Phys. J. E 5 531) for the reduction of the glass transition temperature in supported PS films. We demonstrate the validity of this formula by comparing our simulation results to results from other simulations and experiments.

  5. Effect of incongruent crystallization on glass–liquid transition features of a bulk metal glass

    Energy Technology Data Exchange (ETDEWEB)

    Aji, D.P.B.; Johari, G.P., E-mail: joharig@mcmaster.ca

    2015-09-10

    Highlights: • Ce{sub 66}Al{sub 10}Cu{sub 20}Co{sub 4} glass did not crystallize during aging for nine years. • Crystallization's onset temperature was higher for the aged glass. • Incongruent melt embedding the crystals had higher viscosity and T{sub g}. • Increase in crystallization increased the T{sub g} and broadened the T{sub g}-endotherm. - Abstract: It is known that most multi-component glasses cold-crystallize incongruently on heating through the temperature range of their ultraviscous melt. If the incongruent melt's composition changes with time, its viscosity, η, and the glass–liquid transition temperature, T{sub g}, would change. Since the η, relaxation time, and expansion coefficient of a liquid in its partially crystallized mixture cannot be determined, we used scanning calorimetry to study the liquid–glass–liquid transition during thermal cycling of the incongruently crystallizing Ce{sub 66}Al{sub 10}Cu{sub 20}Co{sub 4} glass. Its T{sub g} is 358 K for 20 K/min and 354 K for 10 K/min heating rates, and its ultraviscous melt crystallized incongruently when heated beyond the hysteresis peak of its heat capacity scan. Its sample that had been aged for nine years at ambient conditions had a higher crystallization-onset temperature than an un-aged sample. Delayed enthalpy gain on heating of the aged glass is ∼1/5th of the enthalpy lost on its crystallization. Crystallization of the melt occurred on both the heating and cooling paths of a thermal cycle and T{sub g} of the un-aged glass increased as the volume fraction of the compositionally different glass, f{sub gl}, decreased. The increase was by 8 K after the 24th cycle of 20 K/min, and by 11 K after the 13th cycle of 10 K/min cooling-heating. The highest T{sub g} values reached differed by ∼1 K, which indicates that closely similar T{sub g}s may be reached if the total time period for thermal cycling (at different rates) is kept the same. As f{sub gl} approached its limiting

  6. Polymer glass transition occurs at the marginal rigidity point with connectivity z* = 4.

    Science.gov (United States)

    Lappala, Anna; Zaccone, Alessio; Terentjev, Eugene M

    2016-09-21

    We re-examine the physical origin of the polymer glass transition from the point of view of marginal rigidity, which is achieved at a certain average number of mechanically active intermolecular contacts per monomer. In the case of polymer chains in a melt/poor solvent, each monomer has two neighbors bound by covalent bonds and also a number of central-force contacts modelled by the Lennard-Jones (LJ) potential. We find that when the average number of contacts per monomer (covalent and non-covalent) exceeds the critical value z* ≈ 4, the system becomes solid and the dynamics arrested - a state that we declare the glass. Coarse-grained Brownian dynamics simulations show that at sufficient strength of LJ attraction (which effectively represents the depth of quenching, or the quality of solvent) the polymer globule indeed crosses the threshold of z*, and becomes a glass with a finite zero-frequency shear modulus, G∝ (z-z*). We verify this by showing the distinction between the 'liquid' polymer droplet at z z*, which changes shape and adopts the spherical conformation in equilibrium, and the glassy 'solid' droplet at z > z*, which retains its shape frozen at the moment of z* crossover. These results provide a robust microscopic criterion to tell the liquid apart from the glass for the linear polymers.

  7. Potential energy landscape of the apparent first-order phase transition between low-density and high-density amorphous ice.

    Science.gov (United States)

    Giovambattista, Nicolas; Sciortino, Francesco; Starr, Francis W; Poole, Peter H

    2016-12-14

    The potential energy landscape (PEL) formalism is a valuable approach within statistical mechanics to describe supercooled liquids and glasses. Here we use the PEL formalism and computer simulations to study the pressure-induced transformations between low-density amorphous ice (LDA) and high-density amorphous ice (HDA) at different temperatures. We employ the ST2 water model for which the LDA-HDA transformations are remarkably sharp, similar to what is observed in experiments, and reminiscent of a first-order phase transition. Our results are consistent with the view that LDA and HDA configurations are associated with two distinct regions (megabasins) of the PEL that are separated by a potential energy barrier. At higher temperature, we find that low-density liquid (LDL) configurations are located in the same megabasin as LDA, and that high-density liquid (HDL) configurations are located in the same megabasin as HDA. We show that the pressure-induced LDL-HDL and LDA-HDA transformations occur along paths that interconnect these two megabasins, but that the path followed by the liquid is different from the path followed by the amorphous solid. At higher pressure, we also study the liquid-to-ice-VII first-order phase transition, and find that the behavior of the PEL properties across this transition is qualitatively similar to the changes found during the LDA-HDA transformation. This similarity supports the interpretation that the LDA-HDA transformation is a first-order phase transition between out-of-equilibrium states. Finally, we compare the PEL properties explored during the LDA-HDA transformations in ST2 water with those reported previously for SPC/E water, for which the LDA-HDA transformations are rather smooth. This comparison illuminates the previous work showing that, at accessible computer times scales, a liquid-liquid phase transition occurs in the case of ST2 water, but not for SPC/E water.

  8. Potential energy landscape of the apparent first-order phase transition between low-density and high-density amorphous ice

    Science.gov (United States)

    Giovambattista, Nicolas; Sciortino, Francesco; Starr, Francis W.; Poole, Peter H.

    2016-12-01

    The potential energy landscape (PEL) formalism is a valuable approach within statistical mechanics to describe supercooled liquids and glasses. Here we use the PEL formalism and computer simulations to study the pressure-induced transformations between low-density amorphous ice (LDA) and high-density amorphous ice (HDA) at different temperatures. We employ the ST2 water model for which the LDA-HDA transformations are remarkably sharp, similar to what is observed in experiments, and reminiscent of a first-order phase transition. Our results are consistent with the view that LDA and HDA configurations are associated with two distinct regions (megabasins) of the PEL that are separated by a potential energy barrier. At higher temperature, we find that low-density liquid (LDL) configurations are located in the same megabasin as LDA, and that high-density liquid (HDL) configurations are located in the same megabasin as HDA. We show that the pressure-induced LDL-HDL and LDA-HDA transformations occur along paths that interconnect these two megabasins, but that the path followed by the liquid is different from the path followed by the amorphous solid. At higher pressure, we also study the liquid-to-ice-VII first-order phase transition, and find that the behavior of the PEL properties across this transition is qualitatively similar to the changes found during the LDA-HDA transformation. This similarity supports the interpretation that the LDA-HDA transformation is a first-order phase transition between out-of-equilibrium states. Finally, we compare the PEL properties explored during the LDA-HDA transformations in ST2 water with those reported previously for SPC/E water, for which the LDA-HDA transformations are rather smooth. This comparison illuminates the previous work showing that, at accessible computer times scales, a liquid-liquid phase transition occurs in the case of ST2 water, but not for SPC/E water.

  9. Theory of activated dynamics and glass transition of hard colloids in two dimensions.

    Science.gov (United States)

    Zhang, Bo-kai; Li, Hui-shu; Tian, Wen-de; Chen, Kang; Ma, Yu-qiang

    2014-03-07

    The microscopic nonlinear Langevin equation theory is applied to study the localization and activated hopping of two-dimensional hard disks in the deeply supercooled and glass states. Quantitative comparisons of dynamic characteristic length scales, barrier, and their dependence on the reduced packing fraction are presented between hard-disk and hard-sphere suspensions. The dynamic barrier of hard disks emerges at higher absolute and reduced packing fractions and correspondingly, the crossover size of the dynamic cage which correlates to the Lindemann length for melting is smaller. The localization lengths of both hard disks and spheres decrease exponentially with packing fraction. Larger localization length of hard disks than that of hard spheres is found at the same reduced packing fraction. The relaxation time of hard disks rises dramatically above the reduced packing fraction of 0.88, which leads to lower reduced packing fraction at the kinetic glass transition than that of hard spheres. The present work provides a foundation for the subsequent study of the glass transition of binary or polydisperse mixtures of hard disks, normally adopted in experiments and simulations to avoid crystallization, and further, the rheology and mechanical response of the two-dimensional glassy colloidal systems.

  10. Finite size scaling study of dynamical phase transitions in two dimensional models: ferromagnet, symmetric and non symmetric spin glasses

    Energy Technology Data Exchange (ETDEWEB)

    Neumann, A.U.; Derrida, B.

    1988-10-01

    We study the time evolution of two configurations submitted to the same thermal noise for several two dimensional models (Ising ferromagnet, symmetric spin glass, non symmetric spin glass). For all these models, we find a non zero critical temperature above which the two configurations always meet. Using finite size scaling ideas, we determine for these three models this dynamical phase transition and some of the critical exponents. For the ferromagnet, the transition T/sub c/ approx. = 2.25 coincides with the Curie temperature whereas for the two spin glass models +- J distribution of bonds) we obtain T/sub c/ approx. = 1.5-1.7.

  11. Properties of high-density, well-ordered, and high-energy metallic glass phase designed by pressurized quenching

    Science.gov (United States)

    Miyazaki, Narumasa; Lo, Yu-Chieh; Wakeda, Masato; Ogata, Shigenobu

    2016-08-01

    We applied gigapascal-level compressive hydrostatic pressure to the melt-quenching process of metallic glass to obtain a unique high-pressure glass state with high density that is well-ordered yet has high energy. This state contradicts the common understanding that high-density, well-ordered metallic glass states have low energy. Through molecular dynamics simulations, we found that the high-pressure glass state of the metallic glass Zr50Cu40Al10 has a rich anti-free volume and that its relaxation is dominated by the annihilation of full icosahedra and the rich anti-free volume. The aging rate of the high-pressure metallic glass state (energy reduction rate) is almost the same as that of typical high-energy metallic glass, suggesting that it has a lifetime similar to that of a typical high-energy metallic glass that has been experimentally realized and reported previously [Wakeda et al., Sci. Rep. 5, 10545 (2015)]. Thus, the high-pressure phase can be realized even under the experimental cooling rate, suggesting its suitability for practical applications.

  12. Disorder-assisted melting and the glass transition in amorphous solids

    Science.gov (United States)

    Zaccone, Alessio; Terentjev, Eugene

    2013-03-01

    The mechanical response of solids depends on temperature because the way atoms and molecules respond collectively to deformation is affected at various levels by thermal motion. This is a fundamental problem of solid state science and plays a crucial role in metallurgy, aerospace engineering, energy. In disordered solids (glass, amorphous semiconductors, ceramics, metallic glass, polymers) the vanishing of rigidity as a function of temperature is not well understood because continuum elasticity is inapplicable due to the disorder leading to nontrivial (nonaffine) components in the atomic displacements. Our theory explains the basic mechanism of the melting transition of amorphous solids in terms of the lattice energy lost to nonaffine motion, compared to which thermal vibrations turn out to play a negligible role. The theory is in good agreement with data on melting of amorphous polymers (where no alternative theory can be found in the literature) and offers new opportunities in materials science.

  13. On the glass transition of the one-component metallic melts

    Science.gov (United States)

    Fedorchenko, A. I.

    2017-10-01

    In this paper, the conditions for one-component metallic melts vitrification by quenching from a liquid state were formulated. It is shown that the tendency to the glass formation drastically increases with the temperature of melting. The maximum glass layer thickness and the associated cooling rates along with the vitrification temperatures was determined for Al, Cu, and Ni melts deposited on the Cu substrate. The results are in agreement with the available experimental data. Based on analytical solution of the impinging droplet solidification, the numerical value of the early-introduced asymptotic Ω criterion, which separates equilibrium and non-equilibrium phase transitions, was determined. Good agreement between the calculated and experimental values of the thickness of the splats shows that Ω criterion indeed predicts a priori a scenario of solidification.

  14. Spin-glass transition in bond-disordered Heisenberg antiferromagnets coupled with local lattice distortions on a pyrochlore lattice.

    Science.gov (United States)

    Shinaoka, Hiroshi; Tomita, Yusuke; Motome, Yukitoshi

    2011-07-22

    Motivated by puzzling characteristics of spin-glass transitions widely observed in pyrochlore-based frustrated materials, we investigate the effects of coupling to local lattice distortions in a bond-disordered antiferromagnet on the pyrochlore lattice by extensive Monte Carlo simulations. We show that the spin-glass transition temperature T(f) is largely enhanced by the spin-lattice coupling and, furthermore, becomes almost independent of Δ in a wide range of the disorder strength Δ. The critical property of the spin-glass transition is indistinguishable from that of the canonical Heisenberg spin glass in the entire range of Δ. These peculiar behaviors are ascribed to a modification of the degenerate manifold from a continuous to semidiscrete one by spin-lattice coupling.

  15. Phase field crystal modelling of the order-to-disordered atomistic structure transition of metallic glasses

    Science.gov (United States)

    Zhang, W.; Mi, J.

    2016-03-01

    Bulk metallic glass composites are a new class of metallic alloy systems that have very high tensile strength, ductility and fracture toughness. This unique combination of mechanical properties is largely determined by the presence of crystalline phases uniformly distributed within the glassy matrix. However, there have been very limited reports on how the crystalline phases are nucleated in the super-cooled liquid and their growth dynamics, especially lack of information on the order-to-disordered atomistic structure transition across the crystalline-amorphous interface. In this paper, we use phase field crystal (PFC) method to study the nucleation and growth of the crystalline phases and the glass formation of the super cooled liquid of a binary alloy. The study is focused on understanding the order-to-disordered transition of atomistic configuration across the interface between the crystalline phases and amorphous matrix of different chemical compositions at different thermal conditions. The capability of using PFC to simulate the order-to-disorder atomistic transition in the bulk material or across the interface is discussed in details.

  16. Effects of temperature and pressure on the glass transitions of plastic bonded explosives

    Energy Technology Data Exchange (ETDEWEB)

    Campbell, M.S.; Garcia, D.; Idar, D.

    1998-12-31

    Various plastic bonded explosives (PBXs) contain about 5-wt% polymer, plasticizer, and stabilizer as binder. The glass-transition temperature (T{sub g}) determines, in part, if the binder will reduce or increase the sensitivity of the PBX to impact. A soft binder reduces the impact sensitivity; however, too soft a binder compromises the mechanical strength below that desirable for dimensional stability. Glass transitions were measured by temperature modulated DSC for PBXs before and after pressing. Pressing temperature was 90 C. The T{sub g} of Estane, a polyester/polyurethane used in some PBX binders, was investigated. Only small changes were observed in the low temperature T{sub g} of the soft segments but larger changes were seen in the higher temperature transitions due to the relaxation of the hard segments. The T{sub g} of Kel F 800, a binder used in insensitive PBX 9502, was observed near ambient temperature. The PBX 9502 had a lower T{sub g} than the neat polymer. Mechanical strength will be measured for the samples.

  17. On the Pr3+ interconfigurational optical transitions in glasses and an comparative study of the Photon Cascade Emission in crystals and glasses

    Science.gov (United States)

    Srivastava, A. M.

    2013-04-01

    This paper offers a study that compares the nature of Pr3+ luminescence in crystalline and glass modifications of LaB3O6, LiLaP4O12 and SrB4O7. In the crystalline derivative of these materials, the crystal-field split Pr3+ 4f15d1 state is higher in energy than the 1S0 state. The resulting energy level structure permits the observation of the Pr3+ 1S0 → 1I6 emission transition and the production of two photons for every absorbed UV photon, a process which is referred to as Photon Cascade Emission. In the corresponding glass derivatives, the Pr3+ 4f15d1 lies below the 1S0 state with the consequence that the emission is dominated by the interconfigurational (broad-band) Pr3+ 4f15d1 → 4f2 transition. The reason for this is traced to increased strength of the crystalline field at the Pr3+ site in the glass phase. The increased crystal-field strength is traceable to decreased local coordination number and to shorter Pr3+-O2- bond distances. In this paper we also analyze the results of the Pr3+ ion luminescence in fluoride, oxyfluoride, borate and phosphate glasses. With the exception of one pure fluoride glass (ZBLAN), the Pr3+ luminescence in all these glasses is dominated by the interconfigurational Pr3+ 4f15d1 → 4f2 emission transition. It is pointed out that under broad-band excitation, emission from the Pr3+ 1S0 state has yet to be observed in an oxide based glass (phosphates and borates).

  18. Differential scanning calorimetry study of glass transition in frozen starch gels.

    Science.gov (United States)

    Tananuwong, Kanitha; Reid, David S

    2004-06-30

    The effects of initial water content, maximum heating temperature, amylopectin crystallinity type, and annealing on the glass transition of starch gels were studied by differential scanning calorimetry (DSC). The glass transition temperatures of the frozen gels measured as the onset (T(g,onset)) or midpoint temperature (T(g,midpoint)), heat capacity change during the glass transition (deltaC(p)), unfrozen water of starch gels, and additional unfrozen water (AUW) arising from gelatinization were reported. The results show that T(g,onset) and T(g,midpoint) of the partially gelatinized gels are independent of the initial water content, while both of the T(g) values of the fully gelatinized gel increase as the initial water content increases. These observations might result from the difference in the level of structural disruption associated with different heating conditions, resulting in different gel structures as well as different concentrations of the sub-T(g) unfrozen matrix. The amylopectin crystallinity type does not greatly affect T(g,onset) and T(g,midpoint) of the gels. Annealing at a temperature near T(g,onset) increases both T(g,onset) and T(g,midpoint) of the gels, possibly due to an increase in the extent of the freeze concentration as evidenced by a decrease in AUW. Annealing results in an increase in the deltaC(p) value of the gels, presumably due to structural relaxation. A devitrification exotherm may be related to AUW. The annealing process decreases AUW, thus also decreasing the size of the exotherm.

  19. Glass transition of polymers in bulk, confined geometries, and near interfaces

    Science.gov (United States)

    Napolitano, Simone; Glynos, Emmanouil; Tito, Nicholas B.

    2017-03-01

    When cooled or pressurized, polymer melts exhibit a tremendous reduction in molecular mobility. If the process is performed at a constant rate, the structural relaxation time of the liquid eventually exceeds the time allowed for equilibration. This brings the system out of equilibrium, and the liquid is operationally defined as a glass—a solid lacking long-range order. Despite almost 100 years of research on the (liquid/)glass transition, it is not yet clear which molecular mechanisms are responsible for the unique slow-down in molecular dynamics. In this review, we first introduce the reader to experimental methodologies, theories, and simulations of glassy polymer dynamics and vitrification. We then analyse the impact of connectivity, structure, and chain environment on molecular motion at the length scale of a few monomers, as well as how macromolecular architecture affects the glass transition of non-linear polymers. We then discuss a revised picture of nanoconfinement, going beyond a simple picture based on interfacial interactions and surface/volume ratio. Analysis of a large body of experimental evidence, results from molecular simulations, and predictions from theory supports, instead, a more complex framework where other parameters are relevant. We focus discussion specifically on local order, free volume, irreversible chain adsorption, the Debye–Waller factor of confined and confining media, chain rigidity, and the absolute value of the vitrification temperature. We end by highlighting the molecular origin of distributions in relaxation times and glass transition temperatures which exceed, by far, the size of a chain. Fast relaxation modes, almost universally present at the free surface between polymer and air, are also remarked upon. These modes relax at rates far larger than those characteristic of glassy dynamics in bulk. We speculate on how these may be a signature of unique relaxation processes occurring in confined or heterogeneous polymeric

  20. Interfacial and topological effects on the glass transition in free-standing polystyrene films

    Science.gov (United States)

    Lyulin, Alexey V.; Balabaev, Nikolay K.; Baljon, Arlette R. C.; Mendoza, Gerardo; Frank, Curtis W.; Yoon, Do Y.

    2017-05-01

    United-atom molecular-dynamics computer simulations of atactic polystyrene (PS) were performed for the bulk and free-standing films of 2 nm-20 nm thickness, for both linear and cyclic polymers comprised of 80 monomers. Simulated volumetric glass-transition temperatures (Tg) show a strong dependence on the film thickness below 10 nm. The glass-transition temperature of linear PS is 13% lower than that of the bulk for 2.5 nm-thick films, as compared to less than 1% lower for 20 nm films. Our studies reveal that the fraction of the chain-end groups is larger in the interfacial layer with its outermost region approximately 1 nm below the surface than it is in the bulk. The enhanced population of the end groups is expected to result in a more mobile interfacial layer and the consequent dependence of Tg on the film thickness. In addition, the simulations show an enrichment of backbone aliphatic carbons and concomitant deficit of phenyl aromatic carbons in the interfacial film layer. This deficit would weaken the strong phenyl-phenyl aromatic (π -π ) interactions and, hence, lead to a lower film-averaged Tg in thin films, as compared to the bulk sample. To investigate the relative importance of the two possible mechanisms (increased chain ends at the surface or weakened π -π interactions in the interfacial region), the data for linear PS are compared with those for cyclic PS. For the cyclic PS, the reduction of the glass-transition temperature is also significant in thin films, albeit not as much as for linear PS. Moreover, the deficit of phenyl carbons in the film interface is comparable to that observed for linear PS. Therefore, chain-end effects alone cannot explain the observed pronounced Tg dependence on the thickness of thin PS films; the weakened phenyl-phenyl interactions in the interfacial region seems to be an important cause as well.

  1. Acoustic and thermal anomalies in a liquid-glass transition of racemic S(+)-R(-) ketoprofen

    Science.gov (United States)

    Shibata, Tomohiko; Takayama, Haruki; Kim, Tae Hyun; Kojima, Seiji

    2014-01-01

    Acoustic and thermal properties of pharmaceutical racemic S(+)-R(-) ketoprofen were investigated in wide temperature range including glassy, supercooled liquid and liquid states by Brillouin scattering and temperature modulated DSC. Sound velocity and acoustic attenuation exhibited clear changes at 265 K indicating a liquid-glass transition and showed the typical structural relaxation above Tg. The high value of the fragility index m = 71 was determined by the dispersion of the complex heat capacity. New relaxation map was suggested in combination with previous study of dielectric measurement.

  2. Liquid droplets on a free-standing glassy membrane: Deformation through the glass transition.

    Science.gov (United States)

    Fortais, Adam; Schulman, Rafael D; Dalnoki-Veress, Kari

    2017-07-01

    In this study, micro-droplets are placed on thin, glassy, free-standing films where the Laplace pressure of the droplet deforms the free-standing film, creating a bulge. The film's tension is modulated by changing temperature continuously from well below the glass transition into the melt state of the film. The contact angle of the liquid droplet with the planar film as well as the angle of the bulge with the film are measured and found to be consistent with the contact angles predicted by a force balance at the contact line.

  3. Random pinning glass transition: hallmarks, mean-field theory and renormalization group analysis.

    Science.gov (United States)

    Cammarota, Chiara; Biroli, Giulio

    2013-03-28

    We present a detailed analysis of glass transitions induced by pinning particles at random from an equilibrium configuration. We first develop a mean-field analysis based on the study of p-spin spherical disordered models and then obtain the three-dimensional critical behavior by the Migdal-Kadanoff real space renormalization group method. We unveil the important physical differences with the case in which particles are pinned from a random (or very high temperature) configuration. We contrast the pinning particles approach to the ones based on biasing dynamical trajectories with respect to their activity and on coupling to equilibrium configurations. Finally, we discuss numerical and experimental tests.

  4. Infrared absorption spectra of transition metals-doped soda lime silica glasses

    Science.gov (United States)

    Khalil, E. M. A.; ElBatal, F. H.; Hamdy, Y. M.; Zidan, H. M.; Aziz, M. S.; Abdelghany, A. M.

    2010-03-01

    Infrared (IR) absorption spectra of some prepared undoped and transition metals-doped soda-lime-silicate glasses have been studied in the region of 400-4000 cm -1. IR spectra were analyzed to determine and differentiate the various vibrational modes by applying a deconvolution method to the IR spectra. Although the first sight reveals close similarity between the different transition metal- (TM) doped samples; careful inspection indicates some minor differences depending on the type of TM ions. These observed data are correlated with similar energy of the 3d orbitals of TM atoms in the neutral state and when the atoms are ionized, the 3d orbitals becomes more stable than the 4 s orbitals.

  5. Optical transitions and upconversion properties of Er3+-doped chloride tellurite glasses

    Institute of Scientific and Technical Information of China (English)

    Wen Lei; Li Shun-Guang; Huang Guo-Song; Hu Li-Li; Jiang Zhong-Hong

    2004-01-01

    Er3+-doped lead chloride tellurite glasses were prepared using the conventional melting and quenching method.The absorption spectra were measured and the Judd-Ofelt analysis was performed. The spectroscopic parameters such as the intensity parameters, transition probabilities, radiative lifetimes, and branching ratios were obtained. Intense infrared emission and visible upconversion luminescence under 976nm excitation were observed. For the 1.55μm emission, the full width at half maximum and the emission cross sections are more than 50 nm and 8×10-20cm2,respectively. Three efficient visible luminescences centred at 525, 547, and 658 nm are assigned to the transitions from the excited states 2H11/2, 4S3/2, and 4F9/2 to the ground state 4I15/2, respectively. The upconversion mechanisms and the power-dependent intensities are also discussed and evaluated.

  6. Structural transition and orbital glass physics in near-itinerant CoV2O4

    Science.gov (United States)

    Reig-i-Plessis, D.; Casavant, D.; Garlea, V. O.; Aczel, A. A.; Feygenson, M.; Neuefeind, J.; Zhou, H. D.; Nagler, S. E.; MacDougall, G. J.

    2016-01-01

    The ferrimagnetic spinel CoV2O4 has been a topic of intense recent interest, both as a frustrated insulator with unquenched orbital degeneracy and as a near-itinerant magnet which can be driven metallic with moderate applied pressure. Here, we report on our recent neutron diffraction and inelastic scattering measurements on powders with minimal cation site disorder. Our main new result is the identification of a weak (Δ/a a ˜10-4 ), first order structural phase transition at T*=90 K, the same temperature where spin canting was seen in recent single crystal measurements. This transition is characterized by a short-range distortion of oxygen octahedral positions, and inelastic data further establish a weak Δ ˜1.25 meV spin gap at low temperature. Together, these findings provide strong support for the local orbital picture and the existence of an orbital glass state at temperatures below T*.

  7. Electrical Conductivity, Relaxation and the Glass Transition: A New Look at a Familiar Phenomenon

    Science.gov (United States)

    Angel, Paul W.; Cooper, Alfred R.; DeGuire, Mark R.

    1996-01-01

    Annealed samples from a single melt of a 10 mol% K2O-90SiO2 glass were reheated to temperatures ranging from 450 to 800 C, held isothermally for 20 min, and then quenched in either air or a silicon oil bath. The complex impedance of both the annealed and quenched samples was measured as a function of temperature from 120 to 250 C using ac impedance spectroscopy from 1 Hz to 1 MHz. The dc conductivity, sigma(sub dc), was measured from the low frequency intercept of depressed semicircle fits to the complex impedance data. When the sigma(sub dc) at 150 C was plotted against soak temperature, the results fell into three separate regions that are explained in terms of the glass structural relaxation time, tau(sub S). This sigma(sub dc) plot provides a new way to look the glass transition range, Delta T(sub r). In addition, sigma(sub dc) was measured for different soak times at 550 C, from which an average relaxation time of 7.3 min was calculated. It was found that the size and position of the Delta T(sub r) is controlled by both the soak time and cooling rate.

  8. Composition and size dependent brittle-to-malleable transitions of Mg-based bulk metallic glasses

    Energy Technology Data Exchange (ETDEWEB)

    Yin, Jian, E-mail: yinjiandonic@yahoo.com; Ma, Xiujun; Zhou, Zhijian

    2014-05-01

    Mg-based bulk metallic glasses (BMGs) were often treated as brittle materials. However, some Mg-based BMGs were recently reported to show malleability. In order to identify the reasons for the achievement of the brittle-to-malleable transitions in the Mg-based BMGs, we systematically investigated the mechanical properties of four Mg-based BMGs (Mg{sub 65}Cu{sub 25}Gd{sub 10}, Mg{sub 65}Cu{sub 20}Ni{sub 5}Gd{sub 10}, Mg{sub 75}Ni{sub 15}Gd{sub 10}, and Mg{sub 75}Ni{sub 15}Gd{sub 5}Nd{sub 5} BMGs) using the uniaxial compression tests on the samples with sizes of ∅1×2 mm{sup 2} and ∅2×4 mm{sup 2}. The corresponding fracture morphology was observed by scanning electron microscopy (SEM). These Mg-based BMGs displayed the composition or size dependent brittle-to-malleable transitions, accompanied by the fracture mode transition from the cleavage fracture to the shear fracture. It appeared that the Mg-based BMGs were sensitive to cleavage cracks upon loading. The brittle-to-malleable transitions of the Mg-based BMGs were related to not only the stability of shear banding but also the nucleation and propagation of cleavage cracks. It was demonstrated that the suppression of the nucleation and propagation of cleavage cracks could favor the transition from the cleavage fracture to the shear fracture and encourage the brittle-to-malleable transition for the Mg-based BMGs. The underlying mechanism for the brittle-to-malleable transitions of the Mg-based BMGs was discussed with respect to both the composition and size effects.

  9. Determination of the Glass Transition Temperature of Freestanding and Supported Azo-Polymer Thin Films by Thermal Assisted Atomic Force Microscopy

    Directory of Open Access Journals (Sweden)

    Chernykh Elena

    2017-01-01

    Full Text Available In this paper we introduce and apply the method for determination of the glass transition temperature of the sub-100 nm thick freestanding and supported polymer films based on thermally assisted atomic force microscopy (AFM. In proposed approach changes of the phase of an oscillating AFM cantilever are used to determine glass transition temperature. An anomalous decrease of the glass transition temperature for both free-standing and supported azobenzene-functionalized polymer thin films is shown.

  10. Glass transition of adsorbed stereoregular PPMA by inverse gas chromatography at infinite dilution

    Science.gov (United States)

    Hamieh, T.; Rezzaki, M.; Grohens, Y.; Schultz, J.

    1998-10-01

    In this paper, we used inverse gas chromatography (IGC) at infinite dilution that proved to be a powerful technique to determine glass transition and other transitions of PMMA adsorbed on α-alumina. We highlighted the glass transition temperature of the system PMMA/α-Al2O3 with defined polymer tacticity at various covered surface fractions. Thus, the Tg of the adsorbed isotactic PMMA increases strongly as compared to the bulk value. The study of the physical chemical properties of PMMA/α-alumina revealed an important difference in the acidic and basic behaviour, in Lewis terms, of aluminium oxide covered by various concentrations of PMMA. It appears that there is a stabilisation of the physical chemical properties of PMMA/α-Al2O3 for a surface coverage above 50%. This study also highlighted an important effect of the tacticity of the polymer on the acid-base character of the system PMMA/Al2O3. Dans cet article, nous montrons que la chromatographie gazeuse inverse (CGI) à dilution infinie se révèle être une technique très intéressante pour la détermination de la transition vitreuse de polymères stéréoréguliers adsorbés sur des substrats solides tels que l'alumine. Nous avons mis en évidence des transitions attribuées aux phénomènes de relaxation béta, transition vitreuse et autres transitions des systèmes PMMA/Al2O3 de tacticité définie à différents taux de recouvrement. Ainsi, la Tg du PMMA isotactique adsorbé augmente de façon significative par rapport a celle du polymère massique. L'étude des propriétés physico-chimiques du système PMMA/Al2O3, révèle une différence importante dans le comportement acido-basique, au sens de Lewis, de l'alumine pour de taux de recouvrement en PMMA variables. Il apparaît qu'il y a stabilisation des propriétés physico-chimiques de PMMA/Al2O3 pour un taux de recouvrement en PMMA supérieur à 50 %. Cette étude a montré également une influence importante de la tacticité du polymère sur le

  11. Calcium chloride effects on the glass transition of condensed systems of potato starch.

    Science.gov (United States)

    Chuang, Lillian; Panyoyai, Naksit; Katopo, Lita; Shanks, Robert; Kasapis, Stefan

    2016-05-15

    The effect of calcium chloride on the structural properties of condensed potato starch undergoing a thermally induced glass transition has been studied using dynamic mechanical analysis and modulated differential scanning calorimetry. Extensive starch gelatinisation was obtained by hot pressing at 120°C for 7 min producing materials that covered a range of moisture contents from 3.7% w/w (11% relative humidity) to 18.8% w/w (75% relative humidity). FTIR, ESEM and WAXD were also performed in order to elucidate the manner by which salt addition affects the molecular interactions and morphology of condensed starch. Experimental protocol ensured the development of amorphous matrices that exhibited thermally reversible glassy consistency. Both moisture content and addition of calcium chloride affected the mechanical strength and glass transition temperature of polymeric systems. Highly reactive calcium ions form a direct interaction with starch to alter considerably its structural properties via an anti-plasticizing effect, as compared to the polymer-water matrix.

  12. RECOVERY OF AMORPHOUS POLY(ETHYLENE TEREPHTHALATE) FILM UNIAXIALLY DRAWN JUST BELOW THE GLASS TRANSITION TEMPERATURE

    Institute of Scientific and Technical Information of China (English)

    Nan-jian Sun; Juan Yang; De-yan Shen; Ren-yuan Qian

    2000-01-01

    Isothermal recovery in the macroscopic length of homogeneously deformed specimens of amorphous poly(ethylene terephthalate) (PET) film sample uniaxially drawn at 69℃ to the draw ratios λ0 = 1.26~2.20 were studied at temperatures around the glass transition temperature (Tg = 73 ℃). Experimental results indicate that the length recovery took place in two distinct steps: a fast first step (fast relaxation) followed by a slow second step (slow relaxation). The relaxation processes were accompanied by the reversion of trans-conformers (1340 cm-1) to gauche, and the dichroic function of the 1340 cm-1 band characterizing the segmental orientation along the chain direction decreased to a very low value at the end of the fast relaxation. This fact led us to assign the fast relaxation as the segmental orientation while the slow relaxation as relaxation of the global chain orientation. It was found that the slow relaxation follows a single exponential function, with relaxation times strongly dependent on the temperature resembling the glass transition process. The fast relaxation does not follow a single exponential decay, presumably a distribution of relaxation times is involved.

  13. On the theoretical determination of the Prigogine-Defay ratio in glass transition

    Science.gov (United States)

    Tropin, Timur V.; Schmelzer, Jürn W. P.; Gutzow, Ivan; Schick, Christoph

    2012-03-01

    In a recent analysis [J. W. P. Schmelzer and I. Gutzow, J. Chem. Phys. 125, 184511 (2006), 10.1063/1.2374894] it was shown for the first time that - in contrast to earlier belief arising from the works of Prigogine and Defay [Chemical Thermodynamics (Longman, London, 1954), Chap. 19; The first French edition of this book was published in 1950] and Davies and Jones [Adv. Phys. 2, 370 (1953), 10.1080/00018735300101252; Davies and Jones Proc. R. Soc. London, Ser. A 217, 26 (1953), 10.1098/rspa.1953.0044] - a satisfactory theoretical interpretation of the experimentally observed values of the so-called Prigogine-Defay ratio Π, being a combination of jumps of thermodynamic coefficients at glass transition, can be given employing only one structural order parameter. According to this analysis, this ratio has to be, in full agreement with experimental findings, larger than one (Π > 1). Its particular value depends both on the thermodynamic properties of the system under consideration and on cooling and heating rates. Based on above-mentioned analysis, latter dependence on cooling rates has been studied in detail in another own preceding paper [T. V. Tropin, J. W. P. Schmelzer, and C. Schick, J. Non-Cryst. Solids 357, 1303 (2011), 10.1016/j.jnoncrysol.2010.12.005]. In the present analysis, an alternative general method of determination of the Prigogine-Defay ratio is outlined, allowing one to determine this ratio having at ones disposal the generalized equation of state of the glass-forming melts under consideration and, in particular, the knowledge of the equilibrium properties of the melts in the glass transformation range. Employing, as an illustration of the method, a particular model for the description of glass-forming melts, theoretical estimates are given for this ratio being, again, in good agreement with experimental data.

  14. E→H mode transition density and power in two types of inductively coupled plasma configuration

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Jian; Du, Yin-chang; Zhang, Xiao; Zheng, Zhe; Liu, Yu; Xu, Liang; Wang, Pi; Cao, Jin-xiang, E-mail: jxcao@ustc.edu.cn [Department of Modern Physics, University of Science and Technology of China, Hefei, Anhui 230026 (China)

    2014-07-15

    E → H transition power and density were investigated at various argon pressures in inductively coupled plasma (ICP) in a cylindrical interlaid chamber. The transition power versus the pressure shows a minimum transition power at 4 Pa (ν/ω=1) for argon. Then the transition density hardly changes at low pressures (ν/ω≪1), but it increases clearly when argon pressure exceeds an appropriate value. In addition, both the transition power and transition density are lower in the re-entrant configuration of ICP compared with that in the cylindrical configuration of ICP. The result may be caused from the decrease of stochastic heating in the re-entrant configuration of ICP. This work is useful to understand E → H mode transition and control the transition points in real plasma processes.

  15. Influence of microwave vacuum drying on glass transition temperature, gelatinization temperature, physical and chemical qualities of lotus seeds.

    Science.gov (United States)

    Zhao, Yingting; Jiang, Yajun; Zheng, Baodong; Zhuang, Weijing; Zheng, Yafeng; Tian, Yuting

    2017-08-01

    This study investigated the effects of microwave power density on effective moisture diffusion coefficient (Deff), glass transition temperature (Tg), gelatinization temperature (TP), physical and chemical qualities of lotus seeds during microwave vacuum drying. Deff increased by 42% and 127% at 15W/g and 20W/g, respectively, when compared with 10W/g. TP was negatively correlated with the relaxation times of T21 and T22, while Tg was negatively correlated with the relative areas A22. The rates of change of color were observed to be divided roughly into two periods, consisting of a rapid change caused by enzymatic browning and a slow change caused by non-enzymatic browning. An equation is provided to illustrate the relationship of k1 and k2 of Peleg's model depending on power density during rehydration kinetics. The samples at 20W/g exhibited the higher content of amino acid (540.19mg/100gd.b.) while lower starch (17.53g/100gd.b.).

  16. Glass transition of aqueous solutions involving annealing-induced ice recrystallization resolves liquid-liquid transition puzzle of water.

    Science.gov (United States)

    Zhao, Li-Shan; Cao, Ze-Xian; Wang, Qiang

    2015-10-27

    Liquid-liquid transition of water is an important concept in condensed-matter physics. Recently, it was claimed to have been confirmed in aqueous solutions based on annealing-induced upshift of glass-liquid transition temperature, T(g) . Here we report a universal water-content, X(aqu) , dependence of T(g) for aqueous solutions. Solutions with X(aqu)>X(cr)(aqu)vitrify/devitrify at a constant temperature, ~T(g) , referring to freeze-concentrated phase with X(aqu)left behind ice crystallization. Those solutions with X(aqu)recrystallization is stabilized at . Experiments on aqueous glycerol and 1,2,4-butanetriol solutions in literature were repeated, and the same samples subject to other annealing treatments equally reproduce the result. The upshift of T(g) by annealing is attributable to freeze-concentrated phase of solutions instead of 'liquid II phase of water'. Our work also provides a reliable method to determine hydration formula and to scrutinize solute-solvent interaction in solution.

  17. Thermodynamic evidence for cluster ordering in Cu46Zr42Al7Y5 ribbons during glass transition

    DEFF Research Database (Denmark)

    Zheng, H.J.; Lv, Y.M.; Sun, Q.J.;

    2016-01-01

    -Tg (Tg, glass transition temperature) relaxation and the crystallization process, respectively. The second one is attributed to a partial overlap between the endothermic response to the glass transition and the exothermic response to the formation of ordered clusters. The cluster ordering, which begins...... at the final stage of glass transition, has been verified by the differences in the activation energy of the sub-Tg relaxation, the cluster ordering and primary crystallization for both the as-spun and annealed ribbons. The cluster ordering could be driven by the large difference between the Zr–Y mixing...... enthalpy and the Al–Y (or Cu–Y) mixing enthalpy. The findings contribute to distinguishing between phase separation and clusters motion scenarios....

  18. Kaplansky Density and Kadison Transitivity Theorems for Irreducible Representations of Real C*-Algebras

    Institute of Scientific and Technical Information of China (English)

    Jeffrey L. BOERSEMA

    2007-01-01

    We prove analogs of the Kaplansky Density Theorem and the Kadison Transitivity Theorem for irreducible representations of a real C*-algebra on a real Hilbert space. Specifically, if a C*-algebra is acting irreducibly on a real Hilbert space, then the Hilbert space has either a real, complex, or quaternionic structure with respect to which the density and transitivity theorems hold.

  19. Effect of AlF3 on the Density and Elastic Properties of Zinc Tellurite Glass Systems

    Directory of Open Access Journals (Sweden)

    Zainal Abidin Talib

    2012-08-01

    Full Text Available This paper presents the results of the physical and elastic properties of the ternary zinc oxyfluoro tellurite glass system. Systematic series of glasses (AlF3x(ZnOy(TeO2z with x = 0–19, y = 0–20 and z = 80, 85, 90 mol% were synthesized by the conventional rapid melt quenching technique. The composition dependence of the physical, mainly density and molar volume, and elastic properties is discussed in term of the AlF3 modifiers addition that are expected to produce quite substantial changes in their physical properties. The absence of any crystalline peaks in the X-ray diffraction (XRD patterns of the present glass samples indicates the amorphous nature. The addition of AlF3 lowered the values of the densities in ternary oxyfluorotellurite glass systems. The longitudinal and transverse ultrasonic waves propagated in each glass sample were measured using a MBS8020 ultrasonic data acquisition system. All the velocity data were taken at 5 MHz frequency and room temperature. The longitudinal modulus (L, shear modulus (G, Young’s modulus (E, bulk modulus (K and Poisson’s ratio ( are obtained from both velocities data and their respective density. Experimental data shows the density and elastic moduli of each AlF3-ZnO-TeO2 series are found strongly depend upon the glass composition. The addition of AlF3 modifiers into the zinc tellurite causes substantial changes in their density, molar volume as well as their elastic properties.

  20. Glass transition and relaxation dynamics of propylene glycol-water solutions confined in clay

    Science.gov (United States)

    Elamin, Khalid; Björklund, Jimmy; Nyhlén, Fredrik; Yttergren, Madeleine; Mârtensson, Lena; Swenson, Jan

    2014-07-01

    The molecular dynamics of aqueous solutions of propylene glycol (PG) and propylene glycol methylether (PGME) confined in a two-dimensional layer-structured Na-vermiculite clay has been studied by broadband dielectric spectroscopy and differential scanning calorimetry. As typical for liquids in confined geometries the intensity of the cooperative α-relaxation becomes considerably more suppressed than the more local β-like relaxation processes. In fact, at high water contents the calorimetric glass transition and related structural α-relaxation cannot even be observed, due to the confinement. Thus, the intensity of the viscosity related α-relaxation is dramatically reduced, but its time scale as well as the related glass transition temperature Tg are for both systems only weakly influenced by the confinement. In the case of the PGME-water solutions it is an important finding since in the corresponding bulk system a pronounced non-monotonic concentration dependence of the glass transition related dynamics has been observed due to the growth of hydrogen bonded relaxing entities of water bridging between PGME molecules [J. Sjöström, J. Mattsson, R. Bergman, and J. Swenson, Phys. Chem. B 115, 10013 (2011)]. The present results suggest that the same type of structural entities are formed in the quasi-two-dimensional space between the clay platelets. It is also observed that the main water relaxation cannot be distinguished from the β-relaxation of PG or PGME in the concentration range up to intermediate water contents. This suggests that these two processes are coupled and that the water molecules affect the time scale of the β-relaxation. However, this is most likely true also for the corresponding bulk solutions, which exhibit similar time scales of this combined relaxation process below Tg. Finally, it is found that at higher water contents the water relaxation does not merge with, or follow, the α-relaxation above Tg, but instead crosses the

  1. Yielding of glass under shear: A directed percolation transition precedes shear-band formation

    Science.gov (United States)

    Shrivastav, Gaurav Prakash; Chaudhuri, Pinaki; Horbach, Jürgen

    2016-10-01

    Under external mechanical loading, glassy materials, ranging from soft matter systems to metallic alloys, often respond via formation of inhomogeneous flow patterns, during yielding. These inhomogeneities can be precursors to catastrophic failure, implying that a better understanding of their underlying mechanisms could lead to the design of smarter materials. Here, extensive molecular dynamics simulations are used to reveal the emergence of heterogeneous dynamics in a binary Lennard-Jones glass, subjected to a constant strain rate. At a critical strain, this system exhibits for all considered strain rates a transition towards the formation of a percolating cluster of mobile regions. We give evidence that this transition belongs to the universality class of directed percolation. Only at low shear rates, the percolating cluster subsequently evolves into a transient (but long-lived) shear band with a diffusive growth of its width. Finally, the steady state with a homogeneous flow pattern is reached. In the steady state, percolation transitions also do occur constantly, albeit over smaller strain intervals, to maintain the stationary plastic flow in the system.

  2. Molecular dynamics simulation for the baryon-quark phase transition at finite baryon density

    Energy Technology Data Exchange (ETDEWEB)

    Akimura, Y. [Saitama University, Department of physics, Sakura-Ku, Saitama City (Japan); Japan Atomic Energy Research Institute, Advanced Science Research Center, Tokai (Japan); Maruyama, T.; Chiba, S. [Japan Atomic Energy Research Institute, Advanced Science Research Center, Tokai (Japan); Yoshinaga, N. [Saitama University, Department of physics, Sakura-Ku, Saitama City (Japan)

    2005-09-01

    We study the baryon-quark phase transition in the molecular dynamics (MD) of the quark degrees of freedom at finite baryon density. The baryon state at low baryon density, and the deconfined quark state at high baryon density are reproduced. We investigate the equations of state of matters with different u-d-s compositions. It is found that the baryon-quark transition is sensitive to the quark width. (orig.)

  3. Thermodynamic behaviour of gliadins mixture and the glass-softening transition of its dried state.

    Science.gov (United States)

    Ferrari, C; Johari, G P

    1997-10-01

    The glass-softening transition of a mixture of gliadins extracted from wheat flour has been studied in its dry state by differential scanning calorimetry (DSC). Further, the rate of removal of its water vapours on its evaporation from a gliadins mixture containing different amounts of water has been investigated, and through this the presence of any exothermic effect that could be attributed to polymerization of gliadins has been examined. The heat absorbed in this evaporation is comparable with the heat of evaporation of pure water measured in a separate experiment in identical conditions. This showed that the gliadins mixture did not polymerize on heating up to 473 K in the presence of moisture. In this respect the behaviour of the gliadins mixture differs remarkably from that of gluten studied before (J Phys Chem 1996:100:19692). The effects of purge gas, helium and argon, on the calorimetric effects during the evaporation of water have been studied. A restudy of gluten shows that helium decreases substantially the endothermic signal in the DSC measurements, and thereby reveals the exothermic effects of polymerization in gluten, but argon does not do so. The structural relaxation time, t, of dry gliadins mixtures at different temperatures has been calculated from an analysis of its glass-softening endotherm. The temperature at which t = 1 ks is 452 K, and the Tg, obtained by the usual method of intersection of the straight lines drawn, is 443 K, 7 K higher than for the polymerized dry gluten, the distribution of relaxation time parameter is 0.25, and increase in the heat capacity in this range is 0.21 J/g K. Physical ageing effects are considerable in the gliadins mixture, which alters the glass-softening endotherm but not the structural relaxation time or its distribution.

  4. A direct test of the correlation between elastic parameters and fragility of ten glass formers and their relationship to elastic models of the glass transition

    Science.gov (United States)

    Torchinsky, Darius H.; Johnson, Jeremy A.; Nelson, Keith A.

    2009-02-01

    We present an impulsive stimulated scattering test of the "shoving model" of the glass transition and of the correlation between the fragility index and the ratio of instantaneous elastic moduli of eight supercooled liquids. Samples of triphenyl phosphite, DC704 (tetramethyl tetraphenyl trisiloxane), m-fluoroaniline, Ca(NO3)2ṡ4H2O, diethyl phthalate, propylene carbonate, m-toluidine, phenyl salicylate (salol), 2-benzylphenol, and Santovac 5 (5-phenyl 4-ether), were cooled to their respective glass transition temperatures and the elastic moduli directly measured at the highest accessible shear frequencies. The shear modulus was then measured every 2 K as deeply as permitted into the liquid state for all liquids except propylene carbonate. Our results, in conjunction with dynamical relaxation data for these liquids obtained from the literature, lend credence to the notion that the dynamics of the glass transition are governed by the evolution of the shear modulus but do not suggest a strong correlation between the fragility index and the ratio of the elastic moduli.

  5. Transition from stress-driven to thermally activated stress relaxation in metallic glasses

    Science.gov (United States)

    Qiao, J. C.; Wang, Yun-Jiang; Zhao, L. Z.; Dai, L. H.; Crespo, D.; Pelletier, J. M.; Keer, L. M.; Yao, Y.

    2016-09-01

    The short-range ordered but long-range disordered structure of metallic glasses yields strong structural and dynamic heterogeneities. Stress relaxation is a technique to trace the evolution of stress in response to a fixed strain, which reflects the dynamic features phenomenologically described by the Kohlrausch-Williams-Watts (KWW) equation. The KWW equation describes a broad distribution of relaxation times with a small number of empirical parameters, but it does not arise from a particular physically motivated mechanistic picture. Here we report an anomalous two-stage stress relaxation behavior in a Cu46Zr46Al8 metallic glass over a wide temperature range and generalize the findings in other compositions. Thermodynamic analysis identifies two categories of processes: a fast stress-driven event with large activation volume and a slow thermally activated event with small activation volume, which synthetically dominates the stress relaxation dynamics. Discrete analyses rationalize the transition mechanism induced by stress and explain the anomalous variation of the KWW characteristic time with temperature. Atomistic simulations reveal that the stress-driven event involves virtually instantaneous short-range atomic rearrangement, while the thermally activated event is the percolation of the fast event accommodated by the long-range atomic diffusion. The insights may clarify the underlying physical mechanisms behind the phenomenological description and shed light on correlating the hierarchical dynamics and structural heterogeneity of amorphous solids.

  6. Retrogradation of Waxy Rice Starch Gel in the Vicinity of the Glass Transition Temperature

    Science.gov (United States)

    Charoenrein, Sanguansri; Udomrati, Sunsanee

    2013-01-01

    The retrogradation rate of waxy rice starch gel was investigated during storage at temperatures in the vicinity of the glass transition temperature of a maximally concentrated system (Tg′), as it was hypothesized that such temperatures might cause different effects on retrogradation. The Tg′ value of fully gelatinized waxy rice starch gel with 50% water content and the enthalpy of melting retrograded amylopectin in the gels were investigated using differential scanning calorimetry. Starch gels were frozen to −30°C and stored at 4, 0, −3, −5, and −8°C for 5 days. The results indicated that the Tg′ value of gelatinized starch gel annealed at −7°C for 15 min was −3.5°C. Waxy rice starch gels retrograded significantly when stored at 4°C with a decrease in the enthalpy of melting retrograded starch in samples stored for 5 days at −3, −5, and −8°C, respectively, perhaps due to the more rigid glass matrix and less molecular mobility facilitating starch chain recrystallization at temperatures below Tg′. This suggests that retardation of retrogradation of waxy rice starch gel can be achieved at temperature below Tg′. PMID:26904602

  7. Retrogradation of Waxy Rice Starch Gel in the Vicinity of the Glass Transition Temperature

    Directory of Open Access Journals (Sweden)

    Sanguansri Charoenrein

    2013-01-01

    Full Text Available The retrogradation rate of waxy rice starch gel was investigated during storage at temperatures in the vicinity of the glass transition temperature of a maximally concentrated system (, as it was hypothesized that such temperatures might cause different effects on retrogradation. The value of fully gelatinized waxy rice starch gel with 50% water content and the enthalpy of melting retrograded amylopectin in the gels were investigated using differential scanning calorimetry. Starch gels were frozen to −30°C and stored at 4, 0, −3, −5, and −8°C for 5 days. The results indicated that the value of gelatinized starch gel annealed at −7°C for 15 min was −3.5°C. Waxy rice starch gels retrograded significantly when stored at 4°C with a decrease in the enthalpy of melting retrograded starch in samples stored for 5 days at −3, −5, and −8°C, respectively, perhaps due to the more rigid glass matrix and less molecular mobility facilitating starch chain recrystallization at temperatures below . This suggests that retardation of retrogradation of waxy rice starch gel can be achieved at temperature below .

  8. Retrogradation of Waxy Rice Starch Gel in the Vicinity of the Glass Transition Temperature.

    Science.gov (United States)

    Charoenrein, Sanguansri; Udomrati, Sunsanee

    2013-01-01

    The retrogradation rate of waxy rice starch gel was investigated during storage at temperatures in the vicinity of the glass transition temperature of a maximally concentrated system (T g '), as it was hypothesized that such temperatures might cause different effects on retrogradation. The T g ' value of fully gelatinized waxy rice starch gel with 50% water content and the enthalpy of melting retrograded amylopectin in the gels were investigated using differential scanning calorimetry. Starch gels were frozen to -30°C and stored at 4, 0, -3, -5, and -8°C for 5 days. The results indicated that the T g ' value of gelatinized starch gel annealed at -7°C for 15 min was -3.5°C. Waxy rice starch gels retrograded significantly when stored at 4°C with a decrease in the enthalpy of melting retrograded starch in samples stored for 5 days at -3, -5, and -8°C, respectively, perhaps due to the more rigid glass matrix and less molecular mobility facilitating starch chain recrystallization at temperatures below T g '. This suggests that retardation of retrogradation of waxy rice starch gel can be achieved at temperature below T g '.

  9. Possible crossover to percolation scenario near superfluid-Bose-glass transition

    Science.gov (United States)

    Syromyatnikov, A. V.; Sizanov, A. V.

    2017-10-01

    We discuss magnetically ordered (;superfluid;) phase near quantum transition to Bose-glass phase in a simple modeling system, Heisenberg antiferromagnet in spatial dimension d > 2 in external magnetic field with disorder in exchange coupling constants. Our analytical consideration is based on hydrodynamic description of long-wavelength excitations and it is valid in the entire critical region near the quantum critical point (QCP). We demonstrate that the system behaves in full agreement with predictions by Fisher et al. (Phys. Rev. B 40, 546 (1989)) in close vicinity of QCP. On the other hand, we show that many recent experimental and numerical results obtained in various 3D systems can be described by our formulas using percolation critical exponents. Then, it is a possibility that a percolation critical regime arises in the ordered phase in some 3D systems not very close to QCP.

  10. Glass and Jamming Transitions: From Exact Results to Finite-Dimensional Descriptions

    Science.gov (United States)

    Charbonneau, Patrick; Kurchan, Jorge; Parisi, Giorgio; Urbani, Pierfrancesco; Zamponi, Francesco

    2017-03-01

    Despite decades of work, gaining a first-principles understanding of amorphous materials remains an extremely challenging problem. However, recent theoretical breakthroughs have led to the formulation of an exact solution of a microscopic glass-forming model in the mean-field limit of infinite spatial dimension. Numerical simulations have remarkably confirmed the dimensional robustness of some of the predictions. This review describes these latest advances. More specifically, we consider the dynamical and thermodynamic descriptions of hard spheres around the dynamical, Gardner, and jamming transitions. Comparing mean-field predictions with the finite-dimensional simulations, we identify robust aspects of the theory and uncover its more sensitive features. We conclude with a brief overview of ongoing research.

  11. Glass-to-Rubber Transition of Polymer Thin Films and Their Surface Dynamical Properties

    Institute of Scientific and Technical Information of China (English)

    X.P.Wang; H.F.Zhang; Xudong Xiao; Ophelia K.C.Tsui

    2000-01-01

    @@ Glass-to-rubber transition temperature, Tg' of polystyrene(PS) (Mw=500K, Mw/Mn=1.03)thin films (thickness, d= 100 to 2000 A) deposited on Si with native oxide was determined by variable angle spectroscopic ellipsometry(VASE. We observed that the Tg of the polymer films decreased monotonically as the film thickness was decreased. It had previously been proposed that this was due to a highly mobile surface rubbery layer that existed even well below Tg' We used atomic force microscopic(AFM)adhesion measurement as a direct probe to investigate the surface dynamical properties of the PS samples and a thin film ofpoly(tert-butyl acrylate) (PtBA) (Mw= 148K, Mw/Mn=17, and Tg bullk=50℃). By comparing the AFM results and those obtained from shear modulus measurements of a bulk sample, we found no enhancement in the molecular relaxation at the free surface of these samples.

  12. Glass transition temperature of PIB, PDMS and PMMA from small-time simulations

    Science.gov (United States)

    Duki, Solomon; Tsige, Mesfin; Taylor, Philip

    2009-03-01

    We have applied some new techniques to obtain predictions of the glass transition temperatures Tg of poly(isobutylene), poly(dimethyl-siloxane), and poly(methyl methacrylate) from small-time atomistic molecular dynamics simulations. The different fragilities of these materials are reflected in the results of the simulations. One approach involved measurement of the apparent softening of the ``cage'' in which a monomer is bound, while another involved studying autocorrelation of a convolution of the velocity with a smoothing function in order to detect the frequency of escapes from the ``cage.'' To check the accuracy of the short-time methods, the Tg of the polymers was also found using conventional diffusion simulations in which the rate of increase of the root mean squared displacement of an atom, monomer, or molecule is measured at very long times. The economical short-time simulations yielded results for Tg that were identical to those of the computer-intensive long-time simulations.

  13. Reduced glass transition temperatures in thin polymer films: surface effect or artifact?

    Science.gov (United States)

    Bäumchen, O; McGraw, J D; Forrest, J A; Dalnoki-Veress, K

    2012-08-03

    We have examined the direct effect of manipulating the number of free surfaces on the measured glass transition temperature T(g) of thin polystyrene films. Thin films in the range 35 nm thickness and refractive index of freestanding films. By noting the change in slope in each of these quantities, a T(g) value can be assigned in quantitative agreement with previously reported results. For thin freestanding films this value is reduced from that of the bulk. The exact same films are then transferred to a Si substrate and the T(g) of the resulting supported film was determined. The T(g) values of the now supported films are the same as the bulk value and the same as previous reports of similar supported films. These experiments unambiguously show that free interfaces are the dominant cause of the T(g) reductions for the film thicknesses studied.

  14. Relation Between Glass Transition Temperatures in Polymer Nanocomposites and Polymer Thin Films

    Science.gov (United States)

    Kropka, Jamie; Pryamitsyn, Victor; Ganesan, Venkat

    2009-03-01

    Motivated by recent experiments, we examine within a percolation model whether there is a quantitative equivalence in the glass transition temperatures of polymer thin films and polymer nanocomposites (PNCs). Our results indicate that while the qualitative behaviors of these systems are similar, a quantitative equivalence cannot be established in general. However, we propose a phenomenological scaling collapse of our results which suggests a simple framework by which the results of the thin films may be used to quantitatively predict the properties of PNCs. Sandia is a multi-program laboratory operated by Sandia Corporation, a Lockheed Martin Company, for the United States Department of Energy's National Nuclear Security Administration under Contract DE-AC04-94AL85000.

  15. High-dimensional surprises neat the glass and the jamming transitions

    Science.gov (United States)

    Charbonneau, Patrick

    2013-03-01

    The glass problem is notoriously hard and controversial. Even at the mean-field level, there is little agreement about how a fluid turns sluggish while exhibiting but unremarkable structural changes. It is clear, however, that the process involves self-caging, which provides an order parameter for the transition. It is also broadly assumed that this cage should have a Gaussian shape in the mean-field limit. Here we show that this ansatz does not hold, and explore its consequences. Non-Gaussian caging, for instance, persists all the way to the jamming limit of infinitely compressed hard spheres, which affects mechanical stability. We thus obtain new scaling relations, and establish clear mileposts for the emergence of a mean-field theory of jamming.

  16. Deformation of Thin Free-standing Films with Sessile Droplets Through the Glass Transition

    Science.gov (United States)

    Fortais, Adam; Schulman, Rafael; Dalnoki-Veress, Kari

    Droplets on a rigid substrate will form a contact angle determined by interfacial tensions according to Young's law. Likewise, the Laplace pressure of a droplet will deform a liquid substrate, and the contact line geometry can be determined through a Neumann construction. We explore the intermediate case of micro-droplets placed on thin, highly compliant, free-standing films. The Laplace pressure of the droplet deforms the free-standing film, creating a spherical bulge. The film's tension is modulated by changing temperature continuously from well below the glass transition into the melt state of the film. The contact angle of the liquid droplet with the undeformed film as well as the angle of the bulge with the film is measured and compared to the contact angles predicted by a force balance at the contact line.

  17. Glass transition of polystyrene (PS) studied by Raman spectroscopic investigation of its phenyl functional groups

    Science.gov (United States)

    Bertoldo Menezes, D.; Reyer, A.; Marletta, A.; Musso, M.

    2017-01-01

    In polymeric materials the glass transition (GT) is a well-known and very important relaxation process related to movements of functional groups in the polymeric chain. In this work, we show the potential of Raman spectroscopy for exploring the GT process in the polymer polystyrene. We collected Raman spectra during a step-by-step heating process of the sample, which allowed us to collect signatures of the GT process from peak parameters of specific vibrational modes, and to verify the GT temperature. Results of the latter were in accordance with published values obtained via other methods. We identified the aromatic ring vibrational modes of the phenyl functional groups to be those which, due to steric hindrance, suffer the largest influence during the GT process. This confirms that Raman spectroscopy can be used as a complementary technique to perform GT investigations in polymeric materials due to its sensitivity to small intermolecular changes affecting vibrational properties of relevant functional side groups.

  18. Effect of atmosphere on reductions in the glass transition of thin polystyrene films

    Science.gov (United States)

    Raegen, A. N.; Massa, M. V.; Forrest, J. A.; Dalnoki-Veress, K.

    2008-12-01

    We have used nulling ellipsometry to measure the glass transition temperature, T g , of thin films of polystyrene in ambient, dry nitrogen, and vacuum environments. For all environments, the measured T g values decrease with decreasing film thickness in a way that is quantitatively similar to previously reported studies in ambient conditions. These results provide strong reinforcement of previous conclusions that such reduced T g values are an intrinsic property of the confined material. Furthermore, the results are in contrast to recent reports which suggest that the T g reductions measured by many researchers are the results of artifacts (i.e. degradation of the polymer due to annealing in ambient conditions, or moisture content).

  19. Coupled effects of substrate adhesion and intermolecular forces on polymer thin film glass-transition behavior.

    Science.gov (United States)

    Xia, Wenjie; Keten, Sinan

    2013-10-15

    Intermolecular noncovalent forces between polymer chains influence the mobility and glass-transition temperature (Tg), where weaker interchain interactions, all else being the same, typically results in lower bulk polymer Tg. Using molecular dynamics simulations, here we show that this relation can become invalid for supported ultrathin films when the substrate-polymer interaction is extremely strong and the polymer-polymer interactions are much weaker. This contrasting trend is found to be due to a more pronounced substrate-induced appreciation of the film Tg for polymers with weaker intermolecular interactions and low bulk Tg. We show that optimizing this coupling between substrate adhesion and bulk Tg maximizes thin film Tg, paving the way for tuning film properties through interface nanoengineering.

  20. Enhancement in the Glass Transition Temperature in Latent Thiol-Epoxy Click Cured Thermosets

    Directory of Open Access Journals (Sweden)

    Dailyn Guzmán

    2015-04-01

    Full Text Available Tri and tetrafunctional thiol were used as curing agent for diglycidyl ether of bisphenol A (DGEBA catalyzed by a commercially available amine precursor, LC-80. Triglycidyl isocianurate (TGIC was added in different proportions to the mixture to increase rigidity and glass transition temperature (Tg. The cooperative effect of increasing functionality of thiol and the presence of TGIC in the formulation leads to an increased Tg without affecting thermal stability. The kinetics of the curing of mixtures was studied by calorimetry under isothermal and non-isothermal conditions. The latent characteristics of the formulations containing amine precursors were investigated by rheometry and calorimetry. The increase in the functionality of the thiol produces a slight decrease in the storage lifetime of the mixture. The materials obtained with tetrathiol as curing agent showed the highest values of Young’s modulus and Tg.

  1. Preparation of high density heavy metal fluoride glasses with extended ultraviolet and infra red ranges, and such high density heavy metal fluoride glasses

    Science.gov (United States)

    Martin, Steven W. (Inventor); Huebsch, Jesse (Inventor)

    2001-01-01

    A heavy metal fluoride glass composition range (in mol percent) consisting essentially of: (16-30)BaF.sub.2.(8-26)HfF.sub.4.(6-24)InF.sub.3 or GaF.sub.3.(4-16)CdF.sub.2.(6-24)YbF.sub.3.(4-22)ZnF.sub.2. In an alternative embodiment, a heavy metal fluoride glass composition range (in mol percent) comprises (16-30)BaF.sub.2.(8-26)HfF.sub.4.(6-24) of (0-24)InF.sub.3, (0-24)GaF.sub.3 and (0-19)AlF.sub.3.(1-16)CdF.sub.2.(6-24)YbF.sub.3.(4-26)ZnF.sub.2. A preferred heavy metal fluoride glass produced in accordance with the present invention comprises a composition (in mol %) and comprises about 26BaF.sub.2.18HfF.sub.4.7InF.sub.3.5GaF.sub.3.10CdF.sub.2.18YbF.sub.3. 16ZnF.sub.2. A preferred heavy metal fluoride glass has maximum thickness of most preferably about 3 mm. Another preferred heavy metal fluoride glass comprises a composition (in mol %) and comprises about 26BaF.sub.2.18HfF.sub.4.12AlF.sub.3.10CdF.sub.2.18YbF.sub.3.16ZnF.sub.2.

  2. Experiments on Transitional Subaqueous Density Flows and Resulting Sediment Deposits

    Science.gov (United States)

    Barnaal, Z. D.; Parker, G.

    2016-12-01

    Much remains unknown regarding the sedimentary deposits of submarine gravity flows. Flows with large concentrations of suspended sediment may transition from a more turbulent to a more coherent flow type. Such transitional flows may be produced when turbulence becomes suppressed due to entrainment of cohesive sediment or from flow deceleration. Argillaceous sandstones and linked turbidite-debrites are types of submarine sediment deposits in a category known as hybrid event beds, and are interpreted to be emplaced by transitional regime flows (Talling, 2007; Davis, 2009; Haughton, 2009; Hodgson, 2009; Sumner, 2009; Baas, 2011; Lee, 2013; and Talling, 2013). Here we report on the physical modelling of such transitional flows. The sediment consists of mixtures of non-cohesive silica flour with a median grain size of 30 microns and kaolin clay with a median size of 4 microns. These sediments were mixed in ratios including 100%, 70%, 60%, 50%, 30% and 0% kaolin. Total volume concentration of the input slurry varied from 0.01 to 0.2, allowing coverage of wide range of transitional flow types. The flow passed over a 4.9-m-long bed with a slope of 7 degrees, and continued another 4.9 m over a horizontal bed before exiting the tank. Measurements of flow velocity profiles, flow concentrations, deposit geometry, and deposit grain-size distributions were conducted. The results of experiments help us to better understand the rheology, and to determine the structure and patterns of deposits including argillaceous sandstones.

  3. Shape transition of state density for bosonic systems

    Indian Academy of Sciences (India)

    Harshal N Deota; N D Chavda; V Potbhare

    2013-12-01

    For a finite boson system, the ensemble-averaged state density has been computed with respect to the body interaction rank . The shape of such a state density changes from Gaussian to semicircle as the body rank of the interaction increases. This state density is expressed as a linear superposition of Gaussian and semicircular states. The nearest-neighbour spacing distribution (NNSD), which is one of the most important spectral properties of a system, is studied. The NNSDs are rather independent of body rank and show a Wigner distribution throughout.

  4. Improvements in processing characteristics and engineering properties of wood flour-filled high density polyethylene composite sheeting in the presence of hollow glass microspheres

    Science.gov (United States)

    Baris Yalcin; Steve E Amos; Andrew S D Souza; Craig M Clemons; I Sedat Gunes; Troy K Ista

    2012-01-01

    Hollow glass microspheres were introduced into wood flour/high density polyethylene composites by melt compounding in a twin-screw extruder. The prepared composites were subsequently converted to extruded profiles in order to obtain composite sheeting. The presence of hollow glass microspheres highly reduced the density of the extruded sheets down to 0.9 g/cc, while...

  5. Effect of molecular weight and glass transition on relaxation and release behaviour of poly(DL-lactic acid) tablets

    NARCIS (Netherlands)

    Steendam, R.; Van Steenbergen, M.J.; Hennink, W.E.; Frijlink, H.W.; Lerk, C.F.

    2001-01-01

    Different molecular weight grades of poly(DL-lactic acid) were applied as release controlling excipients in tablets for oral drug administration. The role of molecular weight and glass transition in the mechanism of water-induced volume expansion and drug release of PDLA tablets was investigated. Mo

  6. Solidification of a colloidal hard sphere like model system approaching and crossing the glass transition.

    Science.gov (United States)

    Franke, Markus; Golde, Sebastian; Schöpe, Hans Joachim

    2014-08-07

    We investigated the process of vitrification and crystallization in a model system of colloidal hard spheres. The kinetics of the solidification process was measured using time resolved static light scattering, while the time evolution of the dynamic properties was determined using time resolved dynamic light scattering. By performing further analysis we confirm that solidification of hard sphere colloids is mediated by precursors. Analyzing the dynamic properties we can show that the long time dynamics and thus the shear rigidity of the metastable melt is highly correlated with the number density of solid clusters (precursors) nucleated. In crystallization these objects convert into highly ordered crystals whereas in the case of vitrification this conversion is blocked and the system is (temporarily) locked in the metastable precursor state. From the early stages of solidification one cannot clearly conclude whether the melt will crystallize or vitrify. Furthermore our data suggests that colloidal hard sphere glasses can crystallize via homogeneous nucleation.

  7. Molecular dynamics simulation for baryon-quark phase transition at finite temperature and density

    CERN Document Server

    Akimura, Y; Yoshinaga, N; Chiba, S; Akimura, Yuka; Maruyama, Toshiki; Yoshinaga, Naotaka; Chiba, Satoshi

    2005-01-01

    We study the baryon-quark phase transition in a molecular dynamics (MD) of quark degrees of freedom at finite temperature and density. The baryon state at low density and temperature, and the deconfined quark state at high density and temperature are reproduced. We investigate the equations of state of matters with different $u$-$d$-$s$ compositions. Then we draw phase diagrams in the temperature-density plane by this simulation. It is found that the baryon-quark transition is sensitive to the quark width.

  8. The glass transition and enthalpy recovery of a single polystyrene ultrathin film using Flash DSC

    Science.gov (United States)

    Koh, Yung P.; Simon, Sindee L.

    2017-05-01

    The kinetics of the glass transition are measured for a single polystyrene ultrathin film of 20 nm thickness using Flash differential scanning calorimetry (DSC). Tg is measured over a range of cooling rates from 0.1 to 1000 K/s and is depressed compared to the bulk. The depression decreases with increasing cooling rate, from 12 K lower than the bulk at 0.1 K/s to no significant change at 1000 K/s. Isothermal enthalpy recovery measurements are performed from 50 to 115 °C, and from these experiments, the temperature dependence of the induction time along the glass line is obtained, as well as the temperature dependence of the time scale required to reach equilibrium, providing a measure of the shortest effective glassy relaxation time and the longest effective equilibrium relaxation time, respectively. The induction time for the ultrathin film is found to be similar to the bulk at all temperatures presumably because the Tg values are the same due to the use of a cooling rate of 1000 K/s prior to the enthalpy recovery measurements. On the other hand, the times required to reach equilibrium for the ultrathin film and bulk are similar at 100 °C, and considerably shorter for the ultrathin film at 90 °C, consistent with faster dynamics under nanoconfinement at low temperatures. The magnitude of the "Tg depression" is smaller when using the equilibrium relaxation time from the structural recovery experiment as a measure of the dynamics than when measuring Tg after a cooling experiment. A relaxation map is developed to summarize the results.

  9. Multidiffusion mechanisms for noble gases (He, Ne, Ar) in silicate glasses and melts in the transition temperature domain: Implications for glass polymerization

    Science.gov (United States)

    Amalberti, Julien; Burnard, Pete; Laporte, Didier; Tissandier, Laurent; Neuville, Daniel R.

    2016-01-01

    Noble gases are ideal probes to study the structure of silicate glasses and melts as the modifications of the silicate network induced by the incorporation of noble gases are negligible. In addition, there are systematic variations in noble gas atomic radii and several noble gas isotopes with which the influence of the network itself on diffusion may be investigated. Noble gases are therefore ideally suited to constrain the time scales of magma degassing and cooling. In order to document noble gas diffusion behavior in silicate glass, we measured the diffusivities of three noble gases (4He, 20Ne and 40Ar) and the isotopic diffusivities of two Ar isotopes (36Ar and 40Ar) in two synthetic basaltic glasses (G1 and G2; 20Ne and 36Ar were only measured in sample G1). These new diffusion results are used to re-interpret time scales of the acquisition of fractionated atmospheric noble gas signatures in pumices. The noble gas bearing glasses were synthesized by exposing the liquids to high noble gas partial pressures at high temperature and pressure (1750-1770 K and 1.2 GPa) in a piston-cylinder apparatus. Diffusivities were measured by step heating the glasses between 423 and 1198 K and measuring the fraction of gas released at each temperature step by noble gas mass spectrometry. In addition we measured the viscosity of G1 between 996 and 1072 K in order to determine the precise glass transition temperature and to estimate network relaxation time scales. The results indicate that, to a first order, that the smaller the size of the diffusing atom, the greater its diffusivity at a given temperature: D(He) > D(Ne) > D(Ar) at constant T. Significantly, the diffusivities of the noble gases in the glasses investigated do not display simple Arrhenian behavior: there are well-defined departures from Arrhenian behavior which occur at lower temperatures for He than for Ne or Ar. We propose that the non-Arrhenian behavior of noble gases can be explained by structural modifications

  10. Closed-Form Expansions for Transition Densities of Convenience Yield Processes

    Directory of Open Access Journals (Sweden)

    Sanae RUJIVAN

    2009-01-01

    Full Text Available In this paper, we derive closed-form expansions for transition densities of convenience yield processes modeled by using extended Cox-Ingersoll-Ross (ECIR processes. The closed-form expansions can be used for all cases of model having appropriate drift and diffusion coefficients. In terms of the efficiency, the closed-form expansions are close to the exact transition densities when the number of terms in the expansions is large and the time step size is small.

  11. Dielectric properties of NaF–B2O3 glasses doped with certain transition metal ions

    Indian Academy of Sciences (India)

    M Krishna Murthy; K S N Murthy; N Veeraiah

    2000-08-01

    Dielectric constant , loss tan , a.c. conductivity and dielectric breakdown strength of NaF–B2O3 glasses doped with certain transition metal ions (viz. Cu2+, VO2+, Ti4+ and Mn4+) are studied in the frequency range 102–107 Hz and in the temperature range 30–250°C. The values of , tan , a.c. are found to be the highest for Cu2+ doped glasses and the lowest for Mn4+ doped glasses. Activation energy for a.c. conduction and the value of dielectric breakdown strength are found to be the lowest for Cu2+ doped glasses and the highest for Mn4+ doped glasses. With the help of infrared spectra, increase in the values of and tan of these glasses with frequency and temperature are identified with space charge polarization. An attempt has been made to explain a.c. conduction phenomenon on the basis of quantum mechanical tunneling model (QMT)/carrier barrier hopping model.

  12. Empirical transverse charge densities in the nucleon and the nucleon-to-Delta transition

    Energy Technology Data Exchange (ETDEWEB)

    Carl Carlson; Marc Vanderhaeghen

    2008-01-01

    Using only the current empirical information on the nucleon electromagnetic form factors we map out the transverse charge density in proton and neutron as viewed from a light front moving towards a transversely polarized nucleon. These charge densities are characterized by a dipole pattern, in addition to the monopole field corresponding with the unpolarized density. Furthermore, we use the latest empirical information on the $N \\to \\Delta$ transition form factors to map out the transition charge density which induces the $N \\to \\Delta$ excitation. This transition charge density in a transversely polarized $N$ and $\\Delta$ contains both monopole, dipole and quadrupole patterns, the latter corresponding with a deformation of the hadron's charge distribution.

  13. THEORY OF THE THRESHOLD FIELD FOR THE DEPINNING TRANSITION OF A CHARGE-DENSITY WAVE

    NARCIS (Netherlands)

    PIETRONERO, L; VERSTEEG, M

    1991-01-01

    The Hamiltonian of an elastic string pinned by random potentials is often used to describe the depinning transition of a charge density wave in the presence of impurity pinning. The properties of the pinned states show close analogies to those of glassy systems, while the depinning transition resemb

  14. Metal-insulator transition and local moment formation: A spin-density functional approach

    Science.gov (United States)

    Ghazali, A.; Leroux-Hugon, P.

    1980-01-01

    A more thorough description of the metal-insulator transition in correlated systems including local moment formation may be achieved through the spin-density functional method when compared to the Hubbard model. We have applied this method to doped semiconductors and found a transition between an insulating phase with local moments and a metallic one without moments.

  15. Exploring effective interactions through transition charge density study of 70,72,74,76Ge nuclei

    Indian Academy of Sciences (India)

    A Shukla; P K Raina; P K Rath

    2005-02-01

    Transition charge densities (TCD) for $0^{+} → 2_{1}^{+}$ excitation have been calculated for 70, 72, 74, 76Ge nuclei within microscopic variational framework employing 23/2, 15/2, 21/2 and 19/2 valence space. The calculated TCDs for different monopole variants of Kuo interaction are compared with available experimental results. Other systematics like reduced transition probabilities (2) and static quadrupole moments (2) are also presented. It is observed that the transition density study acts as a sensitive probe for discriminating the response of different parts of effective interactions.

  16. Manipulating the glass transition behavior of sulfonated polystyrene by functionalized nanoparticle inclusion

    Science.gov (United States)

    Kim, Sung-Kon; Nguyen, Ngoc A.; Wie, Jeong Jae; Park, Ho Seok

    2015-05-01

    Nanoscale interfaces can modify the phase transition behaviors of polymeric materials. Here, we report the double glass transition temperature (Tg) behavior of sulfonated polystyrene (sPS) by the inclusion of 14 nm amine-functionalized silica (NH2-SiO2) nanoparticles, which is different from the single Tg behaviors of neat sPS and silica (SiO2)-filled sPS. The inclusion of 20 wt% NH2-SiO2 nanoparticles results in an increase of Tg by 9.3 °C as well as revealing a second Tg reduced by 44.7 °C compared to the Tg of neat sPS. By contrast, when SiO2 nanoparticles with an identical concentration and size to NH2-SiO2 are dispersed, sPS composites possess a single Tg of 7.3 °C higher than that of the neat sPS. While a nanoscale dispersion is observed for SiO2 nanoparticles, as confirmed by microscopic and X-ray scattering analyses, NH2-SiO2 nanoparticles show the coexistence of micron-scale clustering along with a nanoscale dispersion of the individual nanoparticles. The micro-phase separation contributes to the free volume induced Tg reduction by the plasticization effect, whereas the Tg increase originates from the polymer segment mobility constrained by nanoconfinement and the rigid amorphous fractions deriving from strong polymer-particle interactions.Nanoscale interfaces can modify the phase transition behaviors of polymeric materials. Here, we report the double glass transition temperature (Tg) behavior of sulfonated polystyrene (sPS) by the inclusion of 14 nm amine-functionalized silica (NH2-SiO2) nanoparticles, which is different from the single Tg behaviors of neat sPS and silica (SiO2)-filled sPS. The inclusion of 20 wt% NH2-SiO2 nanoparticles results in an increase of Tg by 9.3 °C as well as revealing a second Tg reduced by 44.7 °C compared to the Tg of neat sPS. By contrast, when SiO2 nanoparticles with an identical concentration and size to NH2-SiO2 are dispersed, sPS composites possess a single Tg of 7.3 °C higher than that of the neat sPS. While a

  17. Soft glassy colloidal arrays in an ionic liquid: colloidal glass transition, ionic transport, and structural color in relation to microstructure.

    Science.gov (United States)

    Ueno, Kazuhide; Sano, Yuta; Inaba, Aya; Kondoh, Masashi; Watanabe, Masayoshi

    2010-10-21

    The colloidal glass transition, ionic transport, and optical properties of soft glassy colloidal arrays (SGCAs) that consist of poly(methyl methacrylate) (PMMA)-grafted silica nanoparticles (PMMA-g-NPs) and a room-temperature ionic liquid, 1-ethyl-3-methylimidazolium bis(trifluoromethane sulfonyl)amide ([C(2)mim][NTf(2)]), were investigated. At lower particle concentrations, PMMA-g-NPs were well-suspended in the IL without any aggregation or sedimentation, and the dilute suspensions showed liquid-like behavior. However, above a certain particle concentration, the suspensions became solidified and exhibited different structural colors depending on the particle concentrations. The liquid-solid transition of the SGCAs was essentially caused by colloidal glass transition. Due to the soft repulsive interaction between the particles, the effective volume fraction of the particle (ϕ(eff)) required for colloidal glass transition was higher than that of the hard sphere system and found to be approximately 0.70-0.74. The SGCA had sufficient ionic conductivity, which was greater than 10(-3) S cm(-1) at room temperature, even in the highly concentrated region. For ionic transport of the cation and the anion in the SGCAs, the decrease in diffusivity observed with the addition of the particles (D(g)/D(0)) was slightly greater for the [NTf(2)] anion than that of the [C(2)mim] cation, suggesting that the [NTf(2)] anion preferentially interacts with the PMMA chains. The SGCAs showed homogeneous, nonbrilliant, and angle-independent structural colors above the glass transition volume fraction. In addition, the color of the SGCAs changed from red to green to blue as the particle concentration increased. A linear relationship was found between the maximum wavelength of the reflection spectra and the center-to-center distance in the SGCAs.

  18. Time evolution of chiral phase transition at finite temperature and density in the linear sigma model

    Energy Technology Data Exchange (ETDEWEB)

    Sato, K.; Koide, Tomoi; Maruyama, Masahiro [Tohoku Univ., Faculty of Science, Sendai, Miyagi (Japan)

    1999-08-01

    There are various approaches to nonequilibrium system. We use the projection operator method investigated by F. Shibata and N. Hashitsume on the linear sigma model at finite temperature and density. We derive a differential equation of the time evolution for the order parameter and pion number density in chiral phase transition. (author)

  19. Phase transition in finite density and temperature lattice QCD

    CERN Document Server

    Wang, Rui; Gong, Ming; Liu, Chuan; Liu, Yu-Bin; Liu, Zhao-Feng; Ma, Jian-Ping; Meng, Xiang-Fei; Zhang, Jian-Bo

    2015-01-01

    We investigate the behavior of the chiral condensate in lattice QCD at finite temperature and finite chemical potential. The study was done using two flavors of light quarks and with a series of $\\beta$ and $ma$ at the lattice size $24\\times12^{2}\\times6$. The calculation was done in the Taylar expansion formalism. We are able to calculate the first and second order derivatives of $\\langle\\bar{\\psi}\\psi\\rangle$ in both isoscalar and isovector channels. With the first derivatives being small, we find that the second derivatives are sizable close to the phase transition and the magnitude of $\\bar{\\psi}\\psi$ decreases under the influence of finite chemical potential in both channels.

  20. Finite density QCD phase transition in the heavy quark region

    CERN Document Server

    Saito, H; Kanaya, K; Ohno, H; Ejiri, S; Nakagawa, Y; Hatsuda, T; Umeda, T

    2012-01-01

    We extend our previous study of the QCD phase structure in the heavy quark region to non-zero chemical potentials. To identify the critical point where the first order deconfining transition terminates, we study an effective potential defined by the probability distribution function of the plaquette and the Polyakov loop. The reweighting technique is shown to be powerful in evaluating the effective potential in a wide range of the plaquette and Polyakov loop expectation values. We adopt the cumulant expansion to overcome the sign problem in the calculation of complex phase of the quark determinant. We find that the method provides us with an intuitive and powerful way to study the phase structure. We estimate the location of the critical point at finite chemical potential in the heavy quark region.

  1. Measurement and modeling of the glass transition temperatures of multi-component solutions

    Energy Technology Data Exchange (ETDEWEB)

    Shah, Binal N. [Department of Chemical and Environmental Engineering, University of Toledo, 2801 W. Bancroft Street, Toledo, OH 43606 (United States); Schall, Constance A. [Department of Chemical and Environmental Engineering, University of Toledo, 2801 W. Bancroft Street, Toledo, OH 43606 (United States)]. E-mail: cschall@eng.utoledo.edu

    2006-04-01

    Protein crystals are usually grown in multi-component aqueous solutions containing salts, buffers and other additives. To measure the X-ray diffraction data of the crystal, crystals are rapidly lowered to cryogenic temperatures. On flash cooling, ice frequently forms affecting the integrity of the sample. In order to eliminate this effect, substances called cryoprotectants are added to produce a glassy (vitrified) state rather than ice. Heretofore, the quantity of cryoprotectant needed to vitrify the sample has largely been established by trial and error. In this study, differential scanning calorimetry (DSC) was used to measure the melting (T {sub m}), devitrification (T {sub d}) and glass transition (T {sub g}) temperatures of solutions with a range of compositions typical of those used for growing protein crystals, with the addition of glycerol as cryoprotectant. The addition of cryoprotectant raises the T {sub g} and lowers the T {sub m} of bulk solution thereby decreasing the cooling rates required for vitrification of protein crystals. The theoretical T {sub g} value was calculated using the apparent volume fraction using the Miller/Fox equation extended for multi-component systems. The experimental values of T {sub g} were within approximately {+-}4% of that predicted by the model. Thus, the use of the model holds the promise of a rational method for the theoretical determination of the composition of cryoprotectant requirement of protein crystallization solutions.

  2. Glass transition dynamics and charge carrier mobility in conjugated polyfluorene thin films

    Science.gov (United States)

    Qin, Hui; Liu, Dan; Wang, Tao

    Conjugated polymers are commonly used in organic optoelectronic devices, e.g. organic photovoltaics (OPVs), light-emitting diodes (LEDs) and field effect transistors (FETs). In these devices, the conjugated polymers are prepared as thin films with thicknesses in the range of tens to hundreds of nanometers, and are interfaced with different function layers made from organic or inorganic materials. We have studied the glass transition temperature (Tg) of poly(9, 9-dioctylfluorene)-co-N-(1, 4-butylphenyl)diphenylamine) (TFB) thin films supported on different substrates, as well as their SCLC charge carrier mobility in photodiodes. Both Monotonic and non-monotonic Tg deviations are observed in TFB thin films supported on Si/SiOx and PEDOT:PSS, respectively. With low to moderate thermal crosslinking, the thickness dependent Tg deviation still exists, which diminishes in TFB films with a high crosslinking degree. The vertical charge carrier mobility of TFB thin films extracted from the SCLC measurements is found increase with film thickness, a value increases from 1 to 50 x 10-6 cm2 V-1 s-1 in the thickness range from 15 to 180 nm. Crosslinking was found to reduce the carrier mobility in TFB thin films. The Tg deviations are also discussed using the classic layered models in the literature. Our results provide a precise guide for the fabrication and design of high performance optoelectronic devices.

  3. Molecular relaxation behavior and isothermal crystallization above glass transition temperature of amorphous hesperetin.

    Science.gov (United States)

    Shete, Ganesh; Khomane, Kailas S; Bansal, Arvind Kumar

    2014-01-01

    The purpose of this paper was to investigate the relaxation behavior of amorphous hesperetin (HRN), using dielectric spectroscopy, and assessment of its crystallization kinetics above glass transition temperature (Tg ). Amorphous HRN exhibited both local (β-) and global (α-) relaxations. β-Relaxation was observed below Tg , whereas α-relaxation prominently emerged above Tg . β-Relaxation was found to be of Johari-Goldstein type and was correlated with α-process by coupling model. Secondly, isothermal crystallization experiments were performed at 363 K (Tg + 16.5 K), 373 K (Tg + 26.5 K), and 383 K (Tg + 36.5 K). The kinetics of crystallization, obtained from the normalized dielectric strength, was modeled using the Avrami model. Havriliak-Negami (HN) shape parameters, αHN and αHN .βHN , were analyzed during the course of crystallization to understand the dynamics of amorphous phase during the emergence of crystallites. HN shape parameters indicated that long range (α-like) were motions affected to a greater extent than short range (β-like) motions during isothermal crystallization studies at all temperature conditions. The variable behavior of α-like motions at different isothermal crystallization temperatures was attributed to evolving crystallites with time and increase in electrical conductivity with temperature.

  4. Using combined computational techniques to predict the glass transition temperatures of aromatic polybenzoxazines.

    Directory of Open Access Journals (Sweden)

    Phumzile Mhlanga

    Full Text Available The Molecular Operating Environment software (MOE is used to construct a series of benzoxazine monomers for which a variety of parameters relating to the structures (e.g. water accessible surface area, negative van der Waals surface area, hydrophobic volume and the sum of atomic polarizabilities, etc. are obtained and quantitative structure property relationships (QSPR models are formulated. Three QSPR models (formulated using up to 5 descriptors are first used to make predictions for the initiator data set (n = 9 and compared to published thermal data; in all of the QSPR models there is a high level of agreement between the actual data and the predicted data (within 0.63-1.86 K of the entire dataset. The water accessible surface area is found to be the most important descriptor in the prediction of T(g. Molecular modelling simulations of the benzoxazine polymer (minus initiator carried out at the same time using the Materials Studio software suite provide an independent prediction of T(g. Predicted T(g values from molecular modelling fall in the middle of the range of the experimentally determined T(g values, indicating that the structure of the network is influenced by the nature of the initiator used. Hence both techniques can provide predictions of glass transition temperatures and provide complementary data for polymer design.

  5. Creep performance of PVC aged at temperature relatively close to glass transition temperature

    Institute of Scientific and Technical Information of China (English)

    Zhi-hong ZHOU; Yao-long HE; Hong-jiu HU; Feng ZHAO; Xiao-long ZHANG

    2012-01-01

    In order to predict the mechanical performance of the polyvinyl chloride (PVC) at a high operating temperature,a series of short-term tensile creep tests (onetenth of the physical aging time) of the PVC are carried out at 63 ℃ with a small constant stress by a dynamic mechanical analyzer (DMA).The Struik-Kohlrausch (SK)formula and Struik shifting methods are used to describe these creep data for various physical aging time.A new phenomenological model based on the multiple relaxation mechanisms of an amorphous polymer is developed to quantitatively characterize the SK parameters (the initial creep compliance,the characteristic retardation time,and the shape factor) determined by the aging time.It is shown that the momentary creep compliance curve of the PVC at 63 ℃ can be very well fitted by the SK formula for each aging time.However,the SK parameters for the creep curves are not constant during the aging process at the elevated temperatures,and the evolution of these parameters and the creep rate versus aging time curves at the double logarithmic coordinates have shown a nonlinear phenomenon. Moreover,the creep master curves obtained by the superposition with the Struik shifting methods are unsatisfactory in such a case.Finally,the predicted results calculated from the present model incorporating with the SK formula are in excellent agreement with the creep experimental data for the PVC isothermally aged at the temperature relatively close to the glass transition temperature.

  6. Random Matrix Theory for Transition Strength Densities in Finite Quantum Systems: Results from Embedded Unitary Ensembles

    CERN Document Server

    Kota, V K B

    2015-01-01

    Embedded random matrix ensembles are generic models for describing statistical properties of finite isolated interacting quantum many-particle systems. For the simplest spinless systems, with say $m$ particles in $N$ single particle states and interacting via $k$-body interactions, we have EGUE($k$) and the embedding algebra is $U(N)$. A finite quantum system, induced by a transition operator, makes transitions from its states to the states of the same system or to those of another system. Examples are electromagnetic transitions (same initial and final systems), nuclear beta and double beta decay (different initial and final systems), particle addition to/removal from a given system and so on. Towards developing a complete statistical theory for transition strength densities, we have derived formulas for lower order bivariate moments of the strength densities generated by a variety of transition operators. For a spinless fermion system, using EGUE($k$) representation for Hamiltonian and an independent EGUE($...

  7. Interfacial stick–slip transition in hydroxyapatite filled high density polyethylene composite

    Indian Academy of Sciences (India)

    Roy Joseph; M T Martyn; K E Tanner; P D Coates

    2006-02-01

    Effect of filler addition and temperature on the stick–slip transition in high density polyethylene melt was studied. Results showed that shear stresses corresponding to stick–slip transition increases with the addition of filler. Increase in temperature also increases the shear stresses for stick–slip transition. The features of the flow curves of composites and that of unfilled system remain identical. Filler addition lowers the shear rate at which the transition occurs. The composite extrudate did not show characteristic extrudate distortions associated with the unfilled polymer.

  8. Transition densities in the context of the generalized rotation-vibration model

    Science.gov (United States)

    Morales Botero, D. F.; Chamon, L. C.; Carlson, B. V.

    2017-10-01

    A collective model for the description of heavy-ion nuclear structure, called the generalized rotation-vibration model (GRVM), was proposed in an earlier paper. In the present work, we use this model to study transition densities for the low-lying states of several nuclei. In order to evaluate the accuracy of the model, we test the GRVM transition densities in the description of experimental results corresponding to elastic and inelastic electron-nucleus scattering. We also compare the GRVM densities with those arising from microscopic Dirac-Hartree-Bogoliubov theoretical calculations. The GRVM transition densities can be used in future works to calculate folding-type coupling potentials in coupled-channel data analyses for heavy-ion systems.

  9. Density and glass forming ability in amorphous atomic alloys: The role of the particle softness

    Science.gov (United States)

    Douglass, Ian; Hudson, Toby; Harrowell, Peter

    2016-04-01

    A key property of glass forming alloys, the anomalously small volume difference with respect to the crystal, is shown to arise as a direct consequence of the soft repulsive potentials between metals. This feature of the inter-atomic potential is demonstrated to be responsible for a significant component of the glass forming ability of alloys due to the decrease in the enthalpy of fusion and the associated depression of the freezing point.

  10. The Doping Effect on Conductivity and Glass Transition Temperature of Solid Polymeric Electrolyte Based on Polyvinylchloride (pvc)

    Science.gov (United States)

    Abd. Rahman, Mohd. Yusri; Mat Salleh, Muhammad; Abu Talib, Ibrahim; Yahaya, Muhamad

    2002-12-01

    Solid electrolyte materials have been widely used in electrochemical devices such as batteries, solar cells and displays. This is because of its advantages over the liquidmaterial.This paper is concerned with the preparation of solid polymeric electrolyte based on polyvinylchloride (PVC) and its conductivity .The effect of percentage by weight of dopant material (LiClO4) on conductivity and glass transition temperature of the electrolyte was studied by using differential scanning calorimeter (DSC) and impedance spectroscopy technique. The electrolyte doped with 4.8%wt LiClO4 exhibits the highest conductivitiy of 7 × 10-6Scm-1 at room temperature but has the lowest glass transition temperature of 36.37°C. The other results are presented in this paper.

  11. Glass transition dynamics of anti-inflammatory ketoprofen studied by Raman scattering and terahertz time-domain spectroscopy

    Science.gov (United States)

    Shibata, Tomohiko; Igawa, Hikaru; Kim, Tae Hyun; Mori, Tatsuya; Kojima, Seiji

    2014-03-01

    A liquid-glass transition and a crystalline state of pharmaceutical racemic ketoprofen were studied by Raman scattering and the broadband terahertz time-domain spectroscopy (THz-TDS) in the frequency range from 9 to 260 cm-1. The low-frequency Raman scattering spectra clearly shows the remarkable change related to a liquid-glass transition at about Tg = 267 K. After melt-quenching at liquid nitrogen temperature, a boson peak appears at about 16.5 cm-1 near and below Tg and the intensity of quasi-elastic scattering related to structural relaxation increases markedly on heating. The crystalline racemic ketoprofen of "conformer A" shows the noncoincidence effect of mode frequencies below 200 cm-1 between Raman scattering spectra and dielectric spectra observed by THz-TDS.

  12. Fragility and glass transition for binary mixtures of 1,2-propanediol and LiBF4

    Science.gov (United States)

    Terashima, Y.; Mori, M.; Sugimoto, N.; Takeda, K.

    2014-04-01

    The fragility and glass transition for binary mixtures of 1,2-propanediol and LiBF4 were investigated by measuring the heating rate dependence of glass transition temperature (Tg) using differential scanning calorimetry. With increasing LiBF4 mole fraction, x, up to 0.25, fragility, m, increased rapidly from 53 to 85, and then remained approximately unchanged for x > 0.25. The concentration dependences of Tg and heat capacity jump at Tg also showed anomalies around x = 0.25. We suggest this mixture transformed from a moderate to quite fragile liquid at x = 0.25 because of a structural change from a hydrogen-bonding- to ionic-interaction-dominant system.

  13. Observation of exchanging role of gold and silver nanoparticles in bimetallic thin film upon annealing above the glass transition temperature

    Science.gov (United States)

    Htet Kyaw, Htet; Tay Zar Myint, Myo; Hamood Al-Harthi, Salim; Maekawa, Toru; Yanagisawa, Keiichi; Sellai, Azzouz; Dutta, Joydeep

    2017-08-01

    The exchange role of gold (Au) and silver (Ag) in bimetallic films co-evaporated onto soda-lime glass substrates with Au-Ag volume ratios of 1:2, 1:1 and 2:1 have been demonstrated. Annealing of the films above the glass transition temperature in air led to non-alloying nature of the films, silver neutrals (Ag0) and gold nanoparticles (AuNPs) on the surface, along with silver nanoparticles (AgNPs) inside the glass matrix. Moreover, the size distribution and interparticle spacing of the AuNPs on the surface were governed by the Ag content in the deposited film. In contrast, the content of Au in the film played an opposite role leading to the migration of Ag ions (i.e. Ag0 being transformed to Ag ions after annealing in oxygen ambient) to form AgNPs inside the glass matrix. The higher the Au content in the film is, the more likely Ag0 to stay on the surface and impacts on the size distribution of AuNPs and consequently on the refractive index sensitivity measurements. Experimental realisation of this fact was reflected from the best performance for localized surface plasmon resonance (LSPR) sensitivity test achieved with Au-Ag ratio of 1:2. The Au/Ag/glass bimetallic dynamic results of this study can be pertinent to sensor applications integrated with optical devices.

  14. PECH和GAP的玻璃化转变温度研究%Glass-transition Temperature of PECH and GAP

    Institute of Scientific and Technical Information of China (English)

    宋晓庆; 周集义; 王文浩; 王建伟; 白森虎

    2008-01-01

    @@ Glycidyl azide polymer (GAP) is one of the most recognized and prominent azide polymer. Because of its superior properties,GAP is used extensively as a high energetic binder or plasticizer in propellants to increase burning and specific impulse. It is very important to research on the glass-transition temperature (Tg) of GAP and its precursor PECH (poly-epichlorohydrin) due to the Tg of binders is the key factor which can influence low temperature properties of solid propellants.

  15. Bonding at Compatible and Incompatible Amorphous Interfaces of Polystyrene and Poly(Methyl Methacrylate) Below the Glass Transition Temperature

    DEFF Research Database (Denmark)

    Boiko, Yuri M.; Lyngaae-Jørgensen, Jørgen

    2004-01-01

    Films of high-molecular-weight amorphous polystyrene (PS, M-w = 225 kg/mol, M-w/M-n = 3, T-g-bulk = 97degreesC, where T-g-bulk is the glass transition temperature of the bulk sample) and poly(methyl methacrylate) (PMMA, M-w = 87 kg/mol, M-w/M-n = 2, Tg-bulk = 109degreesC) were brought into contact...

  16. A mode coupling theory analysis of viscoelasticity near the kinetic glass transition of a copolymer micellar system

    Energy Technology Data Exchange (ETDEWEB)

    Mallamace, Francesco [Department of Nuclear Engineering, Massachusetts Institute of Technology, Cambridge, MA 02139 (United States); Tartaglia, Piero [Dipartimento di Fisica, INFM and Statistical Mechanics and Complexity Center, Universita di Roma La Sapienza, I-00185 Rome (Italy); Chen W R [Department of Nuclear Engineering, Massachusetts Institute of Technology, Cambridge, MA 02139 (United States); Faraone, Antonio [Department of Nuclear Engineering, Massachusetts Institute of Technology, Cambridge, MA 02139 (United States); Chen, S H [Department of Nuclear Engineering, Massachusetts Institute of Technology, Cambridge, MA 02139 (United States)

    2004-10-27

    We report a set of viscoelastic measurements in concentrated aqueous solutions of a copolymer micellar system with short-range inter-micellar attractive interactions, a colloidal system characterized, in different regions of the composition-temperature phase diagram, by the existence of a percolation line (PT) and a kinetic glass transition (KGT). Both these transitions cause dramatic changes in the system viscoelasticity. Whereas the observed variations of the shear moduli at the PT are described in terms of percolation models, for the structural arrest at the KGT we investigate the frequency-dependent shear modulus behaviours by using a mode coupling theory (MCT) approach.

  17. SEM Analysis of the Interfacial Transition Zone between Cement-Glass Powder Paste and Aggregate of Mortar under Microwave Curing

    Directory of Open Access Journals (Sweden)

    Yaning Kong

    2016-08-01

    Full Text Available In order to investigate the effects of microwave curing on the microstructure of the interfacial transition zone of mortar prepared with a composite binder containing glass powder and to explain the mechanism of microwave curing on the improvement of compressive strength, in this study, the compressive strength of mortar under microwave curing was compared against mortar cured using (a normal curing at 20 ± 1 °C with relative humidity (RH > 90%; (b steam curing at 40 °C for 10 h; and (c steam curing at 80 °C for 4 h. The microstructure of the interfacial transition zone of mortar under the four curing regimes was analyzed by Scanning electron microscopy (SEM. The results showed that the improvement of the compressive strength of mortar under microwave curing can be attributed to the amelioration of the microstructure of the interfacial transition zone. The hydration degree of cement is accelerated by the thermal effect of microwave curing and Na+ partially dissolved from the fine glass powder to form more reticular calcium silicate hydrate, which connects the aggregate, calcium hydroxide, and non-hydrated cement and glass powder into a denser integral structure. In addition, a more stable triangular structure of calcium hydroxide contributes to the improvement of compressive strength.

  18. Effects of heating conditions on the glass transition parameters of amorphous sucrose produced by melt-quenching.

    Science.gov (United States)

    Lee, Joo Won; Thomas, Leonard C; Schmidt, Shelly J

    2011-04-13

    This research investigates the effects of heating conditions used to produce amorphous sucrose on its glass transition (T(g)) parameters, because the loss of crystalline structure in sucrose is caused by the kinetic process of thermal decomposition. Amorphous sucrose samples were prepared by heating at three different scan rates (1, 10, and 25 °C/min) using a standard differential scanning calorimetry (SDSC) method and by holding at three different isothermal temperatures (120, 132, and 138 °C) using a quasi-isothermal modulated DSC (MDSC) method. In general, the quasi-isothermal MDSC method (lower temperatures for longer times) exhibited lower T(g) values, larger ΔC(p) values, and broader glass transition ranges (i.e., T(g end) minus T(g onset)) than the SDSC method (higher temperatures for shorter times), except at a heating rate of 1 °C/min, which exhibited the lowest T(g) values, the highest ΔC(p), and the broadest glass transition range. This research showed that, depending on the heating conditions employed, a different amount and variety of sucrose thermal decomposition components may be formed, giving rise to wide variation in the amorphous sucrose T(g) values. Thus, the variation observed in the literature T(g) values for amorphous sucrose produced by thermal methods is, in part, due to differences in the heating conditions employed.

  19. Coupling of gelation and glass transition in a biphasic colloidal mixture--from gel-to-defective gel-toglass

    Science.gov (United States)

    Cheng, He; Jia, Di; Han, Charles

    The state transition from gel to glass is studied in a biphasic mixture of polystyrene core/poly (N-isopropylacrylamide) shell (CS) microgels and sulfonated polystyrene (PSS) particles. At 35 °C, the interaction between CS is due to short-range Van der Waals attraction while that between PSS is from long-range electrostatic repulsion. During variation of the relative ratio of the two species at a fixed apparent total volume fraction, the mixture exhibits a gel-to-defective gel-to-glass transition. When small amounts of PSS are introduced into the CS gel network, some of them are kinetically trapped, causing a change in its fractal structure, and act as defects to weaken the macroscopic gel strength. An increase of PSS content in the mixture promotes the switch from gel to defective gel, e . g . , the typical two-step yielding gel merges into one-step yielding. This phenomenon is an indication that inter-cluster bond breakage coincides with intra-cluster bond fracture. As the relative volume fraction of PSS exceeds a critical threshold, the gel network can no longer be formed; hence, the mixture exhibits characteristics of glass. A state diagram of the biphasic mixture is constructed, and the landscape of the different transitions will be described in future studies The financial support from the National Basic Research Program of China (973 Program, 2012CB821500) is gratefully acknowledged.

  20. How carbon nanotubes affect the cure kinetics and glass transition temperature of their epoxy composites? – A review

    Directory of Open Access Journals (Sweden)

    2009-09-01

    Full Text Available Motivated by the widespread and contradictory results regarding the glass transition temperature of carbon nanotube (CNT/epoxy composites, we reviewed and analyzed the literature results dealing with the effect of unmodified multiwall carbon nanotubes (MWNT on the cure behaviour of an epoxy resin (as a possible source of this discrepancy. The aim of this work was to clarify the effective role of unmodified multiwall carbon nanotubes on the cure kinetics and glass transition temperature (Tg of their epoxy composites. It was found that various authors reported an acceleration effect of CNT. The cure reaction was promoted in its early stage which may be due to the catalyst particles present in the CNT raw material. While SWNT may lead to a decrease of Tg due to their bundling tendency, results reported for MWNT suggested an increased or unchanged Tg of the composites. The present status of the literature does not allow to isolate the effect of MWNT on the Tg due to the lack of a study providing essential information such as CNT purity, glass transition temperature along with the corresponding cure degree.

  1. Roles of water and solids composition in the control of glass transition and stickiness of milk powders.

    Science.gov (United States)

    Silalai, Nattiga; Roos, Yrjö H

    2010-06-01

    Plasticization and glass transition of amorphous components in food powders often result in stickiness and caking. The glass transition temperature (T(g)) of milk powders was measured by differential scanning calorimetry (DSC) and a viscometer method was used to determine sticky-point temperatures. Water sorption isotherms were established for varying solids compositions. Lactose contents were analyzed by high-performance anion exchange chromatography with pulsed amperometric detection (HPAE-PAD) and proteins were identified using SDS-PAGE gel electrophoresis. Solids composition and water affected both the T(g) and stickiness behavior. Stickiness was governed by carbohydrates and water plasticization. At low protein contents, precrystallization of lactose decreased the sticky point temperature, but increasing protein content in all milk powders decreased stickiness at all water activities. The results showed that glass transition can be used to describe time-dependent stickiness and crystallization phenomena, and it can be used as a parameter to control and reduce stickiness of dairy solids with various compositions.

  2. Spatiotemporal Evolution of Ar(3P2) Metastable Density Generated in a Pulsed DC Atmospheric Pressure micro-Plasma Jet Impinging on a Glass Plate

    Science.gov (United States)

    Gazeli, K.; Bauville, G.; Es-Sebbar, Et-T.; Fleury, M.; Neveau, O.; Pasquiers, St.; Santos Sousa, J.; Laboratoire de Physique des gaz et des plasmas Team

    2016-09-01

    Atmospheric Pressure micro-Plasma Jets (APPJs) are promising tools in various domains such as biomedical and material treatments. In this work, APPJs are produced in pure argon at variable flow rates (i.e., 200, 400 and 600 sccm), by applying high voltage positive pulses (250 ns in FWHM and 6 kV in amplitude) at a repetition frequency of 20 kHz. The generated plasma impacts an ungrounded glass plate placed at a distance of 5 mm from the tube's orifice and perpendicular to the streamers propagation. At these conditions, a diffuse discharge is established resulting in a non-filamentary and reproducible plasma, in contrast with the free-jet case (no target). This allows the quantification of the absolute density of the Ar(1s5) metastable state by using laser absorption spectroscopy to probe the transition 1s5 -> 2p9 at 811.531 nm. The experiments show the dependence on the gas flow rate and on the axial and radial positions of the maximum density (6-9x1013 cm-3) . At 200 sccm, it is obtained close to the tube's orifice, while with increasing flow rate it is displaced towards the plate. Regarding the radial variation, density maxima are obtained in a small area around the streamers propagation axis.

  3. Computational modelling of large deformations in layered-silicate/PET nanocomposites near the glass transition

    Science.gov (United States)

    Figiel, Łukasz; Dunne, Fionn P. E.; Buckley, C. Paul

    2010-01-01

    Layered-silicate nanoparticles offer a cost-effective reinforcement for thermoplastics. Computational modelling has been employed to study large deformations in layered-silicate/poly(ethylene terephthalate) (PET) nanocomposites near the glass transition, as would be experienced during industrial forming processes such as thermoforming or injection stretch blow moulding. Non-linear numerical modelling was applied, to predict the macroscopic large deformation behaviour, with morphology evolution and deformation occurring at the microscopic level, using the representative volume element (RVE) approach. A physically based elasto-viscoplastic constitutive model, describing the behaviour of the PET matrix within the RVE, was numerically implemented into a finite element solver (ABAQUS) using an UMAT subroutine. The implementation was designed to be robust, for accommodating large rotations and stretches of the matrix local to, and between, the nanoparticles. The nanocomposite morphology was reconstructed at the RVE level using a Monte-Carlo-based algorithm that placed straight, high-aspect ratio particles according to the specified orientation and volume fraction, with the assumption of periodicity. Computational experiments using this methodology enabled prediction of the strain-stiffening behaviour of the nanocomposite, observed experimentally, as functions of strain, strain rate, temperature and particle volume fraction. These results revealed the probable origins of the enhanced strain stiffening observed: (a) evolution of the morphology (through particle re-orientation) and (b) early onset of stress-induced pre-crystallization (and hence lock-up of viscous flow), triggered by the presence of particles. The computational model enabled prediction of the effects of process parameters (strain rate, temperature) on evolution of the morphology, and hence on the end-use properties.

  4. Optical stability of 3d transition metal ions doped-cadmium borate glasses towards γ-rays interaction

    Science.gov (United States)

    Marzouk, M.; ElBatal, H.; Eisa, W.

    2016-07-01

    This work reports the preparation of glasses of binary cadmium borate with the basic composition (mol% 45 CdO 55 B2O3) and samples of the same composition containing 0.2 wt% dopants of 3d transition metal (TM) oxides (TiO2 → CuO). The glasses have been investigated by combined optical and Fourier Transform infrared spectroscopic measurements before and after being subjected to gamma irradiation with a dose of 8 Mrad (8 × 104 Gy). Optical absorption of the undoped glass before irradiation reveals strong charge transfer UV absorption which is related to the presence of unavoidable contaminated trace iron impurities (mainly Fe3+) within the raw materials used for the preparation of the base cadmium borate glass. The optical spectra of the 3d TM ions exhibit characteristic bands which are related the stable oxidation state of the 3d TM ions within the host glass. Gamma irradiation produces some limited variations in the optical spectra due to the stability of the host glass containing high percent 45 mol% of heavy metal oxide (CdO) which causes some shielding effects towards irradiation. From the absorption edge data, the values of the optical band gap Eopt and Urbach energy (∆E) have been calculated. The values of the optical energy gap are found to be dependent on the glass composition. Infrared absorption spectral measurements reveal characteristic absorption bands due to both triangular and tetrahedral borate groups with the BO3 units vibrations more intense than BO4 units due to the known limit value for the change of BO3 to BO4 groups. The introduction of 3d TM ions with the doping level (0.2 wt%) causes no changes in the number or position of the IR bands because of the presence of TM ions in modifying sites in the glass network. It is observed that gamma irradiation causes some limited changes in the FT-IR spectral bands due to the stability of the host heavy cadmium borate glass.

  5. Confirmation of temperature independence in the fluorescence lifetime of the 3P 0 → 3F 2 transition in praseodymium-doped fluoride glass

    Science.gov (United States)

    Nguyen, Thinh B.; Vella, Vince; Baxter, Greg W.; Collins, Stephen F.; Newman, Peter J.; MacFarlane, Douglas R.

    2006-05-01

    The dependence of the fluorescence lifetime from the 3P0 → 3F2 transition in praseodymium-doped fluoride glass as a function of dopant concentration and temperature was investigated. It was found that the fluorescence lifetime at the concentration of 7000 ppm was constant with temperature, confirming the prediction of temperature independence in the lifetime for this transition in Pr3+-doped ZBLAN glass.

  6. Spin-glass phase transition and behavior of nonlinear susceptibility in the Sherrington-Kirkpatrick model with random fields

    Science.gov (United States)

    Morais, C. V.; Zimmer, F. M.; Lazo, M. J.; Magalhães, S. G.; Nobre, F. D.

    2016-06-01

    The behavior of the nonlinear susceptibility χ3 and its relation to the spin-glass transition temperature Tf in the presence of random fields are investigated. To accomplish this task, the Sherrington-Kirkpatrick model is studied through the replica formalism, within a one-step replica-symmetry-breaking procedure. In addition, the dependence of the Almeida-Thouless eigenvalue λAT (replicon) on the random fields is analyzed. Particularly, in the absence of random fields, the temperature Tf can be traced by a divergence in the spin-glass susceptibility χSG, which presents a term inversely proportional to the replicon λAT. As a result of a relation between χSG and χ3, the latter also presents a divergence at Tf, which comes as a direct consequence of λAT=0 at Tf. However, our results show that, in the presence of random fields, χ3 presents a rounded maximum at a temperature T* which does not coincide with the spin-glass transition temperature Tf (i.e., T*>Tf for a given applied random field). Thus, the maximum value of χ3 at T* reflects the effects of the random fields in the paramagnetic phase instead of the nontrivial ergodicity breaking associated with the spin-glass phase transition. It is also shown that χ3 still maintains a dependence on the replicon λAT, although in a more complicated way as compared with the case without random fields. These results are discussed in view of recent observations in the LiHoxY1 -xF4 compound.

  7. Fabrication of internal diffraction gratings in planar fluoride glass using low-density plasma formation induced by a femtosecond laser

    Energy Technology Data Exchange (ETDEWEB)

    Cho, Sung-Hak [Nano Machining Laboratory, KIMM (Korea Institute of Machinery and Material), 171 Jang-dong, Yuseong-Gu, Daejeon 305-343 (Korea, Republic of); Materials Research and Education Center, Department of Mechanical Engineering, Auburn University, 275 Wilmore Laboratories, Auburn, AL 36849 (United States)], E-mail: shcho@kimm.re.kr; Chang, Won-Seok; Kim, Jae-Goo [Nano Machining Laboratory, KIMM (Korea Institute of Machinery and Material), 171 Jang-dong, Yuseong-Gu, Daejeon 305-343 (Korea, Republic of); Kim, Kwang-Ryul [Department of Electronics and Computer Engineering, Hanyang University, Seoul 133-791 (Korea, Republic of); Hong, Jong Wook [Materials Research and Education Center, Department of Mechanical Engineering, Auburn University, 275 Wilmore Laboratories, Auburn, AL 36849 (United States)

    2008-12-30

    The fabrication of internal diffraction gratings with photo-induced refractive index modification in planar fluoride plates was demonstrated using low-density plasma formation excited by a high-intensity femtosecond (130 fs) Ti:sapphire laser ({lambda}{sub p} = 790 nm). The refractive index modifications with diameters ranging from 350 nm to 5 {mu}m were photoinduced after plasma formation occurred upon irradiation with peak intensities of more than 1 x 10{sup 12} W/cm{sup 2}. The graded refractive index profile was fabricated to be a symmetric around from the center of the point at which low-density plasma occurred. The maximum refractive index change ({delta}n) was estimated to be 1.3 x 10{sup -2}. The low-density plasma formation (n{sub c} < 1.79 x 10{sup 27} m{sup -3}]) causes the increase of the refractive index modification with fluoride glass.

  8. Relaxation processes and glass transition of confined polymer melts: A molecular dynamics simulation of 1,4-polybutadiene between graphite walls

    Science.gov (United States)

    Solar, M.; Binder, K.; Paul, W.

    2017-05-01

    Molecular dynamics simulations of a chemically realistic model for 1,4-polybutadiene in a thin film geometry confined by two graphite walls are presented. Previous work on melts in the bulk has shown that the model faithfully reproduces static and dynamic properties of the real material over a wide temperature range. The present work studies how these properties change due to nano-confinement. The focus is on orientational correlations observable in nuclear magnetic resonance experiments and on the local intermediate incoherent neutron scattering function, Fs(qz, z, t), for distances z from the graphite walls in the range of a few nanometers. Temperatures from about 2Tg down to about 1.15Tg, where Tg is the glass transition temperature in the bulk, are studied. It is shown that weakly attractive forces between the wall atoms and the monomers suffice to effectively bind a polymer coil that is near the wall. For a wide regime of temperatures, the Arrhenius-like adsorption/desorption kinetics of the monomers is the slowest process, while very close to Tg the Vogel-Fulcher-Tammann-like α-relaxation takes over. The α-process is modified only for z ≤1.2 nm due to the density changes near the walls, less than expected from studies of coarse-grained (bead-spring-type) models. The weakness of the surface effects on the glass transition in this case is attributed to the interplay of density changes near the wall with the torsional potential. A brief discussion of pertinent experiments is given.

  9. Time-dependent renormalized Redfield theory II for off-diagonal transition in reduced density matrix

    Science.gov (United States)

    Kimura, Akihiro

    2016-09-01

    In our previous letter (Kimura, 2016), we constructed time-dependent renormalized Redfield theory (TRRT) only for diagonal transition in a reduced density matrix. In this letter, we formulate the general expression for off-diagonal transition in the reduced density matrix. We discuss the applicability of TRRT by numerically comparing the dependencies on the energy gap of the exciton relaxation rate by using the TRRT and the modified Redfield theory (MRT). In particular, we roughly show that TRRT improves MRT for the detailed balance about the excitation energy transfer reaction.

  10. Density functional theory optimized basis sets for gradient corrected functionals: 3d transition metal systems.

    Science.gov (United States)

    Calaminici, Patrizia; Janetzko, Florian; Köster, Andreas M; Mejia-Olvera, Roberto; Zuniga-Gutierrez, Bernardo

    2007-01-28

    Density functional theory optimized basis sets for gradient corrected functionals for 3d transition metal atoms are presented. Double zeta valence polarization and triple zeta valence polarization basis sets are optimized with the PW86 functional. The performance of the newly optimized basis sets is tested in atomic and molecular calculations. Excitation energies of 3d transition metal atoms, as well as electronic configurations, structural parameters, dissociation energies, and harmonic vibrational frequencies of a large number of molecules containing 3d transition metal elements, are presented. The obtained results are compared with available experimental data as well as with other theoretical data from the literature.

  11. Chaotic state to self-organized critical state transition of serrated flow dynamics during brittle-to-ductile transition in metallic glass

    Energy Technology Data Exchange (ETDEWEB)

    Wang, C.; Wang, W. H.; Bai, H. Y., E-mail: hybai@aphy.iphy.ac.cn [Institute of Physics, Chinese Academy of Sciences, Beijing 100190 (China); Sun, B. A. [Centre for Advanced Structural Materials, Department of Mechanical and Biomedical Engineering, City University of Hong Kong, Kowloon Tong, Kowloon (Hong Kong)

    2016-02-07

    We study serrated flow dynamics during brittle-to-ductile transition induced by tuning the sample aspect ratio in a Zr-based metallic glass. The statistical analysis reveals that the serrated flow dynamics transforms from a chaotic state characterized by Gaussian-distribution serrations corresponding to stick-slip motion of randomly generated and uncorrelated single shear band and brittle behavior, into a self-organized critical state featured by intermittent scale-free distribution of shear avalanches corresponding to a collective motion of multiple shear bands and ductile behavior. The correlation found between serrated flow dynamics and plastic deformation might shed light on the plastic deformation dynamic and mechanism in metallic glasses.

  12. Low temperature high density plasma nitriding of stainless steel molds for stamping of oxide glasses

    Directory of Open Access Journals (Sweden)

    Aizawa Tatsuhiko

    2016-01-01

    Full Text Available Various kinds of stainless steels have been widely utilized as a die for mold- and direct-stamping processes of optical oxide glasses. Since they suffered from high temperature transients and thermal cycles in practice, they must be surface-treated by dry and wet coatings, or, by plasma nitriding. Martensitic stainless steel mold was first wet plated by the nickel phosphate (NiP, which was unstable at the high temperature stamping condition; and, was easy to crystalize or to fracture by itself. This issue of nuisance significantly lowered the productivity in fabrication of optical oxide-glass elements. In the present paper, the stainless steel mold was surface-treated by the low-temperature plasma nitriding. The nitrided layer by this surface modification had higher nitrogen solute content than 4 mass%; the maximum solid-solubility of nitrogen is usually 0.1 mass% in the equilibrium phase diagram. Owing to this solid-solution with high nitrogen concentration, the nitrided layer had high hardness over 1400 HV within its thickness of 50 μm without any formation of nitrides after plasma nitriding at 693 K for 14.4 ks. This plasma-nitrided mold was utilized for mold-stamping of two colored oxide glass plates at 833 K; these plates were successfully deformed and joined into a single glass plate by this stamping without adhesion or galling of oxide glasses onto the nitrided mold surface.

  13. Glass transition behavior of octyl β-D-glucoside and octyl β-D-thioglucoside/water binary mixtures.

    Science.gov (United States)

    Ogawa, Shigesaburo; Asakura, Kouichi; Osanai, Shuichi

    2010-11-22

    The lyotropic behavior and glass-forming properties of octyl β-D-glucoside (C8Glu) and octyl β-D-thioglucoside (C8SGlu)/water binary mixtures were evaluated using differential scanning calorimetry (DSC) and polarizing optical microscopy (POM). The results clearly indicate that the mixture forms a glass in the supercooling state of liquid crystalline phases such as cubic, lamellar, and smectic. The glass transition temperature (T(g)) of the mixture was strongly dependent on solute concentration, with a higher concentration correlating with a higher T(g). The experimental T(g) was consistent with the predicted value calculated using the Couchman-Karasz equation in both the C8Glu and C8SGlu/water mixtures. The change of heat capacity at T(g) showed the two bending points under variation of concentrations. And the highest temperature of phase transition from lamellar to isotropic solution was observed at around 50% molar concentration. It was expected that non-percolated state of water existed in extremely higher concentration ranges. Copyright © 2010 Elsevier Ltd. All rights reserved.

  14. Heat capacities and volumetric changes in the glass transition range: a constitutive approach based on the standard linear solid

    Science.gov (United States)

    Lion, Alexander; Mittermeier, Christoph; Johlitz, Michael

    2017-09-01

    A novel approach to represent the glass transition is proposed. It is based on a physically motivated extension of the linear viscoelastic Poynting-Thomson model. In addition to a temperature-dependent damping element and two linear springs, two thermal strain elements are introduced. In order to take the process dependence of the specific heat into account and to model its characteristic behaviour below and above the glass transition, the Helmholtz free energy contains an additional contribution which depends on the temperature history and on the current temperature. The model describes the process-dependent volumetric and caloric behaviour of glass-forming materials, and defines a functional relationship between pressure, volumetric strain, and temperature. If a model for the isochoric part of the material behaviour is already available, for example a model of finite viscoelasticity, the caloric and volumetric behaviour can be represented with the current approach. The proposed model allows computing the isobaric and isochoric heat capacities in closed form. The difference c_p -c_v is process-dependent and tends towards the classical expression in the glassy and equilibrium ranges. Simulations and theoretical studies demonstrate the physical significance of the model.

  15. Transitioning glass-ceramic scintillators for diagnostic x-ray imaging from the laboratory to commercial scale

    Science.gov (United States)

    Beckert, M. Brooke; Gallego, Sabrina; Elder, Eric; Nadler, Jason

    2016-10-01

    This study sought to mitigate risk in transitioning newly developed glass-ceramic scintillator technology from a laboratory concept to commercial product by identifying the most significant hurdles to increased scale. These included selection of cost effective raw material sources, investigation of process parameters with the most significant impact on performance, and synthesis steps that could see the greatest benefit from participation of an industry partner that specializes in glass or optical component manufacturing. Efforts focused on enhancing the performance of glass-ceramic nanocomposite scintillators developed specifically for medical imaging via composition and process modifications that ensured efficient capture of incident X-ray energy and emission of scintillation light. The use of cost effective raw materials and existing manufacturing methods demonstrated proof-of-concept for economical viable alternatives to existing benchmark materials, as well as possible disruptive applications afforded by novel geometries and comparatively lower cost per volume. The authors now seek the expertise of industry to effectively navigate the transition from laboratory demonstrations to pilot scale production and testing to evince the industry of the viability and usefulness of composite-based scintillators.

  16. Non-ergodicity transition and multiple glasses in binary mixtures: on the accuracy of the input static structure in the mode coupling theory.

    Science.gov (United States)

    Tchangnwa Nya, F; Ayadim, A; Germain, Ph; Amokrane, S

    2012-08-15

    We examine the question of the accuracy of the static correlation functions used as input in the mode coupling theory (MCT) of non-ergodic states in binary mixtures. We first consider hard-sphere mixtures and compute the static pair structure from the Ornstein-Zernike equations with the Percus-Yevick closure and more accurate ones that use bridge functions deduced from Rosenfeld's fundamental measures functional. The corresponding MCT predictions for the non-ergodicity lines and the transitions between multiple glassy states are determined from the long-time limit of the density autocorrelation functions. We find that while the non-ergodicity transition line is not very sensitive to the input static structure, up to diameter ratios D(2)/D(1) = 10, quantitative differences exist for the transitions between different glasses. The discrepancies with the more accurate closures become even qualitative for sufficiently asymmetric mixtures. They are correlated with the incorrect behavior of the PY structure at high size asymmetry. From the example of ultra-soft potential it is argued that this issue is of general relevance beyond the hard-sphere model.

  17. Raman scattering study of glass crystallization kinetics

    Science.gov (United States)

    Balkanski, M.; Haro, E.; Espinosa, G. P.; Phillips, J. C.

    1984-08-01

    Laser induced glass-crystalline transition is studied by light scattering. Three significant effects are observed depending on the incident laser energy density: (i) Spectral band narrowing indicating cluster enlargement constitutes a precursor effect, (ii) an intensity increase effect indicates a rapid rise of the density of clusters attaining microcrystalline size and (iii) a dynamical reversal effect indicative of glass-crystalline instability. Cluster volume and crystallization appear as separate but related threshold phenomena.

  18. Transitions of amorphous- crystalline-amorphous in bulk metallic glass under HP and HT

    Institute of Scientific and Technical Information of China (English)

    2002-01-01

    In-situ SR-XRD measurements revealed that the crystallization process in Zr41.2Ti13.sCu12.5Ni10Be22.5 bulk metallic glass is significantly different from that in traditional glasses. Subsequent heating at 10 GPa converts the sample from amorphous phase into the metastable fcc phase and then leads to the fcc phase back to the amorphous phase,nomena in the material under high pressure and high temperature.``

  19. [Calculation and analysis of optical transitions of Pr3+ ions in fluoride glass].

    Science.gov (United States)

    Kang, Dong-guo; Chen, Xiao-bo; Li, Song; Cui, Jian-sheng; Cai, Qing; Yu, Bao-Ting

    2007-01-01

    Intensity parameters of Pr3+ in ZBLAN glass were calculated using Judd-Ofelt(J-O) theory with absorption spectrum measurement. The anomalous behavior of Pr3+ was discussed using J-O theory. Base on the intensity parameters, the optical parameters such as spontaneous emission rate, branching ratio, and integrated emission cross section etc were predicted. The future of the glass as a laser material was discussed, and the probability of photon avalanche in the material was also analysed.

  20. Density functional studies of functionalized graphitic materials with late transition metals for oxygen reduction reactions

    DEFF Research Database (Denmark)

    Vallejo, Federico Calle; Martinez, Jose Ignacio; Rossmeisl, Jan

    2011-01-01

    ) at the cathode. In this contribution, on the basis of Density Functional Theory (DFT) calculations, we show that graphitic materials with active sites composed of 4 nitrogen atoms and transition metal atoms belonging to groups 7 to 9 in the periodic table are active towards ORR, and also towards Oxygen Evolution...

  1. H2 adsorption on 3d transition metal clusters: a combined infrared and density functional study

    NARCIS (Netherlands)

    Swart, I.; de Groot, F.M.F.; Weckhuysen, B.M.; Gruene, P.; Meijer, G.; Fielicke, A.

    2008-01-01

    The adsorption of H2 on a series of gas-phase transition metal (scandium, vanadium, iron, cobalt, and nickel) clusters containing up to 20 metal atoms is studied using IR-multiple photon dissociation spectroscopy complemented with density functional theory based calculations. Comparison of the exper

  2. Damping-Growth Transition for Ion-Acoustic Waves in a Density Gradient

    DEFF Research Database (Denmark)

    D'Angelo, N.; Michelsen, Poul; Pécseli, Hans

    1975-01-01

    A damping-growth transition for ion-acoustic waves propagating in a nonuniform plasma (e-folding length for the density ln) is observed at a wavelength λ∼2πln. This result supports calculations performed in connection with the problem of heating of the solar corona by ion-acoustic waves generated...

  3. TREATMENT OF NONADIABATIC TRANSITIONS BY DENSITY-MATRIX EVOLUTION AND MOLECULAR-DYNAMICS SIMULATIONS

    NARCIS (Netherlands)

    MAVRI, J; BERENDSEN, HJC

    1994-01-01

    A density matrix evolution (DME) method (H.J.C. Berendsen and J. Mavri, J. Phys. Chem., 97 (1993) 13469) to simulate the dynamics of quantum systems embedded in a classical environment is presented. The DME method allows treatment of nonadiabatic transitions. As numerical examples the collinear coll

  4. Separable Transition Density in the Hybrid Model for Tumor-Immune System Competition

    Directory of Open Access Journals (Sweden)

    Carlo Cattani

    2012-01-01

    Full Text Available A hybrid model, on the competition tumor cells immune system, is studied under suitable hypotheses. The explicit form for the equations is obtained in the case where the density function of transition is expressed as the product of separable functions. A concrete application is given starting from a modified Lotka-Volterra system of equations.

  5. Universal dynamics of density correlations at the transition to the many-body localized state

    Science.gov (United States)

    Mierzejewski, M.; Herbrych, J.; Prelovšek, P.

    2016-12-01

    Within one-dimensional disordered models of interacting fermions, we perform a numerical study of several dynamical density correlations, which can serve as hallmarks of the transition to the many-body localized state. The results confirm that density-wave correlations exhibit quite an abrupt change with increasing disorder, with a nonvanishing long-time value characteristic for the nonergodic phase. In addition, our results reveal a logarithmic variation of correlations in time in a wide time window, which we can bring in connection with the anomalous behavior of the dynamical conductivity near the transition. Our results support the view that the transition to many-body localization can be characterized by universal dynamical exponents.

  6. The dipole moment of the spin density as a local indicator for phase transitions

    Science.gov (United States)

    Schmitz, D.; Schmitz-Antoniak, C.; Warland, A.; Darbandi, M.; Haldar, S.; Bhandary, S.; Eriksson, O.; Sanyal, B.; Wende, H.

    2014-07-01

    The intra-atomic magnetic dipole moment - frequently called term - plays an important role in the determination of spin magnetic moments by x-ray absorption spectroscopy for systems with nonspherical spin density distributions. In this work, we present the dipole moment as a sensitive monitor to changes in the electronic structure in the vicinity of a phase transiton. In particular, we studied the dipole moment at the Fe2+ and Fe3+ sites of magnetite as an indicator for the Verwey transition by a combination of x-ray magnetic circular dichroism and density functional theory. Our experimental results prove that there exists a local change in the electronic structure at temperatures above the Verwey transition correlated to the known spin reorientation. Furthermore, it is shown that measurement of the dipole moment is a powerful tool to observe this transition in small magnetite nanoparticles for which it is usually screened by blocking effects in classical magnetometry.

  7. Analysis on insulator–metal transition in yttrium doped LSMO from electron density distribution

    Indian Academy of Sciences (India)

    S Israel; S Saravana Kumar; R Renuretson; R A J R Sheeba; R Saravanan

    2012-02-01

    Yttrium doped LSMO (La1−SrMnO3) was prepared using sol–gel technique and analysed for the insulator–metal transition fromcharge density variation in the unit cell with respect to different stoichiometric inclusion of yttrium. X-ray powder diffraction profiles of the samples were obtained and the well known Rietveld method and a versatile tool called maximum entropy method (MEM) were used for structural and profile refinement. The charge density in the unit cell was constructed using refined structure factors and was analysed. The charge ordering taking place in the insulator–metal transition was investigated and quantified. The insulator–metal transition was found to occur when 20% of La/Sr atoms were replaced by yttrium. The changes in the charge environment have also been analysed.

  8. Ultrafast Spin Density Wave Transition in Chromium Governed by Thermalized Electron Gas

    Science.gov (United States)

    Nicholson, C. W.; Monney, C.; Carley, R.; Frietsch, B.; Bowlan, J.; Weinelt, M.; Wolf, M.

    2016-09-01

    The energy and momentum selectivity of time- and angle-resolved photoemission spectroscopy is exploited to address the ultrafast dynamics of the antiferromagnetic spin density wave (SDW) transition photoexcited in epitaxial thin films of chromium. We are able to quantitatively extract the evolution of the SDW order parameter Δ through the ultrafast phase transition and show that Δ is governed by the transient temperature of the thermalized electron gas, in a mean field description. The complete destruction of SDW order on a sub-100 fs time scale is observed, much faster than for conventional charge density wave materials. Our results reveal that equilibrium concepts for phase transitions such as the order parameter may be utilized even in the strongly nonadiabatic regime of ultrafast photoexcitation.

  9. The dipole moment of the spin density as a local indicator for phase transitions.

    Science.gov (United States)

    Schmitz, D; Schmitz-Antoniak, C; Warland, A; Darbandi, M; Haldar, S; Bhandary, S; Eriksson, O; Sanyal, B; Wende, H

    2014-07-21

    The intra-atomic magnetic dipole moment - frequently called ⟨Tz⟩ term - plays an important role in the determination of spin magnetic moments by x-ray absorption spectroscopy for systems with nonspherical spin density distributions. In this work, we present the dipole moment as a sensitive monitor to changes in the electronic structure in the vicinity of a phase transiton. In particular, we studied the dipole moment at the Fe(2+) and Fe(3+) sites of magnetite as an indicator for the Verwey transition by a combination of x-ray magnetic circular dichroism and density functional theory. Our experimental results prove that there exists a local change in the electronic structure at temperatures above the Verwey transition correlated to the known spin reorientation. Furthermore, it is shown that measurement of the dipole moment is a powerful tool to observe this transition in small magnetite nanoparticles for which it is usually screened by blocking effects in classical magnetometry.

  10. The order parameter of glass transition: Spontaneously delocalized nanoscale solitary wave with transverse ripplon-like soft wave

    Directory of Open Access Journals (Sweden)

    Jia Lin Wu

    2013-06-01

    Full Text Available In macromolecular self-avoiding random walk, movement of each chain-particle accompanies an instantaneous spin system with de Gennes n = 0 that provides extra energy, extra vacancy volume and relaxation time needed for chain-particles co-movement. Using these additional and instantaneous spin systems not only directly yields the same Brownian motion mode in glass transition (GT and reptation-tube model, but also proves that the entangled chain length corresponding to the Reynolds number in hydrodynamics and the inherent diffusion - delocalization mode of entangled chains, from frozen glass state to melt liquid state, is a chain-size solitary wave with transverse ripplon-like soft wave. Thus, the order parameter of GT is found. The various currently available GT theories, such as Static Replica, Random First-Order Transition, Potential Energy Landscape, Mode-Coupling and Nanoscale Heterogeneity, can be unified using the additional and instantaneous spin system. GT served as an inspiration and continues to serve as the paradigm in the universal random delocalization transitions from disorder to more disorder until turbulence.

  11. The glass transition in cured epoxy thermosets: A comparative molecular dynamics study in coarse-grained and atomistic resolution

    Energy Technology Data Exchange (ETDEWEB)

    Langeloth, Michael; Böhm, Michael C.; Müller-Plathe, Florian [Eduard-Zintl-Institut für Anorganische und Physikalische Chemie and Center of Smart Interfaces, Technische Universität Darmstadt, Alarich Weiss Straße 4, D-64287 Darmstadt (Germany); Sugii, Taisuke, E-mail: taisuke.sugii.zs@hitachi.com [Center for Technology Innovation – Mechanical Engineering, Research & Development Group, Hitachi, Ltd., 832-2, Horiguchi, Hitachinaka, Ibaraki 312-0034 (Japan)

    2015-12-28

    We investigate the volumetric glass transition temperature T{sub g} in epoxy thermosets by means of molecular dynamics simulations. The epoxy thermosets consist of the resin bisphenol A diglycidyl ether and the hardener diethylenetriamine. A structure based coarse-grained (CG) force field has been derived using iterative Boltzmann inversion in order to facilitate simulations of larger length scales. We observe that T{sub g} increases clearly with the degree of cross-linking for all-atomistic (AA) and CG simulations. The transition T{sub g} in CG simulations of uncured mixtures is much lower than in AA-simulations due to the soft nature of the CG potentials, but increases all the more with the formation of rigid cross-links. Additional simulations of the CG mixtures in contact with a surface show the existence of an interphase region of about 3 nm thickness in which the network properties deviate significantly from the bulk. In accordance to experimental studies, we observe that T{sub g} is reduced in this interphase region and gradually increases to its bulk value with distance from the surface. The present study shows that the glass transition is a local phenomenon that depends on the network structure in the immediate environment.

  12. Characterization of Phase Transition in Heisenberg Fluids from Density Functional Theory

    Science.gov (United States)

    Li, Liang-Sheng; Li, Li; Chen, Xiao-Song

    2009-02-01

    The phase transition of Heisenberg fluid has been investigated with the density functional theory in mean-field approximation (MF). The matrix of the second derivatives of the grand canonical potential Ω with respect to the particle density fluctuations and the magnetization fluctuations has been investigated and diagonalized. The smallest eigenvalue being 0 signalizes the phase instability and the related eigenvector characterizes this phase transition. We find a Curie line where the order parameter is pure magnetization and a spinodal where the order parameter is a mixture of particle density and magnetization. Along the spinodal, the character of phase instability changes continuously from predominant condensation to predominant ferromagnetic phase transition with the decrease of total density. The spinodal meets the Curie line at the critical endpoint with the reduced density ρ* = ρσ3 = 0.224 and the reduced temperature T* = kT/in = 1.87 (σ is the diameter of Heisenberg hard sphere and in is the coupling constant).

  13. Characterization of Phase Transition in Heisenberg Fluids from Density Functional Theory

    Institute of Scientific and Technical Information of China (English)

    LI Liang-Sheng; LI Li; CHEN Xiao-Song

    2009-01-01

    The phase transition of Heisenberg fluid has been investigated with the density functional theory in mean-field approximation (MF).The matrix of the second derivatives of the grand canonical potential Ω with respect to the particle density fluctuations and the magnetization fluctuations has been investigated and diagonalized.The smallest eigenvalue being 0 signalizes the phase instability and the related eigenvector characterizes this phase transition.We find a Curie line where the order parameter is pure magnetization and a spinodM where the order parameter is a mixture of particle density and magnetization.Along the spinodal, the character of phase instability changes continuously from predominant condensation to predominant ferromagnetic phase transition with the decrease of total density.The spinodal meets the Curie line at the critical endpoint with the reduced density ρ*= ρσ3=0.224 and the reduced temperature T* = kT/ε = 1.87 (σ is the diameter of Heisenberg hard sphere and e is the coupling constant).

  14. Density-driven structural transformations in network forming glasses: a high-pressure neutron diffraction study of GeO2 glass up to 17.5 GPa.

    Science.gov (United States)

    Salmon, Philip S; Drewitt, James W E; Whittaker, Dean A J; Zeidler, Anita; Wezka, Kamil; Bull, Craig L; Tucker, Matthew G; Wilding, Martin C; Guthrie, Malcolm; Marrocchelli, Dario

    2012-10-17

    The structure of GeO(2) glass was investigated at pressures up to 17.5(5) GPa using in situ time-of-flight neutron diffraction with a Paris-Edinburgh press employing sintered diamond anvils. A new methodology and data correction procedure were developed, enabling a reliable measurement of structure factors that are largely free from diamond Bragg peaks. Calibration curves, which are important for neutron diffraction work on disordered materials, were constructed for pressure as a function of applied load for both single and double toroid anvil geometries. The diffraction data are compared to new molecular-dynamics simulations made using transferrable interaction potentials that include dipole-polarization effects. The results, when taken together with those from other experimental methods, are consistent with four densification mechanisms. The first, at pressures up to approximately equal 5 GPa, is associated with a reorganization of GeO(4) units. The second, extending over the range from approximately equal 5 to 10 GPa, corresponds to a regime where GeO(4) units are replaced predominantly by GeO(5) units. In the third, as the pressure increases beyond ~10 GPa, appreciable concentrations of GeO(6) units begin to form and there is a decrease in the rate of change of the intermediate-range order as measured by the pressure dependence of the position of the first sharp diffraction peak. In the fourth, at about 30 GPa, the transformation to a predominantly octahedral glass is achieved and further densification proceeds via compression of the Ge-O bonds. The observed changes in the measured diffraction patterns for GeO(2) occur at similar dimensionless number densities to those found for SiO(2), indicating similar densification mechanisms for both glasses. This implies a regime from about 15 to 24 GPa where SiO(4) units are replaced predominantly by SiO(5) units, and a regime beyond ~24 GPa where appreciable concentrations of SiO(6) units begin to form.

  15. Optical properties and weakening of elastic moduli with increasing glass transition temperature (T{sub g}) in (80-x)TeO{sub 2}-xBaO-20ZnO glasses

    Energy Technology Data Exchange (ETDEWEB)

    Ismail, Muliana; Supardan, Siti Nurbaya; Yahya, Ahmad Kamal [Univ. Teknologi Mara (Malaysia). School of Physics and Materials Studies; Abd-Shukor, Roslan [Univ. Kebangsaan Malaysia (Malaysia). School of Applied Physics

    2015-08-15

    BaO addition to ternary (80-x)TeO{sub 2}-20ZnO-xBaO (x = 0-20 mol.%) glasses resulted in a decrease in ultrasonic velocities and independent elastic moduli; this result indicated that the rigidity of the glass network weakened possibly because non-bridging oxygen increased. Thermal analysis results showed that glass transition temperature increased as BaO content increased because of the stabilizing effect of Ba{sup 2+} on the glass network. Additional analyses using bulk compression and ring deformation models revealed that the ratio between theoretical bulk modulus and experimental bulk modulus increased; this result indicated that the compression mechanism mainly involved isotropic ring compression. Furthermore, the increase in non-bridging oxygen formation with BaO addition caused a decrease in optical energy gap and an increase in refractive index. An increase in Urbach energy indicated that the degree of disorder in the glass system also increased.

  16. Shear Yielding and Shear Jamming of Dense Hard Sphere Glasses

    Science.gov (United States)

    Urbani, Pierfrancesco; Zamponi, Francesco

    2017-01-01

    We investigate the response of dense hard sphere glasses to a shear strain in a wide range of pressures ranging from the glass transition to the infinite-pressure jamming point. The phase diagram in the density-shear strain plane is calculated analytically using the mean-field infinite-dimensional solution. We find that just above the glass transition, the glass generically yields at a finite shear strain. The yielding transition in the mean-field picture is a spinodal point in presence of disorder. At higher densities, instead, we find that the glass generically jams at a finite shear strain: the jamming transition prevents yielding. The shear yielding and shear jamming lines merge in a critical point, close to which the system yields at extremely large shear stress. Around this point, highly nontrivial yielding dynamics, characterized by system-spanning disordered fractures, is expected.

  17. Fully relativistic study of forbidden transitions of OII : Electron density diagnosis for planetary nebulas

    Science.gov (United States)

    Chen, Shaohao; Qing, Bo; Li, Jiaming

    2007-10-01

    Using the multiconfiguration Dirac-Fock method, including the quantum electrodynamics corrections, especially with the Breit interactions, we calculate the electric quadrupole (E2) and magnetic dipole (M1) transition rates for the two transitions D5/2,3/2o2→S3/2o4 of OII . We show systematically that the correlation effects owing to core electron excitations and the Breit interactions are vitally important for the transition rates. We present a benchmark for the intensity ratio between the two transitions in the limit of high electron density in planetary nebulas, i.e., r(∞)=0.345-0.014+0.028 , which is in good agreement with modern astronomical observations.

  18. Turning reduced density matrix theory into a practical tool for studying the Mott transition

    Science.gov (United States)

    Pernal, Katarzyna

    2015-11-01

    Strongly correlated systems pose a challenge for theoretical methods based on an independent electron approximation. Such methods struggle to predict a nonzero gap in Mott insulators or to capture the correct physics of the insulator-to-metal phase transition in strongly correlated materials. In a recent paper by Shinohara et al (2015 New J. Phys. 17 093038) it is shown that strongly correlated materials and correct descriptions of their phase transitions are within the reach of reduced density matrix functional theory (RDMFT) approximations. For a doping-induced phase transition, not only is a satisfactory agreement with experimental spectra found for NiO but it is also shown that the physical picture of the observed Mott transition stays in line with more computationally demanding many-body theories. This is an important step toward providing an RDMFT-based computation tool for studying strongly correlated materials.

  19. Determination of production efficiency, color, glass transition, and sticky point temperature of spray-dried pomegranate juice powder

    OpenAIRE

    Khalid Muzaffar; Sajad Ahmad Wani; Bijamwar Vilas Dinkarrao; Pradyuman Kumar

    2016-01-01

    The aim of the study was to determine the powder recovery, color characteristics, glass transition temperature (Tg), and sticky point (Ts) temperature of spray-dried pomegranate juice powder as affected by different concentrations of maltodextrin (DE 20). Five different combinations of pomegranate juice and maltodextrin (95:5, 90:10, 85:15, 80:20 and 75:25 v/w) were prepared and spray dried in a laboratory-type spray dryer. Increase in concentration of maltodextrin significantly increased the...

  20. Solving the initial condition of the string relaxation equation of the string model for glass transition: part-Ⅱ

    Institute of Scientific and Technical Information of China (English)

    Zhang Jin-Lu; Wang Li-Na; Zhao Xing-Yu; Zhang Li-Li; Zhou Heng-Wei; Wei Lai; Huang Yi-Neng

    2011-01-01

    The string model for the glass transition can quantitatively describe the universal α-relaxation in glassformers. The string relaxation equation (SRE) of the model simplifies the well-known Debye and Rouse-Zimm relaxation equations at high and low enough temperatures, respectively. However, its initial condition, necessary to the further model predictions of glassy dynamics, has not been solved. In this paper, the general initial condition of the SRE for stochastically spatially configurative strings is solved exactly based on the obtained special initial condition of the SRE for straight strings in a previous paper (J. L. Zhang et al. 2010 Chin. Phya. B 19, 056403).

  1. Transition Communities and the Glass Ceiling of Environmental Sustainability Policies at Three Universities

    Science.gov (United States)

    Pardellas Santiago, Miguel; Meira Cartea, Pablo; Iglesias da Cunha, Lucía

    2017-01-01

    Purpose: This paper deals with the experiences of three European universities that have implemented transition initiatives, using the Transition Network's methodology to promote their sustainability plans. The Transition Communities' model for change is presented from a socio-educational perspective as an effective methodology for encouraging…

  2. Multiconfiguration pair-density functional theory: barrier heights and main group and transition metal energetics.

    Science.gov (United States)

    Carlson, Rebecca K; Li Manni, Giovanni; Sonnenberger, Andrew L; Truhlar, Donald G; Gagliardi, Laura

    2015-01-13

    Kohn-Sham density functional theory, resting on the representation of the electronic density and kinetic energy by a single Slater determinant, has revolutionized chemistry, but for open-shell systems, the Kohn-Sham Slater determinant has the wrong symmetry properties as compared to an accurate wave function. We have recently proposed a theory, called multiconfiguration pair-density functional theory (MC-PDFT), in which the electronic kinetic energy and classical Coulomb energy are calculated from a multiconfiguration wave function with the correct symmetry properties, and the rest of the energy is calculated from a density functional, called the on-top density functional, that depends on the density and the on-top pair density calculated from this wave function. We also proposed a simple way to approximate the on-top density functional by translation of Kohn-Sham exchange-correlation functionals. The method is much less expensive than other post-SCF methods for calculating the dynamical correlation energy starting with a multiconfiguration self-consistent-field wave function as the reference wave function, and initial tests of the theory were quite encouraging. Here, we provide a broader test of the theory by applying it to bond energies of main-group molecules and transition metal complexes, barrier heights and reaction energies for diverse chemical reactions, proton affinities, and the water dimerization energy. Averaged over 56 data points, the mean unsigned error is 3.2 kcal/mol for MC-PDFT, as compared to 6.9 kcal/mol for Kohn-Sham theory with a comparable density functional. MC-PDFT is more accurate on average than complete active space second-order perturbation theory (CASPT2) for main-group small-molecule bond energies, alkyl bond dissociation energies, transition-metal-ligand bond energies, proton affinities, and the water dimerization energy.

  3. Thermal transitions in the low-density lipoprotein and lipids of the egg yolk of hens.

    Science.gov (United States)

    Smith, M B; Back, J F

    1975-05-22

    1. Differential sanning calorimetry and light-scattering have been used to investigate temperature-dependent transitions in low-density lipoprotein and in lipids from hens' egg yolk. Yolks of different fatty acid composition were obtained by varying the dietary lipid and by adding methyl sterculate to the hen's diet. 2. Lipoprotein solutions in 50 percent glycerol/water gave characteristic melting curves between -25 degrees C and 50 degrees C, and on cooling showed increases in light-scattering between 10 degrees C and -20 degrees C. The temperatures at which major changes occurred depended on the proportions of saturated and unsaturated fatty acids. 3. The thermal transitions in the intact lipoprotein in glycerol solution were reversible, but with marked hysteresis. Lipid extracted from the lipoprotein did not show temperature hystersis but the transition heats and melting curves similar to those of the intact lipoprotein. The results support the hypothesis of a "lipid-core" structure for low-density lipoproteins. 4. Scanning calorimetry of egg-yolk lecithins indicated a strong dependence of transition temperature on water content in the rane 3 percent-20 percent water. A rise in the mid-temperature of the liquid-crystalline to gel transition as the water content is lowered on freezing may be the primary event in the irreversible gelation of egg yolk and aggregation of lipoprotein.

  4. Phase transitions in Core-Collapse Supernova Matter at sub-saturation densities

    CERN Document Server

    Pais, Helena; Stone, Jirina R

    2014-01-01

    We perform a three-dimensional, finite temperature Skyrme-Hartree-Fock study of inhomogeneous nuclear matter to determine the critical density and temperature for the phase transition between the pasta phase and homogeneous matter and its properties. We employ four different parametrizations of the Skyrme nuclear energy-density functional, SkM$^*$, SLy4, NRAPR and SQMC700, which span a range of saturation-density symmetry energy behaviours constrained by a variety of nuclear experimental probes. For each of these interactions we calculate free energy, pressure, entropy and chemical potentials in the range of particle number densities where the nuclear pasta phases are expected to exist, 0.02 - 0.12 fm$^{-3}$, temperatures 2 - 8 MeV and a proton fraction of 0.3. We find unambiguous evidence for a first-order phase transition to uniform matter, unsoftened by the presence of the pasta phases. No conclusive signs of first-order phase transition between the pasta phases is observed, and it is argued that the therm...

  5. Bulk Properties of Transition Metals: A Challenge for the Design of Universal Density Functionals.

    Science.gov (United States)

    Janthon, Patanachai; Luo, Sijie Andy; Kozlov, Sergey M; Viñes, Francesc; Limtrakul, Jumras; Truhlar, Donald G; Illas, Francesc

    2014-09-09

    Systematic evaluation of the accuracy of exchange-correlation functionals is essential to guide scientists in their choice of an optimal method for a given problem when using density functional theory. In this work, accuracy of one Generalized Gradient Approximation (GGA) functional, three meta-GGA functionals, one Nonseparable Gradient Approximation (NGA) functional, one meta-NGA, and three hybrid GGA functionals was evaluated for calculations of the closest interatomic distances, cohesive energies, and bulk moduli of all 3d, 4d, and 5d bulk transition metals that have face centered cubic (fcc), hexagonal closed packed (hcp), or body centered cubic (bcc) structures (a total of 27 cases). Our results show that including the extra elements of kinetic energy density and Hartree-Fock exchange energy density into gradient approximation density functionals does not usually improve them. Nevertheless, the accuracies of the Tao-Perdew-Staroverov-Scuseria (TPSS) and M06-L meta-GGAs and the MN12-L meta-NGA approach the accuracy of the Perdew-Burke-Ernzerhof (PBE) GGA, so usage of these functionals may be advisable for systems containing both solid-state transition metals and molecular species. The N12 NGA functional is also shown to be almost as accurate as PBE for bulk transition metals, and thus it could be a good choice for studies of catalysis given its proven good performance for molecular species.

  6. Relaxation times of nanoscale deformations on the surface of a polymer thin film near and below the glass transition

    Science.gov (United States)

    Papaléo, R. M.; Leal, R.; Carreira, W. H.; Barbosa, L. G.; Bello, I.; Bulla, A.

    2006-09-01

    We report on measurements of relaxation times of nanometer-sized deformations resulting from the impact of individual energetic ions on poly(methyl methacrylate) surfaces at temperatures close to and below the glass transition Tg . The temporal evolution of the dimensions of the deformations is well described by a stretched exponential function, but with relaxation times τ(T) many orders of magnitude smaller than bulk values at the same T . The local Tg was around 86°C , roughly 30°C below the conventional bulk Tg . At the vicinity of the local Tg , τ(T) follows the Vogel-Fulcher type of T dependence, but at lower T a transition towards a less steep behavior is seen.

  7. Observation of a Dynamic Crossover in RNA Hydration Water which Triggers the Glass Transition in the Biopolymer

    CERN Document Server

    Chu, X; Chen, S H; Faraone, A; Fratini, E; Baglioni, Piero; Chen, Sow-Hsin; Chu, Xiang-qiang; Faraone, Antonio; Fratini, Emiliano

    2007-01-01

    High-resolution quasi-elastic neutron scattering spectroscopy was used to measure H2O and D2O hydrated RNA samples. The contribution of scattering from RNA was subtracted out by taking the difference of the signals between the two samples. The measurements were made at a series of temperatures from 270 K down to 180 K. The Relaxing-Cage Model was used to analyze the difference quasi-elastic spectra. We observed clear evidence of a fragile-to-strong dynamic crossover (FSC) at TL = 220 K in RNA hydration water. We further show that the mean-square displacement of the hydrogen atoms in both RNA and its hydration water exhibit a sharp change in slope at approximately the same temperature 220 K. This latter fact suggests that the dynamic transition (or the glass transition) in RNA is triggered by the abrupt change of mobility of the hydration water at its FSC temperature TL.

  8. Energetics of glass fragmentation: Experiments on synthetic and natural glasses

    Science.gov (United States)

    Kolzenburg, S.; Russell, J. K.; Kennedy, L. A.

    2013-11-01

    Natural silicate glasses are an essential component of many volcanic rock types including coherent and pyroclastic rocks; they span a wide range of compositions, occur in diverse environments, and form under a variety of pressure-temperature conditions. In subsurface volcanic environments (e.g., conduits and feeders), melts intersect the thermodynamically defined glass transition temperature to form glasses at elevated confining pressures and under differential stresses. We present a series of room temperature experiments designed to explore the fundamental mechanical and fragmentation behavior of natural (obsidian) and synthetic glasses (Pyrex™) under confining pressures of 0.1-100 MPa. In each experiment, glass cores are driven to brittle failure under compressive triaxial stress. Analysis of the load-displacement response curves is used to quantify the storage of energy in samples prior to failure, the (brittle) release of elastic energy at failure, and the residual energy stored in the post-failure material. We then establish a relationship between the energy density within the sample at failure and the grain-size distributions (D-values) of the experimental products. The relationship between D-values and energy density for compressive fragmentation is significantly different from relationships established by previous workers for decompressive fragmentation. Compressive fragmentation is found to have lower fragmentation efficiency than fragmentation through decompression (i.e., a smaller change in D-value with increasing energy density). We further show that the stress storage capacity of natural glasses can be enhanced (approaching synthetic glasses) through heat treatment.

  9. Molecular Dynamical Simulation of Ice Phase Transition: Ice Ih to High-Density Amorphous

    Institute of Scientific and Technical Information of China (English)

    DONG Shun-Le; WANG Yan

    2005-01-01

    @@ We put 5kbar and 12kbar on perfect ice Ih lattice at 77K and 180K. After 30000 simulation steps (in units of 10-15 s), high-density amorphous ice is formed. Four-site simple-pair potential TIP4P is used for molecular interactions and the rigid molecular model is employed. Phase transition processes are fitted by an exponential function, and different phase transition times τ are obtained from O-O radial distribution functions (366 and 359fs for 77K and 180K) and O-O-O angle distribution functions (126 and 116fs for 77K and 180K).

  10. Identification of transition bias in oxidized low density lipoprotein receptor 1 gene in buffalo

    Directory of Open Access Journals (Sweden)

    N. Shabir

    2014-03-01

    Full Text Available Aim: Though transition bias has been previously demonstrated in cattle, however, there has not been any study that has explored transition bias in buffalo nuclear genome. The aim of the present study was to evaluate the nucleotide substitution pattern in the Intron I of Oxidised Low Density Lipoprotein Receptor 1 (OLR1 gene in four breeds of Indian buffalo using 24 different nucleotide substitution models and evaluate their association with DNA methylation. Materials and Methods: Transition/transversion bias (R was estimated by 24 different nucleotide substitution models available in MEGA 5.0. The transition/transversion bias (R was estimated under the Kimura 2-parameter model. Substitution patterns and the transitions/transversions rates (r were then estimated by Tamura-Nei-I and Tamura-Nei-II models. The CpG Island search was done by using CpG Plot Island online Software available at European Bioinformatics Institute (EBI website. Results: The frequency of transition was found to be 3.5 times higher than that of the transversion mutation frequency. Out of 9 nucleotide substitutions, 7 transitions and 2 transversions were found. Among all the nucleotide substitutions, thymine to cytosine substitutions was observed to be very high. CpG Island search tool revealed that IntronI of OLR1 genes is a CpG rich region, thus prone to methylation. Conclusions: Higher transition frequency was found in the intronI of OLR1 gene, however due to the richness of methylated CpGs in the evaluated stretch of genome, the higher T↔C transitions could likely be a result of frequent deaminations of the methylated cytosines into thymines during the evolution of four buffalo breeds.

  11. Influence of chain topology and bond potential on the glass transition of polymer chains simulated with the bond fluctuation model

    Energy Technology Data Exchange (ETDEWEB)

    Freire, J J [Departamento de Ciencias y Tecnicas FisicoquImicas, Facultad de Ciencias, Universidad Nacional de Educacion a Distancia (UNED), Senda del Rey 9, 28040 Madrid (Spain)], E-mail: jfreire@invi.uned.es

    2008-07-16

    The bond fluctuation model with a bond potential has been applied to investigation of the glass transition of linear chains and chains with a regular disposition of small branches. Cooling and subsequent heating curves are obtained for the chain energies and also for the mean acceptance probability of a bead jump. In order to mimic different trends to vitrification, a factor B gauging the strength of the bond potential with respect to the long-range potential (i.e. the intramolecular or intermolecular potential between indirectly bonded beads) has been introduced. (A higher value of B leads to a preference for the highest bond lengths and a higher total energy, implying a greater tendency to vitrify.) Different cases have been considered for linear chains: no long-range potential, no bond potential and several choices for B. Furthermore, two distinct values of B have been considered for alternate bonds in linear chains. In the case of the branched chains, mixed models with different values of B for bonds in the main chain and in the branches have also been investigated. The possible presence of ordering or crystallization has been characterized by calculating the collective light scattering function of the different samples after annealing at a convenient temperature below the onset of the abrupt change in the curves associated with a thermodynamic transition. It is concluded that ordering is inherited more efficiently in the systems with branched chains and also for higher values of B. The branched molecules with the highest B values in the main chain bonds exhibit two distinct transitions in the heating curves, which may be associated with two glass transitions. This behavior has been detected experimentally for chains with relatively long flexible branches.

  12. Unraveling protein stabilization mechanisms : Vitrification and water replacement in a glass transition temperature controlled system

    NARCIS (Netherlands)

    Grasmeijer, N; Stankovic, M; de Waard, H; Frijlink, H W; Hinrichs, W L J

    2013-01-01

    The aim of this study was to elucidate the role of the two main mechanisms used to explain the stabilization of proteins by sugar glasses during drying and subsequent storage: the vitrification and the water replacement theory. Although in literature protein stability is often attributed to either v

  13. On the Frequency Correction in Temperature-Modulated Differential Scanning Calorimetry of Glass Transition

    DEFF Research Database (Denmark)

    Guo, Xiaoju; Mauro, J.C.; Allan, D.C.;

    2012-01-01

    Temperature-modulated differential scanning calorimetry (TMDSC) is based on conventional DSC but with a sinusoidally modulated temperature path. Simulations of TMDSC signals were performed for Corning EAGLE XG® glass over a wide range of modulation frequencies. Our results reveal that the frequen...

  14. Thermalization calorimetry: A simple method for investigating glass transition and crystallization of supercooled liquids

    DEFF Research Database (Denmark)

    Jakobsen, Bo; Sanz, Alejandro; Niss, Kristine;

    2016-01-01

    We present a simple method for fast and cheap thermal analysis on supercooled glass-forming liquids. This “Thermalization Calorimetry” technique is based on monitoring the temperature and its rate of change during heating or cooling of a sample for which the thermal power input comes from heat...

  15. Dynamical transition in molecular glasses and proteins observed by spin relaxation of nitroxide spin probes and labels

    Science.gov (United States)

    Golysheva, Elena A.; Shevelev, Georgiy Yu.; Dzuba, Sergei A.

    2017-08-01

    In glassy substances and biological media, dynamical transitions are observed in neutron scattering that manifests itself as deviations of the translational mean-squared displacement, , of hydrogen atoms from harmonic dynamics. In biological media, the deviation occurs at two temperature intervals, at ˜100-150 K and at ˜170-230 K, and it is attributed to the motion of methyl groups in the former case and to the transition from harmonic to anharmonic or diffusive motions in the latter case. In this work, electron spin echo (ESE) spectroscopy—a pulsed version of electron paramagnetic resonance—is applied to study the spin relaxation of nitroxide spin probes and labels introduced in molecular glass former o-terphenyl and in protein lysozyme. The anisotropic contribution to the rate of the two-pulse ESE decay, ΔW, is induced by spin relaxation appearing because of restricted orientational stochastic molecular motion; it is proportional to τc, where is the mean-squared angle of reorientation of the nitroxide molecule around the equilibrium position and τc is the correlation time of reorientation. The ESE time window allows us to study motions with τc τc temperature dependence shows a transition near 240 K, which is in agreement with the literature data on . For spin probes of essentially different size, the obtained data were found to be close, which evidences that motion is cooperative, involving a nanocluster of several neighboring molecules. For the dry lysozyme, the τc values below 260 K were found to linearly depend on the temperature in the same way as it was observed in neutron scattering for . As spin relaxation is influenced only by stochastic motion, the harmonic motions seen in ESE must be overdamped. In the hydrated lysozyme, ESE data show transitions near 130 K for all nitroxides, near 160 K for the probe located in the hydration layer, and near 180 K for the label in the protein interior. For this system, the two latter transitions are not

  16. Development of DMBZ-15 High-Glass-Transition-Temperature Polyimides as PMR-15 Replacements Given R&D 100 Award

    Science.gov (United States)

    Chuang, Kathy

    2004-01-01

    PMR-15, a high-temperature polyimide developed in the mid-1970s at the NASA Lewis Research Center,1 offers the combination of low cost, easy processing, and good high-temperature performance and stability. It has been recognized as the leading polymer matrix resin for carbon-fiber-reinforced composites used in aircraft engine components. The state-of-the-art PMR-15 polyimide composite has a glass-transition temperature (Tg) of 348 C (658 F). Since composite materials must be used at temperatures well below their glass-transition temperature, the long-term use temperatures of PMR-15 composites can be no higher than 288 C (550 F). In addition, PMR-15 is made from methylene dianiline (MDA), a known liver toxin. Concerns about the safety of workers exposed to MDA during the fabrication of PMR-15 components and about the environmental impact of PMR-15 waste disposal have led to the industry-wide implementation of special handling procedures to minimize the health risks associated with this material. These procedures have increased manufacturing and maintenance costs significantly and have limited the use of PMR-15 in commercial aircraft engine components.

  17. Spectroscopic data of the 1.8-, 2.9-, and 4.3- mu m transitions in dysprosium-doped gallium lanthanum sulfide glass

    Science.gov (United States)

    Schweizer, T.; Hewak, D. W.; Samson, B. N.; Payne, D. N.

    1996-10-01

    Infrared emission at 1.8, 2.9, and 4.3 mu m is measured in dysprosium-doped gallium lanthanum sulfide (Ga:La:S) glass excited at 815 nm. Emission cross sections were calculated by Judd-Ofelt analysis, the Fuchtbauer-Ladenburg equation, and the theory of McCumber. The sigma tau value for the 4.3- mu m transition is \\similar 4000 times larger in the Ga:La:S glass than in a dysprosium-doped LiYF4 crystal, which has lased on this transition. The large sigma tau value and the recently reported ability of Ga:La:S glass to be fabricated into fiber form show the potential for an efficient, low-threshold mid-infrared fiber laser. The fluorescence peak at 4.3 mu m coincides with the fundamental absorption of atmospheric carbon dioxide, making the glass a potential laser source for gas-sensing applications.

  18. Spectroscopic data of the 1.8-, 2.9-, and 4.3-microm transitions in dysprosium-doped gallium lanthanum sulfide glass.

    Science.gov (United States)

    Schweizer, T; Hewak, D W; Samson, B N; Payne, D N

    1996-10-01

    Infrared emission at 1.8, 2.9, and 4.3 microm is measured in dysprosium-doped gallium lanthanum sulfide (Ga:La:S) glass excited at 815 nm. Emission cross sections were calculated by Judd-Ofelt analysis, the Füchtbauer- Ladenburg equation, and the theory of McCumber. The sigmatau value for the 4.3-microm transition is ~4000 times larger in the Ga:La:S glass than in a dysprosium-doped LiYF(4) crystal, which has lased on this transition. The large sigmatau value and the recently reported ability of Ga:La:S glass to be fabricated into fiber form show the potential for an efficient, low-threshold mid-infrared fiber laser. The f luorescence peak at 4.3 microm coincides with the fundamental absorption of atmospheric carbon dioxide, making the glass a potential laser source for gas-sensing applications.

  19. Turbulence at the transition to the high density H-mode in Wendelstein 7-AS plasmas

    DEFF Research Database (Denmark)

    Basse, N.P.; Zoletnik, S.; Baumel, S.

    2003-01-01

    Recently a new improved confinement regime was found in the Wendelstein 7-AS (W7-AS) stellarator (Renner H. et al 1989 Plasma Phys. Control. Fusion 31 1579). The discovery of this high density high confinement mode (HDH-mode) was facilitated by the installation of divertor modules. In this paper...... of the fluctuation level associated with the transition from NC- to HDH-mode. Correlation calculations on a 20 mus timescale between magnetic and density fluctuations lead to the result that the fluctuations are correlated in NC- but not in HDH-mode. Finally, a comparative analysis between the enhanced D-alpha H...

  20. Attractive particle interaction forces and packing density of fine glass powders.

    Science.gov (United States)

    Parteli, Eric J R; Schmidt, Jochen; Blümel, Christina; Wirth, Karl-Ernst; Peukert, Wolfgang; Pöschel, Thorsten

    2014-09-02

    We study the packing of fine glass powders of mean particle diameter in the range (4-52) μm both experimentally and by numerical DEM simulations. We obtain quantitative agreement between the experimental and numerical results, if both types of attractive forces of particle interaction, adhesion and non-bonded van der Waals forces are taken into account. Our results suggest that considering only viscoelastic and adhesive forces in DEM simulations may lead to incorrect numerical predictions of the behavior of fine powders. Based on the results from simulations and experiments, we propose a mathematical expression to estimate the packing fraction of fine polydisperse powders as a function of the average particle size.

  1. Large-Scale Density Functional Theory Transition State Searching in Enzymes.

    Science.gov (United States)

    Lever, Greg; Cole, Daniel J; Lonsdale, Richard; Ranaghan, Kara E; Wales, David J; Mulholland, Adrian J; Skylaris, Chris-Kriton; Payne, Mike C

    2014-11-06

    Linear-scaling quantum mechanical density functional theory calculations have been applied to study the rearrangement of chorismate to prephenate in large-scale models of the Bacillus subtilis chorismate mutase enzyme. By treating up to 2000 atoms at a consistent quantum mechanical level of theory, we obtain an unbiased, almost parameter-free description of the transition state geometry and energetics. The activation energy barrier is calculated to be lowered by 10.5 kcal mol(-1) in the enzyme, compared with the equivalent reaction in water, which is in good agreement with experiment. Natural bond orbital analysis identifies a number of active site residues that are important for transition state stabilization in chorismate mutase. This benchmark study demonstrates that linear-scaling density functional theory techniques are capable of simulating entire enzymes at the ab initio quantum mechanical level of accuracy.

  2. Shear-viscosity-to-entropy-density ratio and phase transition in multifragmentation of quasiprojectile

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Fan; Li, Cheng; Wen, Pei-Wei [Beijing Normal University, The Key Laboratory of Beam Technology of Ministry of Education, College of Nuclear Science and Technology, Beijing (China); Beijing Radiation Center, Beijing (China); Liu, Hang [Texas Advanced Computing Center University of Texas at Austin, Austin, TX (United States); Zhang, Feng-Shou [Beijing Normal University, The Key Laboratory of Beam Technology of Ministry of Education, College of Nuclear Science and Technology, Beijing (China); Beijing Radiation Center, Beijing (China); National Laboratory of Heavy Ion Accelerator of Lanzhou, Center of Theoretical Nuclear Physics, Lanzhou (China)

    2016-09-15

    Heavy-ion collisions at relativistic energy are studied by the isospin-dependent quantum molecular dynamics model in the company of the GEMINI model. The present study mainly focuses on the liquid-gas phase transition in nuclear matter. We calculate the shear-viscosity-to-entropy-density ratio η/s, γ{sub 2} and the multiplicity of intermediate-mass fragment (M{sub IMF}) in finite-size nuclear sources. At excitation energy 8 MeV a minimum of η/s is found in the coexistence phase of intermediate-mass fragments and light particles. At similar excitation energy a maximum of the M{sub IMF} is also observed at the same density condition which is an indication of the liquid-gas phase transition. (orig.)

  3. Metal-insulator transition in disordered systems from the one-body density matrix

    DEFF Research Database (Denmark)

    Olsen, Thomas; Resta, Raffaele; Souza, Ivo

    2017-01-01

    systems. In particular, for noninteracting systems the geometrical marker can be obtained from the configurational average of the norm-squared one-body density matrix, which can be calculated within open as well as periodic boundary conditions. This is in sharp contrast to a classification based...... on the static conductivity, which is only sensible within periodic boundary conditions. We exemplify the method by considering a simple lattice model, known to have a metal-insulator transition as a function of the disorder strength, and demonstrate that the transition point can be obtained accurately from...... the one-body density matrix. The approach has a general ab initio formulation and could in principle be applied to realistic disordered materials by standard electronic structure methods....

  4. Prevalence for the universal distribution of relaxation times near the glass transitions in experimental model systems: Rodlike liquid crystals and orientationally disordered crystals

    OpenAIRE

    Martínez García, Julio Cesar; Tamarit Mur, José Luis; Rzosca, S. J.

    2011-01-01

    Recently, Nielsen et al. [J. Chem. Phys. 130, 154508 (2009); Philos. Mag. 88, 4101 (2008)] demonstrated a universal pattern for the high frequency wing of the loss curve for primary relaxation time on approaching the glass transition for organic liquids. In this contribution it is presented that a similar universality occurs for glass-forming liquid crystals and orientationally disordered crystals (plastic crystals). Empirical correlations of the found behavior are also briefly di...

  5. Prevalence for the universal distribution of relaxation times near the glass transitions in experimental model systems: Rodlike liquid crystals and orientationally disordered crystals

    OpenAIRE

    2011-01-01

    Recently, Nielsen et al. [J. Chem. Phys. 130, 154508 (2009); Philos. Mag. 88, 4101 (2008)] demonstrated a universal pattern for the high frequency wing of the loss curve for primary relaxation time on approaching the glass transition for organic liquids. In this contribution it is presented that a similar universality occurs for glass-forming liquid crystals and orientationally disordered crystals (plastic crystals). Empirical correlations of the found behavior are also briefly di...

  6. Steam Reforming on Transition-metal Carbides from Density-functional Theory

    Energy Technology Data Exchange (ETDEWEB)

    Vojvodic, Aleksandra

    2012-05-11

    A screening study of the steam reforming reaction on clean and oxygen covered early transition-metal carbides surfaces is performed by means of density-functional theory calculations. It is found that carbides provide a wide spectrum of reactivities, from too reactive via suitable to too inert. Several molybdenum-based systems are identified as possible steam reforming catalysts. The findings suggest that carbides provide a playground for reactivity tuning, comparable to the one for pure metals.

  7. In situ unravelling structural modulation across the charge-density-wave transition in vanadium disulfide.

    Science.gov (United States)

    Sun, Xu; Yao, Tao; Hu, Zhenpeng; Guo, Yuqiao; Liu, Qinghua; Wei, Shiqiang; Wu, Changzheng

    2015-05-28

    A deep understanding of the relationship between electronic and structure ordering across the charge-density-wave (CDW) transition is crucial for both fundamental study and technological applications. Herein, using in situ X-ray absorption fine structure (XAFS) spectroscopy coupled with high-resolution transmission electron microscopy (HRTEM), we have illustrated the atomic-level information on the local structural evolution across the CDW transition and its influence on the intrinsic electrical properties in VS2 system. The structure transformation, which is highlighted by the formation of vanadium trimers with derivation of V-V bond length (ΔR = 0.10 Å), was clearly observed across the CDW process. Moreover, the corresponding influence of lattice variation on the electronic behavior was clearly characterized by experimental results as well as theoretical analysis, which demonstrated that vanadium trimers drive the deformation of space charge density distribution into √3 ×√3 periodicity, with the conductivity of a1g band reducing by half. These observations directly unveiled the close connection between lattice evolution and electronic property variation, paving a new avenue for understanding the intrinsic nature of electron-lattice interactions in the VS2 system and other isostructural transition metal dichalcogenides across the CDW transition process.

  8. Highly Mobile Metastable State of He-4 Thin Films: A Glass Transition by Mechanical Perturbation?

    Science.gov (United States)

    Minoguchi, Tomoki

    2017-01-01

    Solid layers of helium on graphite surface are known to go into a highly mobile state (HMS) once the solid layer is enforced to slip on the substrate. The HMS collapses to the stable inert state with the lifetime extending over 10^4 s. In this paper, we suggest that the HMS is a structural glass by showing the similarities between the present system and an organic conductor named BEDT-TTF. The latter was recently discovered to be an electronic glass if the cooling rate is rapid enough across the freezing temperature (Wigner crystal formation temperature). We then address a novel annealing process promoted by a local condensate which should be seen for the present He-4 case as the condensation fraction grows in the liquid overlayer.

  9. The characteristic of unsaturated polyester resin wettability toward glass fiber orientation, density and surface treatment

    Directory of Open Access Journals (Sweden)

    Saputra Asep H.

    2017-01-01

    Full Text Available Wettability of composite is one of key to increase mechanical properties of composite that affected by structure of reinforcement and type of resin used. Therefore, this research focused on the effect of orientation, density and surface treatment on fiber to the characteristic of composite’s wettability, which is observed by contact angle and wetting time. The fiber used in this research is fiberglass, and the method for contact angle measurement is direct observation from the camera recorder and the data record will be processed and analyzed by using image processing method. The result for those variations can be obtained from the relation of variations toward contact angle and wetting time. According to result of research, fiber with orientation 45°/45° gives lower contact angle but longer wetting time than fiber with orientation 0°/90°. For orientation 45°/45°, the differences in wetting time is 15 second longer than orientation 0°/90°. In case of fiber density, the sheet with fiber density of 900 has 7 second faster for wetting time than sheet with fiber density of 1250. The surface treatment with NaOH 5% can accelerate the wetting time until 10 second.

  10. Study on the spin crossover transition and glass transition for Fe(II) complex film, [Fe(II)(H-triazole){sub 3}]-Nafion, by means of Moessbauer spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Nakamoto, Akio; Kamebuchi, Hajime, E-mail: cc106909@mail.ecc.u-tokyo.ac.jp [University of Tokyo, Graduate School of Arts and Sciences (Japan); Enomoto, Masaya [Tokyo University of Science, Department of Chemistry, Faculty of Science Division I (Japan); Kojima, Norimichi [University of Tokyo, Graduate School of Arts and Sciences (Japan)

    2012-03-15

    [Fe(II)(H-trz){sub 3}]-Nafion (trz = triazole) is a transparent spin crossover complex film, where the spin crossover transition between the low-spin (S = 0) and the high-spin (S = 2) states takes place between 225 K and 300 K. In this film, two doublets corresponding to the low-spin and high-spin states were observed in the {sup 57}Fe Moessbauer spectra, reflecting the spin crossover transition. From the analysis of {sup 57}Fe Moessbauer spectra, the Debye temperatures of the low-spin and high-spin sites were estimated at 185 K and 176 K, respectively, in the temperature range between 10 K and 150 K. In this film, the total intensity of the Moessbauer spectra corresponding to the low-spin and high-spin sites drastically decreases above 200 K, reflecting the glass transition of Nafion, where the lattice vibration of [Fe(H-trz){sub 3}]{sub n}{sup 2n+} is softened just as in solution due to micro-Brown motion of the segment of Nafion polymer membrane.

  11. HATS-8b: A Low-Density Transiting Super-Neptune

    CERN Document Server

    Bayliss, D; Bakos, G Á; Penev, K; Zhou, G; Brahm, R; Rabus, M; Jordán, A; Mancini, L; de Val-Borro, M; Bhatti, W; Espinoza, N; Csubry, Z; Howard, A W; Fulton, B J; Buchhave, L A; Henning, T; Schmidt, B; Ciceri, S; Noyes, R W; Isaacson, H; Marcy, G W; Suc, V; Lázár, J; Papp, I; Sári, P

    2015-01-01

    HATS-8b is a low density transiting super-Neptune discovered as part of the HATSouth project. The planet orbits its solar-like G dwarf host (V=14.03 $\\pm$ 0.10 and T$_{eff}$ =5679 $\\pm$ 50 K) with a period of 3.5839 d. HATS-8b is the third lowest mass transiting exoplanet to be discovered from a wide-field ground based search, and with a mass of 0.138 $\\pm$ 0.019 M$_J$ it is approximately half-way between the masses of Neptune and Saturn. However HATS-8b has a radius of 0.873 (+0.123,-0.075) R$_J$, resulting in a bulk density of just 0.259 $\\pm$ 0.091 g.cm$^{-3}$. The metallicity of the host star is super-Solar ([Fe/H]=0.210 $\\pm$ 0.080), arguing against the idea that low density exoplanets form from metal-poor environments. The low density and large radius of HATS-8b results in an atmospheric scale height of almost 1000 km, and in addition to this there is an excellent reference star of near equal magnitude at just 19 arcsecond separation on the sky. These factors make HATS-8b an exciting target for future a...

  12. Theoretical Study of Role of Sb in Se_0.85-xTe_0.15Sbx Chalcogenide Glass in Influencing Glass Transition Temperature

    Science.gov (United States)

    Maharjan, N. B.; Paudyal, D. D.; Jeong, J.; Scheicher, R. H.; Das, T. P.

    2001-03-01

    The influence of Sb impurity on glass transition temperature (Tg) has recently been studied using Differential Scanning Calorimetry(N. B. Maharjan et al., Phy. Stat. Sol. (a) 178, 663 (2000)). The results indicate that Tg initially increases with Sb concentration (x), reaching a maximum at 0.04, subsequently decreasing till x=0.06 and then becoming constant. Qualitative explanation of this behavior for Tg has been suggested^1 using earlier ideas in the literature regarding the role of Sb in the interaction between chains in the Se_1-xTex system and bond energy strength considerations involving Se-Se and Sb-Se bonds. These ideas are being tested quantitatively using Hartree-Fock Cluster procedures, previously utilized by our group for study(H. S. Cho et al., (to be published); H. S. Cho et al., Hyperfine Interactions 96, 213 (1995)) of nuclear quadrupole interactions including that of ^125Te in Selenium and Tellurium(P. Boolchand et al., Phys. Rev. Lett. 30, 1292 (1973)).

  13. Crystallization of Ti33Cu67 metallic glass under high-current density electrical pulses

    Directory of Open Access Journals (Sweden)

    Mali Vyacheslav

    2011-01-01

    Full Text Available Abstract We have studied the phase and structure evolution of the Ti33Cu67 amorphous alloy subjected to electrical pulses of high current density. By varying the pulse parameters, different stages of crystallization could be observed in the samples. Partial polymorphic nanocrystallization resulting in the formation of 5- to 8-nm crystallites of the TiCu2 intermetallic in the residual amorphous matrix occurred when the maximum current density reached 9.7·108 A m-2 and the pulse duration was 140 μs, though the calculated temperature increase due to Joule heating was not enough to reach the crystallization temperature of the alloy. Samples subjected to higher current densities and higher values of the evolved Joule heat per unit mass fully crystallized and contained the Ti2Cu3 and TiCu3 phases. A common feature of the crystallized ribbons was their non-uniform microstructure with regions that experienced local melting and rapid solidification. PACS: 81; 81.05.Bx; 81.05.Kf.

  14. Many-body localization and transition by density matrix renormalization group and exact diagonalization studies

    Science.gov (United States)

    Lim, S. P.; Sheng, D. N.

    2016-07-01

    A many-body localized (MBL) state is a new state of matter emerging in a disordered interacting system at high-energy densities through a disorder-driven dynamic phase transition. The nature of the phase transition and the evolution of the MBL phase near the transition are the focus of intense theoretical studies with open issues in the field. We develop an entanglement density matrix renormalization group (En-DMRG) algorithm to accurately target highly excited states for MBL systems. By studying the one-dimensional Heisenberg spin chain in a random field, we demonstrate the accuracy of the method in obtaining energy eigenstates and the corresponding statistical results of quantum states in the MBL phase. Based on large system simulations by En-DMRG for excited states, we demonstrate some interesting features in the entanglement entropy distribution function, which is characterized by two peaks: one at zero and another one at the quantized entropy S =ln2 with an exponential decay tail on the S >ln2 side. Combining En-DMRG with exact diagonalization simulations, we demonstrate that the transition from the MBL phase to the delocalized ergodic phase is driven by rare events where the locally entangled spin pairs develop power-law correlations. The corresponding phase diagram contains an intermediate or crossover regime, which has power-law spin-z correlations resulting from contributions of the rare events. We discuss the physical picture for the numerical observations in this regime, where various distribution functions are distinctly different from results deep in the ergodic and MBL phases for finite-size systems. Our results may provide new insights for understanding the phase transition in such systems.

  15. Nanoscale confinement and interfacial effects on the dynamics and glass transition/crystallinity of thin adsorbed films on silica nanoparticles

    Science.gov (United States)

    Madathingal, Rajesh Raman

    hydrogen bonded to the silanols, and was independent of particle morphology. For methylated silica, (CH3) 3-SiO2, the adsorption isotherms were identical for colloidal and fumed silica, but Tg was depressed for the former, and comparable to the bulk value for the latter. The increased Tg of PMMA adsorbed onto fumed (CH3)3-SiO2 was attributed to the larger loops formed by the bridging PMMA chains between the silica aggregates. For nanocomposites the interphase region becomes more important as the surface/volume ratio of the nanoparticles increases. Polymers have chain dimensions (characterized by the radius of gyration, Rg) similar to the nanoparticles (Rnanoparticle) themselves, so that chain conformation, mobility and crystallinity can be affected by Rg/Rnanoparticle. Here, both the glass transition temperature (Tg) and degree of crystallinity (Xc) of polyethylene oxide (PEO) on individual SiO 2 nanoparticles of nominal 15, 50 and 100 nm diameter (2 RSiO2 ) , in which Rg (PEO) was greater, equal to or less than RSiO2 was investigated. Plateau adsorption of PEO on SiO2 nanoparticles (PEO-SiO2) increased in the order PEO-SiO 2 (100 nm) > PEO-SiO2 (50 nm) > PEO-SiO2 (15 nm). At plateau adsorption after melting and solidification, the samples were completely amorphous. The Tg of the adsorbed PEO increased in the order PEO-SiO 2 (100 nm) > PEO-SiO2 (50 nm) > PEO-SiO2 (15 nm); since the Tgs were above 25°C in all cases, the PEO behaved more like a brittle solid than an elastomer. For comparable amounts of PEO that were adsorbed from solution but not melted, the melt endotherm increased in the order PEO-SiO2 (15 nm) > PEO-SiO2 (50 nm) > PEO-SiO 2 (100 nm). These trends were interpreted as due to an increase in loop/tail lengths and thus flexibility, with a concomitant ability to crystallize, as Rg (PEO)/RSiO2 decreased and which was the result of less hydrogen bond formation between the oxygens of PEO and the silanols (SiOH) of the SiO 2 as the nanoparticle size decreased. This

  16. Final Report on DE-FG02-04ER46107: Glasses, Noise and Phase Transitions

    Energy Technology Data Exchange (ETDEWEB)

    Yu, Clare C. [Univ. of California, Irvine, CA (United States)

    2011-12-31

    We showed that noise has distinct signatures at phase transitions in spin systems. We also studied charge noise, critical current noise, and flux noise in superconducting qubits and Josephson junctions.

  17. Snapshotted glass and gel transitions of stable colloidal dispersions after shear-driven aggregation in a microchannel.

    Science.gov (United States)

    Meng, Xia; Wu, Hua; Morbidelli, Massimo

    2015-02-07

    Intense shear can lead to aggregation of colloids that are highly stable at rest. The aggregation process typically has an induction time, and then becomes explosive, leading to rapid phase transitions. We study the phase evolution during shear-driven aggregation in a short microchannel (MC) under intense shear for a colloid with a high interaction energy barrier that ensures high stability of particles and clusters before and after intense shear. The short residence time allows us to snapshot the phase evolution by repeatedly cycling the colloid in the MC. It is found that, depending on the particle concentration, in addition to a fluid of clusters and a solid-like gel, there is another solid-like state between them: Wigner glass of clusters. Their transitions occur over a large range of particle concentrations. We have proposed a phase diagram that describes how the transitions of the three phases evolve in the aggregation steady state in the colloidal interaction vs. particle concentration plane.

  18. Transition from glass to digital slide microscopy in the teaching of oral pathology in a Brazilian dental school.

    Science.gov (United States)

    Fonseca, Felipe-Paiva; Santos-Silva, Alan-Roger; Lopes, Márcio-Ajudarte; Almeida, Oslei-Paes de; Vargas, Pablo-Agustin

    2015-01-01

    Several medical and dental schools have described their experience in the transition from conventional to digital microscopy in the teaching of general pathology and histology disciplines; however, this transitional process has scarcely been reported in the teaching of oral pathology. Therefore, the objective of the current study is to report the transition from conventional glass slide to virtual microscopy in oral pathology teaching, a unique experience in Latin America. An Aperio ScanScope® scanner was used to digitalize histological slides used in practical lectures of oral pathology. The challenges and benefits observed by the group of Professors from the Piracicaba Dental School (Brazil) are described and a questionnaire to evaluate the students' compliance to this new methodology was applied. An improvement in the classes was described by the Professors who mainly dealt with questions related to pathological changes instead of technical problems; also, a higher interaction with the students was described. The simplicity of the software used and the high quality of the virtual slides, requiring a smaller time to identify microscopic structures, were considered important for a better teaching process. Virtual microscopy used to teach oral pathology represents a useful educational methodology, with an excellent compliance of the dental students.

  19. Transition from glass to digital slide microscopy in the teaching of oral pathology in a Brazilian dental school

    Science.gov (United States)

    Fonseca, Felipe-Paiva; Santos-Silva, Alan-Roger; Lopes, Márcio-Ajudarte; de Almeida, Oslei-Paes

    2015-01-01

    Objectives: Several medical and dental schools have described their experience in the transition from conventional to digital microscopy in the teaching of general pathology and histology disciplines; however, this transitional process has scarcely been reported in the teaching of oral pathology. Therefore, the objective of the current study is to report the transition from conventional glass slide to virtual microscopy in oral pathology teaching, a unique experience in Latin America. Study Design: An Aperio ScanScope® scanner was used to digitalize histological slides used in practical lectures of oral pathology. The challenges and benefits observed by the group of Professors from the Piracicaba Dental School (Brazil) are described and a questionnaire to evaluate the students’ compliance to this new methodology was applied. Results: An improvement in the classes was described by the Professors who mainly dealt with questions related to pathological changes instead of technical problems; also, a higher interaction with the students was described. The simplicity of the software used and the high quality of the virtual slides, requiring a smaller time to identify microscopic structures, were considered important for a better teaching process. Conclusions: Virtual microscopy used to teach oral pathology represents a useful educational methodology, with an excellent compliance of the dental students. Key words:Digital microscopy, virtual microscopy, dental education, virtual slides, oral pathology. PMID:25129250

  20. Study of rigidity of semiconducting vanadate glasses and its importance in use of coatings

    Indian Academy of Sciences (India)

    Yasser B Saddeek; M S Gaafar

    2014-05-01

    The elastic moduli of some multicomponent vanadate based glasses were analysed in terms of the bond compression model by some physical parameters such as, the density, average stretching force constant and average atomic ring size. These parameters were calculated for all the glass series and for all the glass composition to estimate the rigidity of these glasses. The results showed that the average force constant and the elastic moduli of these glasses are sensitive to the decrease in PbO content. This behaviour was attributed to the increase in the molar volume and the role of different modifiers. These parameters along with the coordination number of the glasses affect the glass transition temperature. The correlation between the elastic moduli and thermal properties of these samples showed that 0.25MoO3–0.25PbO–0.5V2O5 glass is the most rigid and has an applicable glass transition temperature for coating.

  1. Density functional calculations on electronic circular dichroism spectra of chiral transition metal complexes.

    Science.gov (United States)

    Autschbach, Jochen; Jorge, Francisco E; Ziegler, Tom

    2003-05-05

    Time-dependent density functional theory (TD-DFT) has for the first time been applied to the computation of circular dichroism (CD) spectra of transition metal complexes, and a detailed comparison with experimental spectra has been made. Absorption spectra are also reported. Various Co(III) complexes as well as [Rh(en)(3)](3+) are studied in this work. The resulting simulated CD spectra are generally in good agreement with experimental spectra after corrections for systematic errors in a few of the lowest excitation energies are applied. This allows for an interpretation and assignment of the spectra for the whole experimentally accessible energy range (UV/vis). Solvent effects on the excitations are estimated via inclusion of a continuum solvent model. This significantly improves the computed excitation energies for charge-transfer bands for complexes of charge +3, but has only a small effect on those for neutral or singly charged complexes. The energies of the weak d-to-d transitions of the Co complexes are systematically overestimated due to deficiencies of the density functionals. These errors are much smaller for the 4d metal complex. Taking these systematic errors and the effect of a solvent into consideration, TD-DFT computations are demonstrated to be a reliable tool in order to assist with the assignment and interpretation of CD spectra of chiral transition metal complexes.

  2. Particle Density in Zero Temperature Symmetry Restoring Phase Transitions in Four-Fermion Interaction Models

    Institute of Scientific and Technical Information of China (English)

    ZHOU Bang-Rong

    2004-01-01

    By means of critical behaviors of the dynamical fermion mass in four-fermion interaction models, we show by explicit calculations that when T = 0 the particle density will have a discontinuous jumping across the critical chemical potential μc in 2D and 3D Gross-Neveu (GN) model and these physically explain the first-order feature of the corresponding symmetry restoring phase transitions. For the second-order phase transitions in the 3D GN model when T → 0 and in 4D Nambu-Jona-Lasinio (NJL) model when T = 0, it is proven that the particle density itself will be continuous across μc but its derivative over the chemical potential μ will have a discontinuous jumping. The results give a physical explanation of implications of the tricritical point (T, μ) = (0,μc) in the 3D GN model. The discussions also show effectiveness of the critical analysis approach of phase transitions.

  3. A Density Functional Theory Study on the Deformation Behaviors of Fe-Si-B Metallic Glasses

    Directory of Open Access Journals (Sweden)

    Guang-Ping Zheng

    2012-08-01

    Full Text Available Density functional theory has been employed to investigate the deformation behaviors of glassy Fe-Si-B model systems prepared by ab initio molecular dynamics. The atomistic deformation defects which are closely related to the local dilation volumes or excess volumes and unstable bonding have been systematically analyzed. It has been found that the icosahedral structures are relatively stable under shear deformation until fracture occurs. Plastic flow is indicated by interruption of percolating icosahedral structures, caused by unstable Fe-Si bonding of p-s hybridization in nature.

  4. Weak K→π generalized form factors and transverse transition quark-spin density from the instanton vacuum

    Directory of Open Access Journals (Sweden)

    Hyeon-Dong Son

    2015-07-01

    Full Text Available We investigate the generalized K→π transition vector and tensor form factors, from which we derive the transverse quark spin density in the course of the K→π transition, based on the nonlocal chiral quark model from the instanton vacuum. The results of the transition tensor form factor are in good agreement with recent data of lattice QCD. The behavior of the transverse quark spin density of the K→π transition turns out to be very similar to those of the pion and the kaon.

  5. From boiling point to glass transition temperature: Transport coefficients in molecular liquids follow three-parameter scaling

    Science.gov (United States)

    Schmidtke, B.; Petzold, N.; Kahlau, R.; Hofmann, M.; Rössler, E. A.

    2012-10-01

    The phenomenon of the glass transition is an unresolved problem in condensed matter physics. Its prominent feature, the super-Arrhenius temperature dependence of the transport coefficients, remains a challenge to be described over the full temperature range. For a series of molecular glass formers, we combined τ(T) collected from dielectric spectroscopy and dynamic light scattering covering a range 10-12 s < τ(T) < 102 s. Describing the dynamics in terms of an activation energy E(T), we distinguish a high-temperature regime characterized by an Arrhenius law with a constant activation energy E∞ and a low-temperature regime for which Ecoop(T) ≡ E(T)-E∞ increases exponentially while cooling. A scaling is introduced, specifically Ecoop(T)/E∞ ∝ exp[-λ(T/TA-1)], where λ is a fragility parameter and TA a reference temperature proportional to E∞. In order to describe τ(T) still the attempt time τ∞ has to be specified. Thus, a single interaction parameter E∞ describing the high-temperature regime together with λ controls the temperature dependence of low-temperature cooperative dynamics.

  6. Electronic and magnetic properties of spiral spin-density-wave states in transition-metal chains

    Science.gov (United States)

    Tanveer, M.; Ruiz-Díaz, P.; Pastor, G. M.

    2016-09-01

    The electronic and magnetic properties of one-dimensional (1D) 3 d transition-metal nanowires are investigated in the framework of density functional theory. The relative stability of collinear and noncollinear (NC) ground-state magnetic orders in V, Mn, and Fe monoatomic chains is quantified by computing the frozen-magnon dispersion relation Δ E (q ⃗) as a function of the spin-density-wave vector q ⃗. The dependence on the local environment of the atoms is analyzed by varying systematically the lattice parameter a of the chains. Electron correlation effects are explored by comparing local spin-density and generalized-gradient approximations to the exchange and correlation functional. Results are given for Δ E (q ⃗) , the local magnetic moments μ⃗i at atom i , the magnetization-vector density m ⃗(r ⃗) , and the local electronic density of states ρi σ(ɛ ) . The frozen-magnon dispersion relations are analyzed from a local perspective. Effective exchange interactions Ji j between the local magnetic moments μ⃗i and μ⃗j are derived by fitting the ab initio Δ E (q ⃗) to a classical 1D Heisenberg model. The dominant competing interactions Ji j at the origin of the NC magnetic order are identified. The interplay between the various Ji j is revealed as a function of a in the framework of the corresponding magnetic phase diagrams.

  7. Freeze-Drying Above the Glass Transition Temperature in Amorphous Protein Formulations While Maintaining Product Quality and Improving Process Efficiency.

    Science.gov (United States)

    Depaz, Roberto A; Pansare, Swapnil; Patel, Sajal Manubhai

    2016-01-01

    This study explored the ability to conduct primary drying during lyophilization at product temperatures above the glass transition temperature of the maximally freeze-concentrated solution (Tg′) in amorphous formulations for four proteins from three different classes. Drying above Tg′ resulted in significant reductions in lyophilization cycle time. At higher protein concentrations, formulations freeze dried above Tg′ but below the collapse temperature yielded pharmaceutically acceptable cakes. However, using an immunoglobulin G type 4 monoclonal antibody as an example, we found that as protein concentration decreased, minor extents of collapse were observed in formulations dried at higher temperatures. No other impacts to product quality, physical stability, or chemical stability were observed in this study among the different drying conditions for the different proteins. Drying amorphous formulations above Tg′, particularly high protein concentration formulations, is a viable means to achieve significant time and cost savings in freeze-drying processes.

  8. Spin-glass transition in Ni carbide single crystal nanoparticles with Ni3C − type structure

    Directory of Open Access Journals (Sweden)

    S. Fujieda

    2016-05-01

    Full Text Available Hexagonal shaped nanoparticles about 60 nm in size were successfully synthesized in tetraethylene glycol solution containing polyvinylpyrrolidone. By the analysis of the electron diffraction pattern, these were identified as a single crystal of Ni carbide with Ni3C − type structure. Their magnetization curve at 5 K was not completely saturated under a magnetic field of 5 T. The thermomagnetization curves after zero-field cooling and after field cooling exhibited the magnetic cooling effect at low temperatures. Furthermore, the 2nd order nonlinear term of AC magnetic susceptibility exhibited a negative divergence at about 17 K. It is concluded that Ni carbide single crystal nanoparticles with the Ni3C − type structure exhibit spin-glass transition at low temperatures.

  9. Phenomenological theory of a renormalized simplified model based on time-convolutionless mode-coupling theory near the glass transition

    Science.gov (United States)

    Tokuyama, Michio

    2017-01-01

    The renormalized simplified model is proposed to investigate indirectly how the static structure factor plays an important role in renormalizing a quadratic nonlinear term in the ideal mode-coupling memory function near the glass transition. The renormalized simplified recursion equation is then derived based on the time-convolutionless mode-coupling theory (TMCT) proposed recently by the present author. This phenomenological approach is successfully applied to check from a unified point of view how strong liquids are different from fragile liquids. The simulation results for those two types of liquids are analyzed consistently by the numerical solutions of the recursion equation. Then, the control parameter dependence of the renormalized nonlinear exponent in both types of liquids is fully investigated. Thus, it is shown that there exists a novel difference between the universal behavior in strong liquids and that in fragile liquids not only for their transport coefficients but also for their dynamics.

  10. Observation and modeling of deflagration-to-detonation transition (DDT) in low-density HMX

    Science.gov (United States)

    Tringe, Joseph W.; Vandersall, Kevin S.; Reaugh, John E.; Levie, Harold W.; Henson, Bryan F.; Smilowitz, Laura B.; Parker, Gary R.

    2017-01-01

    We employ simultaneous flash x-ray radiography and streak imaging, together with a multi-phase finite element model, to understand deflagration-to-detonation transition (DDT) phenomena in low-density (˜1.2 gm/cm3) powder of the explosive cyclotetramethylene-tetranitramine (HMX). HMX powder was lightly hand-tamped in a 12.7 mm diameter column, relatively lightly-confined in an optically-transparent polycarbonate cylinder with wall thickness 25.4 mm. We observe apparent compaction of the powder in advance of the detonation transition by the motion of small steel spheres pre-emplaced throughout the length of explosive. High-speed imaging along the explosive cylinder length provides a more temporally continuous record of the transition that is correlated with the high-resolution x-ray image record. Preliminary simulation of these experiments with the HERMES model implemented in the ALE3D code enables improved understanding of the explosive particle burning, compaction and detonation phenomena which are implied by the observed reaction rate and transition location within the cylinder.

  11. Observation and modeling of deflagration-to-detonation (DDT) transition in low-density HMX

    Science.gov (United States)

    Tringe, Joseph; Vandersall, Kevin; Reaugh, Jack; Levie, Harold; Henson, Bryan; Smilowitz, Laura; Parker, Gary

    2015-06-01

    We employ simultaneous flash x-ray radiography and streak imaging, together with a multi-phase finite element model, to understand deflagration-to-detonation transition (DDT) phenomena in low-density (~ 1.2 gm/cm3) powder of the explosive cyclotetramethylene-tetranitramine (HMX). HMX powder was lightly hand-tamped in a 12.7 mm diameter column, relatively lightly-confined in an optically-transparent polycarbonate cylinder with wall thickness 25.4 mm. We observe apparent compaction of the powder in advance of the detonation transition, both by x-ray contrast and by the motion of small steel spheres pre-emplaced throughout the length of explosive. High-speed imaging along the explosive cylinder length provides a temporally continuous record of the transition that is correlated with the high-resolution x-ray image record. Preliminary simulation of these experiments with the HERMES model implemented in the ALE3D code enables improved understanding of the explosive particle burning, compaction and detonation phenomena which are implied by the observed reaction rate and transition location within the cylinder. This work performed under the auspices of the U.S. Department of Energy by Lawrence Livermore National Laboratory under Contract DE-AC52-07NA27344.

  12. Hilbert-Glass Transition: New Universality of Temperature-Tuned Many-Body Dynamical Quantum Criticality

    Directory of Open Access Journals (Sweden)

    David Pekker

    2014-03-01

    Full Text Available We study a new class of unconventional critical phenomena that is characterized by singularities only in dynamical quantities and has no thermodynamic signatures. One example of such a transition is the recently proposed many-body localization-delocalization transition, in which transport coefficients vanish at a critical temperature with no singularities in thermodynamic observables. Describing this purely dynamical quantum criticality is technically challenging as understanding the finite-temperature dynamics necessarily requires averaging over a large number of matrix elements between many-body eigenstates. Here, we develop a real-space renormalization group method for excited states that allows us to overcome this challenge in a large class of models. We characterize a specific example: the 1 D disordered transverse-field Ising model with generic interactions. While thermodynamic phase transitions are generally forbidden in this model, using the real-space renormalization group method for excited states we find a finite-temperature dynamical transition between two localized phases. The transition is characterized by nonanalyticities in the low-frequency heat conductivity and in the long-time (dynamic spin correlation function. The latter is a consequence of an up-down spin symmetry that results in the appearance of an Edwards-Anderson-like order parameter in one of the localized phases.

  13. Reorientational dynamics in molecular liquids as revealed by dynamic light scattering: From boiling point to glass transition temperature

    Science.gov (United States)

    Schmidtke, B.; Petzold, N.; Kahlau, R.; Rössler, E. A.

    2013-08-01

    We determine the reorientational correlation time τ of a series of molecular liquids by performing depolarized light scattering experiments (double monochromator, Fabry-Perot interferometry, and photon correlation spectroscopy). Correlation times in the range 10-12 s-100 s are compiled, i.e., the full temperature interval between the boiling point and the glass transition temperature Tg is covered. We focus on low-Tg liquids for which the high-temperature limit τ ≅ 10-12 s is easily accessed by standard spectroscopic equipment (up to 440 K). Regarding the temperature dependence three interpolation formulae of τ(T) with three parameters each are tested: (i) Vogel-Fulcher-Tammann equation, (ii) the approach recently discussed by Mauro et al. [Proc. Natl. Acad. Sci. U.S.A. 106, 19780 (2009)], and (iii) our approach decomposing the activation energy E(T) in a constant high temperature value E∞ and a "cooperative part" Ecoop(T) depending exponentially on temperature [Schmidtke et al., Phys. Rev. E 86, 041507 (2012)], 10.1103/PhysRevE.86.041507. On the basis of the present data, approaches (i) and (ii) are insufficient as they do not provide the correct crossover to the high-temperature Arrhenius law clearly identified in the experimental data while approach (iii) reproduces the salient features of τ(T). It allows to discuss the temperature dependence of the liquid's dynamics in terms of a Ecoop(T)/E∞ vs. T/E∞ plot and suggests that E∞ controls the energy scale of the glass transition phenomenon.

  14. Glass transition and dynamics in BSA-water mixtures over wide ranges of composition studied by thermal and dielectric techniques.

    Science.gov (United States)

    Panagopoulou, A; Kyritsis, A; Sabater I Serra, R; Gómez Ribelles, J L; Shinyashiki, N; Pissis, P

    2011-12-01

    Protein-water dynamics in mixtures of water and a globular protein, bovine serum albumin (BSA), was studied over wide ranges of composition, in the form of solutions or hydrated solid pellets, by differential scanning calorimetry (DSC), thermally stimulated depolarization current technique (TSDC) and dielectric relaxation spectroscopy (DRS). Additionally, water equilibrium sorption isotherm (ESI) measurements were performed at room temperature. The crystallization and melting events were studied by DSC and the amount of uncrystallized water was calculated by the enthalpy of melting during heating. The glass transition of the system was detected by DSC for water contents higher than the critical water content corresponding to the formation of the first sorption layer of water molecules directly bound to primary hydration sites, namely 0.073 (grams of water per grams of dry protein), estimated by ESI. A strong plasticization of the T(g) was observed by DSC for hydration levels lower than those necessary for crystallization of water during cooling, i.e. lower than about 0.3 (grams of water per grams of hydrated protein) followed by a stabilization of T(g) at about -80°C for higher water contents. The α relaxation associated with the glass transition was also observed in dielectric measurements. In TSDC a microphase separation could be detected resulting in double T(g) for some hydration levels. A dielectric relaxation of small polar groups of the protein plasticized by water, overlapped by relaxations of uncrystallized water molecules, and a separate relaxation of water in the crystallized water phase (bulk ice crystals) were also recorded.

  15. Possibility of charge density wave transition in a SrPt2Sb2 superconductor.

    Science.gov (United States)

    Ibuka, Soshi; Imai, Motoharu

    2016-04-27

    The first-order transition at T(0) =  270 K for the platinum-based SrPt2Sb2 superconductor was investigated using x-ray diffraction and magnetic susceptibility measurements. When polycrystalline SrPt2Sb2 was cooled down through T(0), the structure was transformed from monoclinic to a modulated orthorhombic structure, and no magnetic order was formed, which illustrates the possibility of a charge density wave (CDW) transition at T(0). SrPt2Sb2 can thus be a new example to examine the interplay of CDW and superconductivity in addition to SrPt2As2, BaPt2As2, and LaPt2Si2. It is unique that the average structure of the low-temperature phase has higher symmetry than that of the high-temperature phase.

  16. Density-transition based electron injector for laser driven wakefield accelerators

    Science.gov (United States)

    Schmid, K.; Buck, A.; Sears, C. M. S.; Mikhailova, J. M.; Tautz, R.; Herrmann, D.; Geissler, M.; Krausz, F.; Veisz, L.

    2010-09-01

    We demonstrate a laser wakefield accelerator with a novel electron injection scheme resulting in enhanced stability, reproducibility, and ease of use. In order to inject electrons into the accelerating phase of the plasma wave, a sharp downward density transition is employed. Prior to ionization by the laser pulse this transition is formed by a shock front induced by a knife edge inserted into a supersonic gas jet. With laser pulses of 8 fs duration and with only 65 mJ energy on target, the accelerator produces a monoenergetic electron beam with tunable energy between 15 and 25 MeV and on average 3.3 pC charge per electron bunch. The shock-front injector is a simple and powerful new tool to enhance the reproducibility of laser-driven electron accelerators, is easily adapted to different laser parameters, and should therefore allow scaling to the energy range of several hundred MeV.

  17. Drying and wetting transitions of a Lennard-Jones fluid: Simulations and density functional theory

    Science.gov (United States)

    Evans, Robert; Stewart, Maria C.; Wilding, Nigel B.

    2017-07-01

    We report a theoretical and simulation study of the drying and wetting phase transitions of a truncated Lennard-Jones fluid at a flat structureless wall. Binding potential calculations predict that the nature of these transitions depends on whether the wall-fluid attraction has a long ranged (LR) power law decay or is instead truncated, rendering it short ranged (SR). Using grand canonical Monte Carlo simulation and classical density functional theory, we examine both cases in detail. We find that for the LR case wetting is first order, while drying is continuous (critical) and occurs exactly at zero attractive wall strength, i.e., in the limit of a hard wall. In the SR case, drying is also critical but the order of the wetting transition depends on the truncation range of the wall-fluid potential. We characterize the approach to critical drying and wetting in terms of the density and local compressibility profiles and via the finite-size scaling properties of the probability distribution of the overall density. For the LR case, where the drying point is known exactly, this analysis allows us to estimate the exponent ν∥, which controls the parallel correlation length, i.e., the extent of vapor bubbles at the wall. Surprisingly, the value we obtain is over twice that predicted by mean field and renormalization group calculations, despite the fact that our three dimensional system is at the upper critical dimension where mean field theory for critical exponents is expected to hold. Possible reasons for this discrepancy are discussed in the light of fresh insights into the nature of near critical finite-size effects.

  18. Composition-driven spin glass to ferromagnetic transition in the quasicrystal approximant Au-Al-Gd

    Science.gov (United States)

    Ishikawa, A.; Hiroto, T.; Tokiwa, K.; Fujii, T.; Tamura, R.

    2016-01-01

    We investigated the composition dependence of the magnetic susceptibility of the quasicrystal approximant Au-Al-Gd. A composition-driven ferromagnetic transition is observed in a quasicrystal approximant, which is attributed to the Ruderman-Kittel-Kasuya-Yosida (RKKY) oscillation via a variation in the Fermi wave vector. The ferromagnetic transition is most simply understood as a result of the close matching of the nearest and second-nearest spin distances with the maximum positions of the RKKY potential. The present work provides an idea that allows us to tailor the magnetic order via the electron concentration in quasicrystal approximants as well as in quasicrystals.

  19. Density dependence of relaxation dynamics in glass formers, and the dependence of their fragility on the softness of inter-particle interactions

    Indian Academy of Sciences (India)

    ANSHUL D S PARMAR; PALLABI KUNDU; SRIKANTH SASTRY

    2017-07-01

    Fragility, quantifying the rapidity of variation of relaxation times, is analysed for a series of model glass formers, which differ in the softness of their interparticle interactions. In an attempt to rationalize experimental observations in colloidal suspensions that softer interactions lead to stronger (less fragile) glassformers, we study the variation of relaxation dynamics with density, rather than temperature, as a control parameter.We employ density-temperature scaling, analyzed in recent studies, to address the question.We find that while employing inverse density in place of temperature leads to the conclusion that softer interactions lead to stronger behaviour, the use of scaled variables involving temperature and density lead to the opposite conclusion, similarly to earlier investigations where temperature variation of relaxation dynamics was analysed for the same systems. We rationalize our results by considering the Adam-Gibbs (AG) fragility, which incorporates the density dependence of the configurational entropy and an activation energy that may arise from other propertiesof a glass former.Within the framework of the Adam-Gibbs relation, by employing density temperature scaling for the analysis, we find that softer particles make more fragile glasses, as deduced from dynamical quantities, which is found to be consistent with the Adam-Gibbs fragility.

  20. Superfluid density and superconducting transition temperature in Bi-based cuprate single crystals.

    Science.gov (United States)

    Gasparov, L.; Tanner, D.; Berger, H.; Forro, L.; Margaritondo, G.

    2000-03-01

    We present temperature-dependent reflectance measurements for Bi-based cuprate single crystals in the frequency range from 100 to 40,000 cm-1 (0.012--5 eV). The optical conductivity is obtained by Kramers-Kronig analysis. We compare differently doped Bi-2212 (particularly in the underdoped regime) as well as Pr-doped Bi-2212 crystals by analyzing optical conductivity in the framework of a two-fluid approach. This approach allows us to study correlations between superfluid density and superconducting transition temperature of these materials.

  1. First order phase transition in finite density QCD using the modulus of the Dirac determinant

    CERN Document Server

    Aloisio, R; Di Carlo, G; Galante, A; Grillo, A F

    1998-01-01

    We report results of simulations of strong coupling, finite density QCD obtained within a MFA inspired approach where the fermion determinant in the integration measure is replaced by its absolute value. Contrary to the standard wisdom, we show that within this approach a clear signal of a phase transition appears with a critical chemical potential in extremely good agreement with the results obtained with the Glasgow algorithm. The modulus of the fermion determinant seems therefore to preserve some of the relevant physical properties of the system. We also analyze the dependence of our results on the quark mass, including both the chiral and large mass limit, and the theory in the quenched approximation.

  2. Calculation of the Nuclear Transition Charge Density in a Microscopic sdgIBM-1

    Institute of Scientific and Technical Information of China (English)

    ZHANG Zhan-Jun; SANG Jian-ping; LIU Yong

    2000-01-01

    Formulae of proton and neutron boson structure functions (BSF's) are deduced in terms of a microscopic approach of sdgIBM (namely, microscopic sdgIBM). For the nucleus 190Os, the value of BSF's is worked out. Due to the high similarity, the maximum F-spin truncation is made under the full-symmetry approximation. Thereafter, calculations of E2 and E4 transition charge densities (TCD's) are performed in the sdgIBM-1. It is found that the E2 and E4 TCD's can be reproduced quite satisfactorily in the uniform frame of microscopic sdgIBM-1.

  3. Thermodynamic prediction of glass formation tendency, cluster-in-jellium model for metallic glasses, ab initio tight-binding calculations, and new density functional theory development for systems with strong electron correlation

    Energy Technology Data Exchange (ETDEWEB)

    Yao, Yongxin [Iowa State Univ., Ames, IA (United States)

    2009-01-01

    also plays an important role, as it may directly track the movement of every atom. Simulation time is a major limit for molecular dynamics, not only because of “slow” computer speed, but also because of the accumulation error in the numerical treatment of the motion equations. There is also a great concern about the reliability of the emperical potentials if using classical molecular dynamics. Ab initio methods based on density functional theory(DFT) do not have this problem, however, it suffers from small simulation cells and is more demanding computationally. When crystal phase is involved, size effect of the simulation cell is more pronounced since long-range elastic energy would be established. Simulation methods which are more efficient in computation but yet have similar reliability as the ab initio methods, like tight-binding method, are highly desirable. While the complexity of metallic glasses comes from the atomistic level, there is also a large field which deals with the complexity from electronic level. The only “ab initio” method applicable to solid state systems is density functional theory with local density approximation( LDA) or generalized gradient approximation(GGA) for the exchange-correlation energy. It is very successful for simple sp element, where it reaches an high accuracy for determining the surface reconstruction. However, there is a large class of materials with strong electron correlation, where DFT based on LDA or GGA fails in a fundamental way. An “ab initio” method which can generally apply to correlated materials, as LDA for simple sp element, is still to be developed. The thesis is prepared to address some of the above problems.

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

    Science.gov (United States)

    Bharadwaj, Atul S.; Singh, Yashwant

    2017-03-01

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

  5. Molecular Dynamic Simulations of Glass Transition Temperature and Mechanical Properties in the Amorphous Region of Oil-Immersed Transformer Insulation Paper

    Science.gov (United States)

    Wang, You-Yuan; Yang, Tao; Liao, Rui-Jin

    2012-07-01

    The glass transition temperature (Tg) in the amorphous region of an insulation paper is one of the most important characteristics for thermal stability. Molecular dynamic simulations have been performed on three micro-structural models, namely, amorphous pure cellulose, amorphous cellulose with water and amorphous cellulose with oil, to study the microscopic mechanism of the glass transition process for oil-immersed transformer insulation paper. Using the method of specific volume versus temperature curve, the Tg of amorphous pure cellulose, cellulose with water, and cellulose with oil was determined as 448, 418 and 440 K, respectively. The current study may provide some information for thermal aging. The simulation results show that during the glass transition process, both the chain motion and mechanical properties of cellulose changes significantly. Relative to the oil molecules, water molecules immersed in the amorphous region of insulation paper can disrupt hydrogen bonds between cellulose chains. This phenomenon results in a significant reduction in the glass transition temperature and affects the thermal stability of the insulation paper.

  6. Molecular dynamics simulation of cross-linked urea-formaldehyde polymers for self-healing nanocomposites: prediction of mechanical properties and glass transition temperature.

    Science.gov (United States)

    Arab, Behrouz; Shokuhfar, Ali

    2013-11-01

    Urea-formaldehyde polymers, which are utilized in the adhesives industry, have recently been shown to be suitable materials for synthesizing micro/nanocapsules for use in self-healing (nano)composites. In this study, molecular dynamics was employed to simulate the process in which urea and formaldehyde are cross-linked via methylene and ether cross linkers, and to study the structure and mechanical/thermal properties of simulated poly(urea-formaldehyde)s (PUFs). The elastic stiffness constants of the simulated materials were calculated using the constant-strain (static) method. A temperature cycle was applied to the cross-linked PUFs, and the glass transition behavior of each material was investigated through the mean squared displacement (MSD) and temperature evolution of the energy and the specific volume of the polymer. The simulation results confirmed that there was considerable improvement in the properties of the poly(UF) materials upon cross linking. The radial distribution function was also used to study the local structures of the polymers, and this revealed that increasing the temperature and cross linking density results in a significant drop in hydrogen bonding intensity in the cross-linked PUF systems.

  7. Self-Focusing of Hermite-Cosh-Gaussian Laser Beams in Plasma under Density Transition

    Directory of Open Access Journals (Sweden)

    Manzoor Ahmad Wani

    2014-01-01

    Full Text Available Self-focusing of Hermite-Cosh-Gaussian (HChG laser beam in plasma under density transition has been discussed here. The field distribution in the medium is expressed in terms of beam-width parameters and decentered parameter. The differential equations for the beam-width parameters are established by a parabolic wave equation approach under paraxial approximation. To overcome the defocusing, localized upward plasma density ramp is considered, so that the laser beam is focused on a small spot size. Plasma density ramp plays an important role in reducing the defocusing effect and maintaining the focal spot size up to several Rayleigh lengths. To discuss the nature of self-focusing, the behaviour of beam-width parameters with dimensionless distance of propagation for various values of decentered parameters is examined by numerical estimates. The results are presented graphically and the effect of plasma density ramp and decentered parameter on self-focusing of the beams has been discussed.

  8. Physical Aging of Thin and Ultrathin Free-Standing Polymer Films: Effect of Stress and Reduced Glass Transitions

    Science.gov (United States)

    Pye, Justin; Roth, Connie

    2014-03-01

    While great effort has been made in elucidating the effect of confinement on the glass transition (Tg) in polymers, considerably less work has been done on physical aging. Starting with supported films, we have previously shown that the reduced physical aging rates in ultrathin polystyrene (PS) films can be linked to the reduced Tg near the free surface [Macromolecules 2010, 43, 8296]. We then showed that high molecular weight (MW) free-standing PS films have two reduced Tgs suggesting that two separate mechanisms are acting simultaneously to propagate enhanced mobility at the free surface deeper into the film [PRL 2011, 107, 235701]. To help determine the mechanisms of these two reduced Tgs, we performed physical aging measurements on these high MW free-standing PS films. For thick films (220-1800 nm) in which there are no Tg reductions, we find that the physical aging rate depends strongly on stress caused by thermal expansion mismatch between film and support. This stress, applied to the films as they are quenched into the glassy state, can nearly double the physical aging rate when changing the frame material from polycarbonate to silicon [Macromolecules 2013, DOI:10.1021/ma401872u]. Finally, ultrathin high MW PS films held at a temperature between the two Tgs do exhibit physical aging, indicating that at least some of the film is glassy between these two transitions.

  9. [Validity of PSA density of the transition zone in the diagnosis of prostate cancer].

    Science.gov (United States)

    Anastasi, G; Magno, C; Carmignani, A; Inferrera, A; Petrelli, A; Broccio, G

    2000-12-01

    One hundred four patients (mean age 70.6 years) with prostatic specific antigen (PSA) values between 4 and 10 ng/ml (average 7.9 ng/ml), and with no suspects for neoplasia by digital rectal examination (DRE) and transrectal ultrasound (TRUS) were studied. In all patients PSA density for the entire prostate (PSAD) and PSA density for the transition zone (PSAT) were calculated. TRUS was performed using a 5 MHz probe. Prostate and transition zone volumes were obtained by ellipsoid formula. Aim of the study was to evaluate the PSAT predictivity for prostate cancer compared to the PSAD. Sixteen out of 104 patients (15.4%) had histologically confirmed prostate cancer, and 88 (84.6%) had benign prostatic hyperplasia. When cut-off for PSAD was 0.15 ng/ml/cc, specificity and sensitivity were respectively 75% and 68% with positive and negative predictive values of 54% and 17%; when cut-off for PSAT was 0.34% ng/ml/cc, sensitivity and specificity were respectively 100% and 68% with positive and negative predictive values of 60% and 18%. Our results, according to the literature data, suggest that PSAT seems to have a higher predictivity for prostate cancer than PSAD, providing an optimization for the employ of prostatic biopsy, especially for those patients with PSA values between 4 and 10 ng/ml.

  10. Structural transitions in electron beam deposited Co–carbonyl suspended nanowires at high electrical current densities

    Directory of Open Access Journals (Sweden)

    Gian Carlo Gazzadi

    2015-06-01

    Full Text Available Suspended nanowires (SNWs have been deposited from Co–carbonyl precursor (Co2(CO8 by focused electron beam induced deposition (FEBID. The SNWs dimensions are about 30–50 nm in diameter and 600–850 nm in length. The as-deposited material has a nanogranular structure of mixed face-centered cubic (FCC and hexagonal close-packed (HCP Co phases, and a composition of 80 atom % Co, 15 atom % O and 5 atom % C, as revealed by transmission electron microscopy (TEM analysis and by energy-dispersive X-ray (EDX spectroscopy, respectively. Current (I–voltage (V measurements with current densities up to 107 A/cm2 determine different structural transitions in the SNWs, depending on the I–V history. A single measurement with a sudden current burst leads to a polycrystalline FCC Co structure extended over the whole wire. Repeated measurements at increasing currents produce wires with a split structure: one half is polycrystalline FCC Co and the other half is graphitized C. The breakdown current density is found at 2.1 × 107 A/cm2. The role played by resistive heating and electromigration in these transitions is discussed.

  11. Structural transitions in electron beam deposited Co-carbonyl suspended nanowires at high electrical current densities.

    Science.gov (United States)

    Gazzadi, Gian Carlo; Frabboni, Stefano

    2015-01-01

    Suspended nanowires (SNWs) have been deposited from Co-carbonyl precursor (Co2(CO)8) by focused electron beam induced deposition (FEBID). The SNWs dimensions are about 30-50 nm in diameter and 600-850 nm in length. The as-deposited material has a nanogranular structure of mixed face-centered cubic (FCC) and hexagonal close-packed (HCP) Co phases, and a composition of 80 atom % Co, 15 atom % O and 5 atom % C, as revealed by transmission electron microscopy (TEM) analysis and by energy-dispersive X-ray (EDX) spectroscopy, respectively. Current (I)-voltage (V) measurements with current densities up to 10(7) A/cm(2) determine different structural transitions in the SNWs, depending on the I-V history. A single measurement with a sudden current burst leads to a polycrystalline FCC Co structure extended over the whole wire. Repeated measurements at increasing currents produce wires with a split structure: one half is polycrystalline FCC Co and the other half is graphitized C. The breakdown current density is found at 2.1 × 10(7) A/cm(2). The role played by resistive heating and electromigration in these transitions is discussed.

  12. A simple method for finding explicit analytic transition densities of diffusion processes with general diploid selection.

    Science.gov (United States)

    Song, Yun S; Steinrücken, Matthias

    2012-03-01

    The transition density function of the Wright-Fisher diffusion describes the evolution of population-wide allele frequencies over time. This function has important practical applications in population genetics, but finding an explicit formula under a general diploid selection model has remained a difficult open problem. In this article, we develop a new computational method to tackle this classic problem. Specifically, our method explicitly finds the eigenvalues and eigenfunctions of the diffusion generator associated with the Wright-Fisher diffusion with recurrent mutation and arbitrary diploid selection, thus allowing one to obtain an accurate spectral representation of the transition density function. Simplicity is one of the appealing features of our approach. Although our derivation involves somewhat advanced mathematical concepts, the resulting algorithm is quite simple and efficient, only involving standard linear algebra. Furthermore, unlike previous approaches based on perturbation, which is applicable only when the population-scaled selection coefficient is small, our method is nonperturbative and is valid for a broad range of parameter values. As a by-product of our work, we obtain the rate of convergence to the stationary distribution under mutation-selection balance.

  13. Novel charge density wave transition in crystals of R5Ir4Si10

    Indian Academy of Sciences (India)

    S Ramakrishnan

    2002-05-01

    We review the observation of novel charge density wave (CDW) transitions in ternary R5Ir4Si10 compounds. A high quality single crystal of Lu5Ir4Si10 shows the formation of a commensurate CDW along -axis below 80 K in the (ℎ, 0, ) plane that coexists with BCS type superconductivity below 3.9 K. However, in a single crystal of Er5Ir4Si10, one observes the development of a 1D-incommensurate CDW at 155 K, which then locks into a purely commensurate state below 55 K. The well-localized Er3 moments are antiferromagnetically ordered below 2.8 K which results in the coexistence of strongly coupled CDW with local moment antiferromagnetism in Er5Ir4Si10. Unlike conventional CDW systems, extremely sharp transition (width ∼ 1.5 K) in all bulk properties along with huge heat capacity anomalies in these compounds makes this CDW transition an interesting one.

  14. Matrix infrared spectra and density functional calculations of transition metal hydrides and dihydrogen complexes.

    Science.gov (United States)

    Andrews, Lester

    2004-02-20

    Metal hydrides are of considerable importance in chemical synthesis as intermediates in catalytic hydrogenation reactions. Transition metal atoms react with dihydrogen to produce metal dihydrides or dihydrogen complexes and these may be trapped in solid matrix samples for infrared spectroscopic study. The MH(2) or M(H(2)) molecules so formed react further to form higher MH(4), (H(2))MH(2), or M(H(2))(2), and MH(6), (H(2))(2)MH(2), or M(H(2))(3) hydrides or complexes depending on the metal. In this critical review these transition metal and dihydrogen reaction products are surveyed for Groups 3 though 12 and the contrasting behaviour in Groups 6 and 10 is discussed. Minimum energy structures and vibrational frequencies predicted by Density Functional Theory agree with the experimental results, strongly supporting the identification of novel binary transition metal hydride species, which the matrix-isolation method is well-suited to investigate. 104 references are cited.

  15. A Novel Conversion Process for Waste Slag: The Preparation of Aluminosilicate Glass with Evaluation of the Dielectric Properties from Blast Furnace Slag

    Science.gov (United States)

    Li, Sheng; Huang, Sanxi; Liu, Hongting; Wu, Fengnian; Chang, Ziyuan; Yue, Yunlong

    2015-11-01

    In this paper, aluminosilicate glass was prepared from blast furnace slag and quartz sand. Fourier transform infrared, differential scanning calorimetry and density measurements were carried out to investigate the effects of SiO2 on the aluminosilicate glass network rigidity. The results indicate that glass structure would be enhanced if more SiO2 was introduced into the glass system. Meanwhile, both the glass transition temperature ( T g) and the glass crystallization temperature ( T c) increase slightly; the increase in density of the glass being further evidence of the enhancement in glass network rigidity. Dielectric measurements show that the dielectric constant and dielectric loss decrease with more SiO2. The properties of the prepared aluminosilicate glasses are comparable to those of E glass, indicating that blast furnace slags are suitable for producing aluminosilicate glass with low dielectric constant and dielectric loss.

  16. Phase-glass scaling near the coherence transition in granular HoBa{sub 2}Cu{sub 3}O{sub 7-{delta}} superconducting thin films

    Energy Technology Data Exchange (ETDEWEB)

    Roa-Rojas, J.; Landinez Tellez, D.A. [Grupo de Fisica de Nuevos Materiales, Departamento de Fisica, Universidad Nacional de Colombia, A. A. 14490, Bogota DC (Colombia); Prieto, P. [Grupo de Peliculas Delgadas, Departamento de Fisica, Universidad del Valle, A. A. 25360, Cali (Colombia)

    2005-07-01

    Systematic measurements of electrical magnetoconductivity near the coherence transition of granular HoBa{sub 2}Cu{sub 3}O{sub 7-{delta}} thin films are reported. Experiments performed in magnetic fields ranging from 0 to 2500 Oe reveal that close to the coherence transition temperature T{sub c0}(H), the correlation length scales as a power law of temperature with a thermal-dependent critical exponent, {nu}. In low external fields the corresponding value of {nu} is consistent with the two-dimensional phase-glass model, which is in the same dynamical universality class of the so-called vortex-glass model. At applied fields H > 1000 Oe, the vortex dynamics becomes stronger and the coherence transition is not observed. (copyright 2005 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim) (orig.)

  17. Deformation and structure evolution of glassy poly(lactic acid) below the glass transition temperature

    DEFF Research Database (Denmark)

    Zhou, Chengbo; Li, Hongfei; Zhang, Yao;

    2015-01-01

    Poly(lactic acid) (PLA) is a bio-based and compostable thermoplastic polyester that has rapidly evolved into a competitive commodity material over the last decade. One key bottleneck in expanding the field of application of PLA is the control of its structure and properties. Therefore, in situ...... by differential scanning calorimetry (DSC). The obtained results showed that the deformation and yield stress of glassy PLA are strongly dependent on the stretching temperatures together with the transition from mesophase to mesocrystal and the formation of cavities. With the increase in drawing temperature...

  18. PAL signature of physical ageing in chalcogenide glasses

    Energy Technology Data Exchange (ETDEWEB)

    Ingram, Adam; Kozdras, Andrzej [Physics Faculty of Opole University of Technology, 75, Ozimska Str., Opole 45370 (Poland); Shpotyuk, Oleh [Institute of Physics of Jan Dlugosz University, 13/15, al. Armii Krajowej, Czestochowa 42201 (Poland); Golovchak, Roman [Physics Faculty of Opole University of Technology, 75, Ozimska Str., Opole 45370 (Poland); Lviv Scientific Research Institute of Materials of SRC ' ' Carat' ' , 202, Stryjska Str., Lviv 79031 (Ukraine)

    2012-05-15

    Kinetics of physical ageing (PhA) far below the glass transition temperature (T{sub g}) is studied by positron annihilation lifetime and differential scanning calorimetry techniques for vitreous As{sub 20}Se{sub 80} as typical representative of network glasses. The increased density fluctuations are shown to be responsible for the initial stage of PhA in this glass at below-T{sub g} temperatures. These fluctuations are correlated with changes in thermodynamic parameters of structural relaxation through the glass-to-supercooled liquid transition interval. General shrinkage, occurred during the next stage of PhA, is shown to be determined by the ability of system to release these redundant open volumes from the glass bulk through densification process of glass network. (Copyright copyright 2012 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  19. Practical aspects of using Hertzian ring crack initiation to measure surface flaw densities in glasses: influence of humidity, friction and searched areas

    Science.gov (United States)

    Tandon, Rajan; Paliwal, Bhasker; Gibson, Cory

    2013-07-01

    Ring crack initiation loads on glass, using spherical Tungsten carbide (WC) and glass (G) indenters, are measured and analysed. Our measurements demonstrate that environmental humidity plays a key role in determining the load to fracture; experiments conducted without controlling this variable cannot be used to obtain material properties. The role of friction is explicitly considered for dissimilar (WC-G) elastic contacts. For this material pair, the stresses at fracture are well described by a boundary lubrication value of friction coefficient. The fracture loads are used in a fracture-mechanics formulation to calculate crack sizes on glass surfaces. The 'searched-area' concept for dissimilar contacts is described, and used to provide crack density values for these surfaces.

  20. Quantum phase transitions and collective enhancement of level density in odd–A and odd–odd nuclei

    Energy Technology Data Exchange (ETDEWEB)

    Karampagia, S., E-mail: karampag@nscl.msu.edu [National Superconducting Cyclotron Laboratory, Michigan State University, East Lansing, MI 48824-1321 (United States); Renzaglia, A. [Department of Physics and Astronomy, Michigan State University, East Lansing, MI 48824-1321 (United States); Zelevinsky, V. [National Superconducting Cyclotron Laboratory, Michigan State University, East Lansing, MI 48824-1321 (United States); Department of Physics and Astronomy, Michigan State University, East Lansing, MI 48824-1321 (United States)

    2017-06-15

    The nuclear shell model assumes an effective mean-field plus interaction Hamiltonian in a specific configuration space. We want to understand how various interaction matrix elements affect the observables, the collectivity in nuclei and the nuclear level density for odd–A and odd–odd nuclei. Using the sd and pf shells, we vary specific groups of matrix elements and study the evolution of energy levels, transition rates and the level density. In all cases studied, a transition between a “normal” and a collective phase is induced, accompanied by an enhancement of the level density in the collective phase. In distinction to neighboring even–even nuclei, the enhancement of the level density is observed already at the transition point. The collective phase is reached when the single-particle transfer matrix elements are dominant in the shell model Hamiltonian, providing a sign of their fundamental role.

  1. An investigation of iron phosphate glasses

    Science.gov (United States)

    Fang, Xiangyu

    The effect of melting history on the iron redox equilibrium, structure, crystallization and properties of a binary iron phosphate glass with a 40Fe 2O3-60P2O5, mol%, batch composition were investigated. The structure and properties of single and mixed alkali iron phosphate glasses were also studied. Mossbauer, Raman and infrared spectroscopy were used to determine the changes in the concentration of iron ions and phosphate units in the structure. Differential thermal analysis, X-ray diffraction and thermogravimetric analysis were used to investigate crystallization. Density, molar volume, thermal expansion, dc electrical conductivity and dielectric constant and loss tangent were measured. The heat capacity and glass transition behavior of the glasses was also measured by the differential scanning calorimeter method. The effect of the melting temperature is stronger than the melting time on the concentration of Fe2+ ions in iron phosphate glasses. The pyrophosphate network in iron phosphate glasses and their general properties do not change either with melting temperature and time or with adding up to 20 mol% of single and mixed alkali oxides. The dissolution rate (in deionized water) of these glasses is generally very low (˜10-9 g/cm2/min) and nearly independent of the relative concentration of Fe 2+ or Fe3+ ions. The dissolution rate of the iron phosphate glasses containing 20 mol% of single or mixed alkali oxide can be comparable to that of window glass. There is no mixed alkali effect in the iron phosphate glasses. The crystallization tendency indicates that the glass structure becomes closer to that of crystalline Fe3(P2O 7)2 with increasing concentration of Fe2+ ions in the glass. The large fragility parameters indicates that the iron phosphate glasses belong in the category of the fragile glass-forming liquids.

  2. Exploring finite density QCD phase transition with canonical approach -Power of multiple precision computation-

    CERN Document Server

    Oka, Shotaro

    2015-01-01

    The canonical approach for finite density lattice QCD has a numerical instability. This instability makes it difficult to use the method reliably at the finite real chemical potential region. We studied this instability in detail and found that it is caused by the cancellation of significant digits. In order to reduce the effect of this cancellation, we adopt the multiple precision calculation for our discrete Fourier transformation (DFT) program, and we get the canonical partition function Zc(n,T) with required accuracy. From the obtained Zc(n,T), we calculate Lee--Yang zero distribution varying the number of significant digits. As a result, some curves surround the origin in the fugacity plane, but they are moved by varying the number of significant digits. Hence, we conclude that these curves are pseudo phase transition lines, and not real ones.

  3. Comment on the "Influence of Cosmological Transitions on the Evolution of Density Perturbations"

    CERN Document Server

    Grishchuk, L P

    1998-01-01

    The "standard inflationary result" has been confirmed once again. This time, by Martin and Schwarz [1]. The fallacy - "the closer the inflationary epoch is to the de Sitter space-time, the less important are large-scale gravitational waves in the CMBR today" - has been repeated and has been claimed to be finally proved. The paper [1] is somewhat better than many other incorrect inflationary papers on the subject of cosmological perurbations. This paper at least operates with correct equations (taken from the criticized work of Grishchuk [2, 3]). Martin and Schwarz say that Grishchuk's conclusion about approximate equality of metric amplitudes for gravitational waves and density perturbations "is wrong because the time evolution of the scalar metric perturbation through the (smooth) reheating transition was not calculated correctly". They reiterate an old inflationary fantasy about "big amplification" of scalar perturbations (in contrast to gravitational waves) during "reheating". They say that after appropria...

  4. Quasiparticle bands and structural phase transition of iron from Gutzwiller density-functional theory

    Science.gov (United States)

    Schickling, Tobias; Bünemann, Jörg; Gebhard, Florian; Boeri, Lilia

    2016-05-01

    We use the Gutzwiller density-functional theory to calculate ground-state properties and band structures of iron in its body-centered-cubic (bcc) and hexagonal-close-packed (hcp) phases. For a Hubbard interaction U =9 eV and Hund's-rule coupling J =0.54 eV , we reproduce the lattice parameter, magnetic moment, and bulk modulus of bcc iron. For these parameters, bcc is the ground-state lattice structure at ambient pressure up to a pressure of pc=41 GPa where a transition to the nonmagnetic hcp structure is predicted, in qualitative agreement with experiment (pcexp=10 ,...,15 GPa ) . The calculated band structure for bcc iron is in good agreement with ARPES measurements. The agreement improves when we perturbatively include the spin-orbit coupling.

  5. Contrasting dynamics of fragile and non-fragile polyalcohols through the glass, and dynamical, transitions: A comparison of neutron scattering and dielectric relaxation data for sorbitol and glycerol.

    Science.gov (United States)

    Migliardo, F; Angell, C A; Magazù, S

    2017-01-01

    Glycerol and sorbitol are glass-forming hydrogen-bonded systems characterized by intriguing properties which make these systems very interesting also from the applications point of view. The goal of this work is to relate the hydrogen-bonded features, relaxation dynamics, glass transition properties and fragility of these systems, in particular to seek insight into their very different liquid fragilities. The comparison between glycerol and sorbitol is carried out by collecting the elastic incoherent neutron scattering (EINS) intensity as a function of temperature and of the instrumental energy resolution. Intensity data vs temperature and resolution are analyzed in terms of thermal restraint and Resolution Elastic Neutron Scattering (RENS) approaches. The number of OH groups, which are related to the connecting sites, is a significant parameter both in the glass transition and in the dynamical transition. On the other hand, the disordered nature of sorbitol is confirmed by the existence of different relaxation processes. From the applications point of view, glycerol and sorbitol have remarkable bioprotectant properties which make these systems useful in different technological and industrial fields. Furthermore, polyols are rich in glassforming liquid phenomenology and highly deserving of study in their own right. The comparison of EINS and calorimetric data on glycerol and sorbitol helps provide a connection between structural relaxation, dynamical transition, glass transition, and fragility. The evaluation of the inflection point in the elastic intensity behavior as a function of temperature and instrumental energy resolution provides a confirmation of the validity of the RENS approach. This article is part of a Special Issue entitled "Science for Life" Guest Editor: Dr. Austen Angell, Dr. Salvatore Magazù and Dr. Federica Migliardo. Copyright © 2016. Published by Elsevier B.V.

  6. Density-transition based electron injector for laser driven wakefield accelerators

    Directory of Open Access Journals (Sweden)

    K. Schmid

    2010-09-01

    Full Text Available We demonstrate a laser wakefield accelerator with a novel electron injection scheme resulting in enhanced stability, reproducibility, and ease of use. In order to inject electrons into the accelerating phase of the plasma wave, a sharp downward density transition is employed. Prior to ionization by the laser pulse this transition is formed by a shock front induced by a knife edge inserted into a supersonic gas jet. With laser pulses of 8 fs duration and with only 65 mJ energy on target, the accelerator produces a monoenergetic electron beam with tunable energy between 15 and 25 MeV and on average 3.3 pC charge per electron bunch. The shock-front injector is a simple and powerful new tool to enhance the reproducibility of laser-driven electron accelerators, is easily adapted to different laser parameters, and should therefore allow scaling to the energy range of several hundred MeV.

  7. The Sherrington-Kirkpatrick spin glass model in the presence of a random field with a joint Gaussian probability density function for the exchange interactions and random fields

    Science.gov (United States)

    Hadjiagapiou, Ioannis A.

    2014-03-01

    The magnetic systems with disorder form an important class of systems, which are under intensive studies, since they reflect real systems. Such a class of systems is the spin glass one, which combines randomness and frustration. The Sherrington-Kirkpatrick Ising spin glass with random couplings in the presence of a random magnetic field is investigated in detail within the framework of the replica method. The two random variables (exchange integral interaction and random magnetic field) are drawn from a joint Gaussian probability density function characterized by a correlation coefficient ρ. The thermodynamic properties and phase diagrams are studied with respect to the natural parameters of both random components of the system contained in the probability density. The de Almeida-Thouless line is explored as a function of temperature, ρ and other system parameters. The entropy for zero temperature as well as for non zero temperatures is partly negative or positive, acquiring positive branches as h0 increases.

  8. Multiple charge density wave transitions in the antiferromagnets R NiC2 (R =Gd ,Tb)

    Science.gov (United States)

    Shimomura, S.; Hayashi, C.; Hanasaki, N.; Ohnuma, K.; Kobayashi, Y.; Nakao, H.; Mizumaki, M.; Onodera, H.

    2016-04-01

    X-ray scattering and electrical resistivity measurements were performed on GdNiC2 and TbNiC2. We found a set of satellite peaks characterized by q1=(0.5 ,η ,0 ) below T1, at which the resistivity shows a sharp inflection, suggesting the charge density wave (CDW) formation. The value of η decreases with decreasing temperature below T1, and then a transition to a commensurate phase with q1 C=(0.5 ,0.5 ,0 ) takes place. The diffuse scattering observed above T1 indicates the presence of soft phonon modes associated with CDW instabilities at q1 and q2=(0.5 ,0.5 ,0.5 ) . The long-range order given by q2 is developed in addition to that given by q1 C in TbNiC2, while the short-range correlation with q2 persists even at 6 K in GdNiC2. The amplitude of the q1 C lattice modulation is anomalously reduced below an antiferromagnetic transition temperature TN in GdNiC2. In contrast, the q2 order vanishes below TN in TbNiC2. We demonstrate that R NiC2 (R = rare earth) compounds exhibit similarities with respect to their CDW phenomena, and discuss the effects of magnetic transitions on CDWs. We offer a possible displacement pattern of the modulated structure characterized by q1 C and q2 in terms of frustration.

  9. Universal amorphous-amorphous transition in GexSe100-x glasses under pressure

    DEFF Research Database (Denmark)

    Yildirim, Can; Micoulaut, Matthieu; Boolchand, Punit

    2016-01-01

    distributions are observed when scaled to reduced densities. All compositions are observed to remain amorphous under pressure values up to 42 GPa. The Ge-Se interatomic distances extracted from XAS data show a two-step response to the applied pressure; a gradual decrease followed by an increase at around 15...... simulations and compared to the experimental results. The evolution of bond angle distributions, interatomic distances and coordination numbers are examined and lead to similar pressure-induced structural changes for any composition.......Pressure induced structural modifications in vitreous GexSe100−x (where 10 ≤ x ≤ 25) are investigated using X-ray absorption spectroscopy (XAS) along with supplementary X-ray diffraction (XRD) experiments and ab initio molecular dynamics (AIMD) simulations. Universal changes in distances and angle...

  10. First principles study on the charge density and the bulk modulus of the transition metals and their carbides and nitrides

    Institute of Scientific and Technical Information of China (English)

    Li Cheng-Bin; Li Ming-Kai; Yin Dong; Liu Fu-Qing; Fan Xiang-Jun

    2005-01-01

    A first principles study of the electronic properties and bulk modulus (B0) of the fcc and bcc transition metals,transition metal carbides and nitrides is presented. The calculations were performed by plane-wave pseudopotential method in the framework of the density functional theory with local density approximation. The density of states and the valence charge densities of these solids are plotted. The results show that B0 does not vary monotonically when the number of the valence d electrons increases. B0 reaches a maximum and then decreases for each of the four sorts of solids. It is related to the occupation of the bonding and anti-bonding states in the solid. The value of the valence charge density at the midpoint between the two nearest metal atoms tends to be proportional to B0.

  11. Effect of hydrolyzed whey protein on surface morphology, water sorption, and glass transition temperature of a model infant formula.

    Science.gov (United States)

    Kelly, Grace M; O'Mahony, James A; Kelly, Alan L; O'Callaghan, Donal J

    2016-09-01

    Physical properties of spray-dried dairy powders depend on their composition and physical characteristics. This study investigated the effect of hydrolyzed whey protein on the microstructure and physical stability of dried model infant formula. Model infant formulas were produced containing either intact (DH 0) or hydrolyzed (DH 12) whey protein, where DH=degree of hydrolysis (%). Before spray drying, apparent viscosities of liquid feeds (at 55°C) at a shear rate of 500 s(-1) were 3.02 and 3.85 mPa·s for intact and hydrolyzed infant formulas, respectively. On reconstitution, powders with hydrolyzed whey protein had a significantly higher fat globule size and lower emulsion stability than intact whey protein powder. Lactose crystallization in powders occurred at higher relative humidity for hydrolyzed formula. The Guggenheim-Anderson-de Boer equation, fitted to sorption isotherms, showed increased monolayer moisture when intact protein was present. As expected, glass transition decreased significantly with increasing water content. Partial hydrolysis of whey protein in model infant formula resulted in altered powder particle surface morphology, lactose crystallization properties, and storage stability.

  12. Dramatic slowing of compositional relaxations in the approach to the glass transition for a bimodal colloidal suspension

    Science.gov (United States)

    Hannam, S. D. W.; Daivis, P. J.; Bryant, G.

    2017-08-01

    Molecular dynamics simulation was used to study a model colloidal suspension with two species of slightly different sized colloidal particles in an explicit solvent. In this work we calculated the four interdiffusion coefficients for the ternary system, which were then used to calculate the decay coefficients D± of the two independent diffusive modes. We found that the slower D- decay mode, which is associated with the system's ability to undergo compositional changes, was responsible for the long-time decay in the intermediate scattering function. We also found that a decrease in D- to negligible values at a packing fraction of Φg=0.592 resulted in an extreme slow-down in the long-time decay of the intermediate scattering function often associated with the glass transition. Above Φg, the system formed a long-lived metastable state that did not relax to its equilibrium crystal state within the simulation time window. We concluded that the inhibition of crystallization was caused by the inability of the quenched fluid to undergo the compositional changes needed for the formation of the equilibrium crystal.

  13. Glass transition with decreasing correlation length during cooling of Fe50Co50 superlattice and strong liquids

    CERN Document Server

    Wei, Shuai; Busch, Ralf; Angell, C Austen

    2010-01-01

    The glass transition GT is usually thought of as a structural arrest that occurs during the cooling of a liquid, or sometimes a plastic crystal, trapping a metastable state of the system before it can recrystallize to stabler forms1. This phenomenon occurs in liquids of all classes, most recently in bulk metallic glassformers2. Much theoretical interest has been generated by the dynamical heterogeneity observed in cooling of fragile liquids3, 4, and many have suggested that the slow-down is caused by a related increasing correlation length 5-9. Here we report both kinetics and thermodynamics of arrest in a system that disorders while in its ground state, exhibits a large !Cp on arrest (!Cp = Cp,mobile - Cp,arrested), yet clearly is characterized by a correlation length that is decreasing as GT is approached from above. We show that GT kinetics in our system, the disordering superlattice Fe50Co50, satisfy the kinetic criterion for ideally 'strong' glassformers10, and since !Cp behavior through Tg also correlat...

  14. Influence of compression on water sorption, glass transition, and enthalpy relaxation behavior of freeze-dried amorphous sugar matrices.

    Science.gov (United States)

    Imamura, Koreyoshi; Kagotani, Ryo; Nomura, Mayo; Tanaka, Kazuhiro; Kinugawa, Kohshi; Nakanishi, Kazuhiro

    2011-04-15

    An amorphous matrix comprised of sugar molecules are frequently used in the pharmaceutical industry. The compression of the amorphous sugar matrix improves the handling. Herein, the influence of compression on the water sorption of an amorphous sugar matrix was investigated. Amorphous sugar samples were prepared by freeze-drying, using several types of sugars, and compressed at 0-443 MPa. The compressed amorphous sugar samples as well as uncompressed samples were rehumidified at given RHs, and the equilibrium water content and glass transition temperature (T(g)) were then measured. Compression resulted in a decrease in the equilibrium water content of the matrix, the magnitude of which was more significant for smaller sized sugars. Diffusivity of water vapor in the sample was also decreased to one-hundredth by the compression. The T(g) value for a given RH remained unchanged, irrespective of the compression. Accordingly, the decrease in T(g) with increasing water content increased as the result of compression. The structural relaxation of the amorphous sugar matrices were also examined and found to be accelerated to the level of a non-porous amorphous sugar matrix as the result of the compression. The findings indicate that pores contained in freeze-dried sugar samples interfere with the propagation of structural relaxation.

  15. The glass transition and sub-T(g)-relaxation in pharmaceutical powders and dried proteins by thermally stimulated current.

    Science.gov (United States)

    Reddy, Renuka; Chang, Liuquan ' Lucy '; Luthra, Suman; Collins, George; Lopez, Ciro; Shamblin, Sheri L; Pikal, Michael J; Gatlin, Larry A; Shalaev, Evgenyi Y

    2009-01-01

    The main goal of the study was to evaluate the applicability of thermally stimulated current (TSC) as a measure of molecular mobility in dried globular proteins. Three proteins, porcine somatotropin, bovine serum albumin, and immunoglobulin, as well as materials with a strong calorimetric glass transition (T(g)), that is, indomethacin and poly(vinypyrrolidone) (PVP), were studied by both TSC and differential scanning calorimetry (DSC). Protein/sugar colyophilized mixtures were also studied by DSC, to estimate calorimetric T(g) for proteins using extrapolation procedure. In the majority of cases, TSC detected relaxation events that were not observed by DSC. For example, a sub-T(g) TSC event (beta-relaxation) was observed for PVP at approximately 120 degrees C, which was not detected by the DSC. Similarly, DSC did not detect events in any of the three proteins below the thermal denaturation temperature whereas a dipole relaxation was detected by TSC in the range of 90-140 degrees C depending on the protein studied. The TSC signal in proteins was tentatively assigned as localized mobility of protein segments, which is different from a large-scale cooperative motions usually associated with calorimetric T(g). TSC is a promising method to study the molecular mobility in proteins and other materials with weak calorimetric T(g). (c) 2008 Wiley-Liss, Inc. and the American Pharmacists Association

  16. QSPR Analysis of Copolymers by Recursive Neural Networks: Prediction of the Glass Transition Temperature of (Meth)acrylic Random Copolymers.

    Science.gov (United States)

    Bertinetto, Carlo Giuseppe; Duce, Celia; Micheli, Alessio; Solaro, Roberto; Tiné, Maria Rosaria

    2010-09-17

    The glass transition temperature (Tg ) of acrylic and methacrylic random copolymers was investigated by means of Quantitative Structure-Property Relationship (QSPR) methodology based on Recursive Neural Networks (RNN). This method can directly take molecular structures as input, in the form of labelled trees, without needing predefined descriptors. It was applied to three data sets containing up to 615 polymers (340 homopolymers and 275 copolymers). The adopted representation was able to account for the structure of the repeating unit as well as average macromolecular characteristics, such as stereoregularity and molar composition. The best result, obtained on a data set focused on copolymers, showed a Mean Average Residual (MAR) of 4.9 K, a standard error of prediction (S) of 6.1 K and a squared correlation coefficient (R(2) ) of 0.98 for the test set, with an optimal rate with respect to the training error. Through the treatment of homopolymers and copolymers both as separated and merged data sets, we also showed that the proposed approach is particularly suited for generalizing prediction of polymer properties to various types of chemical structures in a uniform setting.

  17. Sorption isotherms, thermodynamic properties and glass transition temperature of mucilage extracted from chia seeds (Salvia hispanica L.).

    Science.gov (United States)

    Velázquez-Gutiérrez, Sandra Karina; Figueira, Ana Cristina; Rodríguez-Huezo, María Eva; Román-Guerrero, Angélica; Carrillo-Navas, Hector; Pérez-Alonso, César

    2015-05-05

    Freeze-dried chia mucilage adsorption isotherms were determined at 25, 35 and 40°C and fitted with the Guggenheim-Anderson-de Boer model. The integral thermodynamic properties (enthalpy and entropy) were estimated with the Clausius-Clapeyron equation. Pore radius of the mucilage, calculated with the Kelvin equation, varied from 0.87 to 6.44 nm in the temperature range studied. The point of maximum stability (minimum integral entropy) ranged between 7.56 and 7.63kg H2O per 100 kg of dry solids (d.s.) (water activity of 0.34-0.53). Enthalpy-entropy compensation for the mucilage showed two isokinetic temperatures: (i) one occurring at low moisture contents (0-7.56 kg H2O per 100 kg d.s.), controlled by changes in water entropy; and (ii) another happening in the moisture interval of 7.56-24 kg H2O per 100 kg d.s. and was enthalpy driven. The glass transition temperature Tg of the mucilage fluctuated between 42.93 and 57.93°C.

  18. Structural characterization of tellurite glasses doped with transition metal oxides using Raman spectra and ab initio calculations

    Science.gov (United States)

    Mohamed, Tarek A.; Shaltout, I.; Al Yahyaei, K. M.

    2006-05-01

    Systems of iron tellurite glasses were prepared by melt quenching with compositions of [85%TeO 2 + 5%Fe 2O 3 + 10%TMO], where transition metal oxides (TMO) are TiO 2, V 2O 5, MnO, CoO, NiO and CuO. Furthermore, the main structural units of these samples have been characterized by means of Raman spectra (150-1200 cm -1) as well as wavenumber predictions by means of Gaussian 98 ab initio calculations for the proposed site symmetries of TeO 44- triagonal bipyramid ( C2v) and Te 2O 76- bridged tetrahedra ( Cs and C1). Aided by normal coordinate analysis, calculated vibrational frequencies, Raman scattering activities, force constants in internal coordinates and potential energy distributions (PEDs), revised vibrational assignments for the fundamental modes have been proposed. The main structural features are correlated to the dominant units of triagonal bipyramid (tbp) or bridged tetrahedral (TeO 3+1 binds to TeO 3 through TeOTe bridge; corner sharing). Moreover, the Raman spectra of the investigated tellurites reflect a structural change from tbp (coordination number is four) to triagonal pyramidal (coordination number is three).

  19. Selecting polymers for two-phase partitioning bioreactors (TPPBs): Consideration of thermodynamic affinity, crystallinity, and glass transition temperature.

    Science.gov (United States)

    Bacon, Stuart L; Peterson, Eric C; Daugulis, Andrew J; Parent, J Scott

    2015-01-01

    Two-phase partitioning bioreactor technology involves the use of a secondary immiscible phase to lower the concentration of cytotoxic solutes in the fermentation broth to subinhibitory levels. Although polymeric absorbents have attracted recent interest due to their low cost and biocompatibility, material selection requires the consideration of properties beyond those of small molecule absorbents (i.e., immiscible organic solvents). These include a polymer's (1) thermodynamic affinity for the target compound, (2) degree of crystallinity (wc ), and (3) glass transition temperature (Tg ). We have examined the capability of three thermodynamic models to predict the partition coefficient (PC) for n-butyric acid, a fermentation product, in 15 polymers. Whereas PC predictions for amorphous materials had an average absolute deviation (AAD) of ≥16%, predictions for semicrystalline polymers were less accurate (AAD ≥ 30%). Prediction errors were associated with uncertainties in determining the degree of crystallinity within a polymer and the effect of absorbed water on n-butyric acid partitioning. Further complications were found to arise for semicrystalline polymers, wherein strongly interacting solutes increased the polymer's absorptive capacity by actually dissolving the crystalline fraction. Finally, we determined that diffusion limitations may occur for polymers operating near their Tg , and that the Tg can be reduced by plasticization by water and/or solute. This study has demonstrated the impact of basic material properties that affects the performance of polymers as sequestering phases in TPPBs, and reflects the additional complexity of polymers that must be taken into account in material selection.

  20. Reformulation of time-convolutionless mode-coupling theory near the glass transition

    Science.gov (United States)

    Tokuyama, Michio

    2017-10-01

    The time-convolutionless mode-coupling theory (TMCT) recently proposed is reformulated under the condition that one of two approximations, which have been used to formulate the original TMCT in addition to the MCT approximations done on a derivation of nonlinear memory function in terms of the intermediate-scattering function, is not employed because it causes unphysical results for intermediate times. The improved TMCT equation is then derived consistently under another approximation. It is first checked that the ergodic to non-ergodic transition obtained by a new equation is exactly the same as that obtained by an old one because the long-time dynamics of both equations coincides with each other. However, it is emphasized that a difference between them appears in the intermediate-time dynamics of physical quantities. Such a difference is explored numerically in the dynamics of a non-Gaussian parameter by employing the Percus-Yevick static structure factor to calculate the nonlinear memory function.

  1. Molecular weight dependence of surface flow near the bulk glass transition temperature

    Science.gov (United States)

    Chai, Yu; Salez, Thomas; Benzaquen, Michael; Raphael, Elie; Forrest, James A.

    2014-03-01

    We present the study on molecular weight dependent sub-Tg surface dynamics of polymer thin films by using the Nano-step experiment [McGraw et al. Soft Matter 7, 7832 (2011)]. By varying the molecular weight, we are able to probe the surface dynamics of the free surface below Tg with the polymer size comparable to the surface depth. In particular, we define and use a correlation function to compare measured and calculated profiles to analyze the transition from the bulk flow to flow restricted to the surface region. Surprisingly, even for the polymers with Mw = 22,000 surface flow is still observed below the bulk Tg value. A numerical simulation of random walk is used to find the fraction of polymer of which all of the polymer segments are located in the free surface region. The simulation results indicate that there are still a significant fraction of polymer molecules where all segments are in the near free surface region. These molecules can undergo flow consistent with the experimental results.

  2. Glass and glass-ceramics along the SrTiO3-NaPO3 line

    Directory of Open Access Journals (Sweden)

    Sinouh H.

    2013-09-01

    Full Text Available The xSrTiO3-(1−xNaPO3 (x = 0−0.20 mol% glasses were prepared by the conventional melt-quenching method. The amorphous state of the samples was verified by X-ray diffraction. The glass-ceramic materials were obtained by the well known thermal controlled crystallization process. It is found that several physical properties such as the density, molar volume, and the glass transition temperature depend strongly on the chemical composition. Vickers test on the glasses showed that the micro-hardness increases with the SrTiO3 content. The structural approach of the glasses was realized by IR spectroscopy. This technique has highlighted the co-existence of different phosphate and titanium structural units in the glassy-matrix. Crystallization of the glasses was enhanced by heat treatments and followed by X-ray diffraction. A mechanism for this glass crystallization was proposed.

  3. Effects of the embedding kinetics on the surface nano-morphology of nano-grained Au and Ag films on PS and PMMA layers annealed above the glass transition temperature

    Energy Technology Data Exchange (ETDEWEB)

    Ruffino, F.; Grimaldi, M.G. [Dipartimento di Fisica ed Astronomia, Universita di Catania, Catania (Italy); MATIS IMM-CNR, Catania (Italy); Torrisi, V.; Marletta, G. [University of Catania, CSGI, Laboratory for Molecular Surface and Nanotechnology (LAMSUN), Department of Chemical Sciences, Catania (Italy)

    2012-06-15

    The morphology evolution of nano-grained Ag and Au films deposited on polystyrene (PS) and poly(methyl methacrylate) (PMMA) polymeric layers were studied, using the atomic force microscopy technique, when annealed above the polymers glass transition temperature. The main effects on the morphology changes were identified with those concerning the embedding kinetics of the Ag and Au nanoparticles in the PS or PMMA layers. The embedding process of the nanoparticles follows as a consequence of the long-range mobility of the polymeric chains above the glass transition temperature. In particular, the dependence of the nanoparticles mean height and surface density on the annealing time at various temperatures was quantified. The analyses of these behaviors allowed us: (1) to distinguish the overall embedding process in a first stage in which a thin wetting layer of the polymer coats the nanoparticles followed by a true embedding process of the nanoparticles into the polymer layer; (2) to evaluate the characteristic coating time for the Ag and Au nanoparticles in the PS and PMMA in the first stage; (3) to evaluate the characteristic embedding velocity for the Ag and Au nanoparticles in the PS and PMMA in the second stage; (4) to derive the activation energies for the embedding process of the Ag and Au nanoparticles in PS and PMMA; (5) to identify the embedding statistics of the Ag and Au nanoparticles in PS and PMMA with a ''failure'' Weibull statistics. (orig.)

  4. The influence of topological phase transition on the superfluid density of overdoped copper oxides.

    Science.gov (United States)

    Shaginyan, V R; Stephanovich, V A; Msezane, A Z; Japaridze, G S; Popov, K G

    2017-08-23

    We show that a quantum phase transition, generating flat bands and altering Fermi surface topology, is a primary reason for the exotic behavior of the overdoped high-temperature superconductors represented by La2-xSrxCuO4, whose superconductivity features differ from what is predicted by the classical Bardeen-Cooper-Schrieffer theory. This observation can open avenues for chemical preparation of high-Tc materials. We demonstrate that (1) at temperature T = 0, the superfluid density ns turns out to be considerably smaller than the total electron density; (2) the critical temperature Tc is controlled by ns rather than by doping, and is a linear function of the ns; (3) at T > Tc the resistivity ρ(T) varies linearly with temperature, ρ(T) ∝ αT, where α diminishes with Tc → 0, whereas in the normal (non superconducting) region induced by overdoping, Tc = 0, and ρ(T) ∝ T(2). Our results are in good agreement with recent experimental observations.

  5. Hydrostatic pressure effects on the state density and optical transitions in quantum dots

    Energy Technology Data Exchange (ETDEWEB)

    Galindez-Ramirez, G; Perez-Merchancano, S T [Departamento de Fisica, Universidad del Cauca, calle 5 4-70, Popayan (Colombia); Paredes Gutierrez, H [Escuela de Fisica, Universidad Industrial de Santander, A. A. 678, Bucaramanga (Colombia); Gonzalez, J D, E-mail: jdavid0831@gmail.co [Grupo de Investigacion en teorIa de la Materia Condensada, Universidad del Magdalena, A.A. 731, Santa Marta (Colombia)

    2010-09-01

    Using the effective mass approximation and variational method we have computed the effects of hydrostatic pressure on the absorption and photoluminescence spectra in spherical quantum dot GaAs-(Ga, Al) As, considering a finite confinement potential of this particular work we show the optical transitions in quantum of various sizes in the presence of hydrogenic impurities and hydrostatic pressure effects. Our first result describes the spectrum of optical absorption of 500 A QD for different values of hydrostatic pressure P = 0, 20 and 40 Kbar. The absorption peaks are sensitive to the displacement of the impurity center to the edge of the quantum dot and even more when the hydrostatic pressure changes in both cases showing that to the extent that these two effects are stronger quantum dots respond more efficiently. Also this result can be seen in the study of the photoluminescence spectrum as in the case of acceptor impurities consider them more efficiently capture carriers or electrons that pass from the conduction band to the valence band. Density states with randomly distributed impurity show that the additional peaks in the curves of the density of impurity states appear due to the presence of the additional hydrostatic pressure effects.

  6. Laser reflection method for determination of shear stress in low density transitional flows

    Science.gov (United States)

    Sathian, Sarith P.; Kurian, Job

    2006-03-01

    The details of laser reflection method (LRM) for the determination of shear stress in low density transitional flows are presented. The method is employed to determine the shear stress due to impingement of a low density supersonic free jet issuing out from a convergent divergent nozzle on a flat plate. The plate is smeared with a thin oil film and kept parallel to the nozzle axis. For a thin oil film moving under the action of aerodynamic boundary layer, the shear stress at the air-oil interface is equal to the shear stress between the surface and air. A direct and dynamic measurement of the oil film slope generated by the shear force is done using a position sensing detector (PSD). The thinning rate of the oil film is directly measured which is the major advantage of the LRM. From the oil film slope history, calculation of the shear stress is done using a three-point formula. The range of Knudsen numbers investigated is from 0.028 to 0.516. Pressure ratio across the nozzle varied from 3,500 to 8,500 giving highly under expanded free jets. The measured values of shear, in the overlapping region of experimental parameters, show fair agreement with those obtained by force balance method and laser interferometric method.

  7. Superfluid density in He II near the lambda transition: First principles theory

    Energy Technology Data Exchange (ETDEWEB)

    Jackson, H.W., E-mail: hwjackson2@gmail.com

    2015-03-15

    A first principles theory of the λ transition in liquid {sup 4}He was introduced in a recent paper [H. W. Jackson, J. Low Temp. Phys. 155, 1 (2009)]. In that theory critical fluctuations consisting of isothermal fourth sound waves are treated with quantum statistical mechanics methods in deriving formulas for constant volume conditions for specific heat, correlation length, equal time pair correlation function, and isothermal compressibility. To leading order terms in (T{sub λ}−T) the theory yields exact results α′=0 and ν′=2/3 for critical exponents at constant volume. A follow-up study in the present paper demonstrates by a least squares fit that a logarithmic function accurately describes the specific heat at svp when (T{sub λ}−T) is between 10{sup −9} K and 10{sup −5} K. This logarithmic divergent behavior conflicts with previous analyses of experimental data and predictions of renormalization group theory that constant pressure specific heat is finite at T{sub λ}, but Is thermodynamically consistent with logarithmic asymptotic behavior of specific heat at constant volume predicted in the new theory. The first principles theory is extended in this paper to derive formulas for superfluid density and for a relation between superfluid density and correlation length in He II near T{sub λ}. Numerical results based on these formulas are in good agreement with experimental data produced by second sound measurements.

  8. Quantum Monte Carlo studies of a metallic spin-density wave transition

    Energy Technology Data Exchange (ETDEWEB)

    Gerlach, Max Henner

    2017-01-20

    Plenty experimental evidence indicates that quantum critical phenomena give rise to much of the rich physics observed in strongly correlated itinerant electron systems such as the high temperature superconductors. A quantum critical point of particular interest is found at the zero-temperature onset of spin-density wave order in two-dimensional metals. The appropriate low-energy theory poses an exceptionally hard problem to analytic theory, therefore the unbiased and controlled numerical approach pursued in this thesis provides important contributions on the road to comprehensive understanding. After discussing the phenomenology of quantum criticality, a sign-problem-free determinantal quantum Monte Carlo approach is introduced and an extensive toolbox of numerical methods is described in a self-contained way. By the means of large-scale computer simulations we have solved a lattice realization of the universal effective theory of interest. The finite-temperature phase diagram, showing both a quasi-long-range spin-density wave ordered phase and a d-wave superconducting dome, is discussed in its entirety. Close to the quantum phase transition we find evidence for unusual scaling of the order parameter correlations and for non-Fermi liquid behavior at isolated hot spots on the Fermi surface.

  9. Densities and eccentricities of 139 Kepler planets from transit time variations

    Energy Technology Data Exchange (ETDEWEB)

    Hadden, Sam; Lithwick, Yoram [Department of Physics and Astronomy, Northwestern University, Evanston, IL 60208 (United States)

    2014-05-20

    We extract densities and eccentricities of 139 sub-Jovian planets by analyzing transit time variations (TTVs) obtained by the Kepler mission through Quarter 12. We partially circumvent the degeneracies that plague TTV inversion with the help of an analytical formula for the TTV. From the observed TTV phases, we find that most of these planets have eccentricities of the order of a few percent. More precisely, the rms eccentricity is 0.018{sub −0.004}{sup +0.005}, and planets smaller than 2.5 R {sub ⊕} are around twice as eccentric as those bigger than 2.5 R {sub ⊕}. We also find a best-fit density-radius relationship ρ ≈ 3 g cm{sup –3} × (R/3 R {sub ⊕}){sup –2.3} for the 56 planets that likely have small eccentricity and hence small statistical correction to their masses. Many planets larger than 2.5 R {sub ⊕} are less dense than water, implying that their radii are largely set by a massive hydrogen atmosphere.

  10. Foaming of CRT panel glass powder using Na2CO3

    DEFF Research Database (Denmark)

    Petersen, Rasmus Rosenlund; König, Jakob; Smedskjær, Morten Mattrup

    2014-01-01

    to its non-hazardous composition. Here we report on the foaming of CRT panel glass using Na2CO3 as the foaming agent. We explore how heat treatment temperature and concentration of Na2CO3 affect the density and porosity of the foam glasses, and whether Na2O is incorporated in the glass network......The recycling of glass from obsolete cathode ray tubes (CRT) has hitherto only occurred to a very limited extent, but the production of foam glass used as an insulation material component has recently been proposed as a promising recycling method. CRT panel glass has high recycling potential due......% Na2CO3 is added and the heat treatment temperature is 1023 K. Interestingly, the glass transition temperature (Tg) of the final foam glass decreases linearly with increasing [Na2CO3], indicating that the Na2O is incorporated into the glass network....

  11. Visualizing the Contributions of Virtual States to Two-Photon Absorption Cross Sections by Natural Transition Orbitals of Response Transition Density Matrices.

    Science.gov (United States)

    Nanda, Kaushik D; Krylov, Anna I

    2017-07-20

    Observables such as two-photon absorption cross sections cannot be computed from the wave functions of initial and final states alone because of their nonlinear nature. Rather, they depend on the entire manifold of the excited states, which follows from the familiar sum-over-states expressions of second- and higher-order properties. Consequently, the interpretation of the computed nonlinear optical properties in terms of molecular orbitals is not straightforward and usually relies on approximate few-states models. Here, we show that the two-photon absorption (2PA) transitions can be visualized using response one-particle transition density matrices, which are defined as transition density matrices between the zero-order and first-order perturbed states. We also extend the concept of natural transition orbitals to 2PA transitions. We illustrate the utility of this new tool, which provides a rigorous black box alternative to traditional qualitative few-states analysis, by considering 2PA transitions in ethylene, trans-stilbene, and para-nitroaniline.

  12. Two Glass Transitions Associated to Different Dynamic Disorders in the Nematic Glassy State of a Non-Symmetric Liquid Crystal Dimer Dopped with g-Alumina Nanoparticles

    Directory of Open Access Journals (Sweden)

    Sergio Diez-Berart

    2015-06-01

    Full Text Available In the present work, the nematic glassy state of the non-symmetric LC dimer α-(4-cyanobiphenyl-4′-yloxy-ω-(1-pyrenimine-benzylidene-4′-oxy undecane is studied by means of calorimetric and dielectric measurements. The most striking result of the work is the presence of two different glass transition temperatures: one due to the freezing of the flip-flop motions of the bulkier unit of the dimer and the other, at a lower temperature, related to the freezing of the flip-flop and precessional motions of the cyanobiphenyl unit. This result shows the fact that glass transition is the consequence of the freezing of one or more coupled dynamic disorders and not of the disordered phase itself. In order to avoid crystallization when the bulk sample is cooled down, the LC dimer has been confined via the dispersion of γ-alumina nanoparticles, in several concentrations.

  13. Structure-Property Relationships and the Mixed Network Former Effect in Boroaluminosilicate Glasses

    DEFF Research Database (Denmark)

    Zheng, Qiuju; Potuzak, Marcel; Mauro, John C.

    compositions by substituting Al2O3 for SiO2. We also investigate the various roles of sodium in the glasses including charge compensation of tetrahedral aluminum and boron atoms and formation of non-bridging oxygen. We find that mechanical properties (density, elastic moduli, and hardness), glass transition...

  14. Structure-Property Relationships and the Mixed Network Former Effect in Boroaluminosilicate Glasses

    DEFF Research Database (Denmark)

    Zheng, Qiuju; Potuzak, Marcel; Mauro, John C.

    compositions by substituting Al2O3 for SiO2. We also investigate the various roles of sodium in the glasses including charge compensation of tetrahedral aluminum and boron atoms and formation of non-bridging oxygen. We find that mechanical properties (density, elastic moduli, and hardness), glass transition...

  15. Facile aqueous synthesis and thermal insulating properties of low-density glass/TiO2 core/shell composite hollow spheres

    Institute of Scientific and Technical Information of China (English)

    Jing Yuan; Zhenguo An; Bing Li; Jinjie Zhang

    2012-01-01

    Anatase TiO2 shells assembled on hollow glass microspheres (HGM) with tunable morphologies were successfully prepared through a controllable chemical precipitation method with urea as the precipitator.Thus,glass/TiO2 core/shell composite hollow spheres with low particle density (0.40 g/cm3) were fabricated.The phase structures,morphologies,particle sizes,shell thicknesses,and chemical compositions of the composite microspheres were characterized by X-ray diffraction (XRD),scanning electron microscopy (SEM),and energy dispersive X-ray spectroscopy (EDS).The morphology of the TiO2 shell can be tailored by properly monitoring the reaction system component and parameters.The probable growth mechanism and fabrication process of the core/shell products involving the nucleation and oriented growth of TiO2 nanocrystals on hollow glass microspheres was proposed.A low infrared radiation study revealed that the radiation properties of the products are greatly influenced by the unique product shell structures.A thermal conductivity study showed that the TiO2/HGM possess low thermal conductivity that is similar to that of the pristine HGMs.This work provides an additional strategy to prepare low-density thermal insulating particles with tailored morphologies and properties.

  16. When is a single molecule heterogeneous? A multidimensional answer and its application to dynamics near the glass transition

    Science.gov (United States)

    Verma, Sachin Dev; Vanden Bout, David A.; Berg, Mark A.

    2015-07-01

    Even for apparently simple condensed-phase processes, bulk measurements of relaxation often yield nonexponential decays; the rate appears to be dispersed over a range of values. Taking averages over individual molecules is an intuitive way to determine whether heterogeneity is responsible for such rate dispersion. However, this method is in fundamental conflict with ergodic behavior and often yields ambiguous results. This paper proposes a new definition of rate heterogeneity for ergodic systems based on multidimensional time correlation functions. Averages are taken over both time and molecules. Because the data set is not subdivided, the signal-to-noise ratio is improved. Moment-based quantities are introduced to quantify the concept of rate dispersion. As a result, quantitative statements about the fraction of the dispersion due to heterogeneity are possible, and the experimental noise is further averaged. The practicality of this approach is demonstrated on single-molecule, linear-dichroism trajectories for R6G in poly(cyclohexyl acrylate) near its glass transition. Single-molecule averaging of these data does not provide useful conclusions [C. Y. Lu and D. A. Vanden Bout, J. Chem. Phys. 125, 124701 (2006)]. However, full-ensemble, two- and three-dimensional averages of the same data give clear and quantitative results: the rate dispersion is 95% ± 5% due to heterogeneity, and the rate exchange is at least 11 times longer than the mean rotation time and possibly much longer. Based on these results, we suggest that the study of heterogeneous materials should not focus on "ensemble" versus "single-molecule" experiments, but on one-dimensional versus multidimensional measurements.

  17. Effects of molecular characteristics of on konjac glucomannan glass transitions of potato amylose, amylopection and their mixtures.

    Science.gov (United States)

    Guo, Li; Liang, Qin; Du, Xianfeng

    2011-03-15

    The purpose of this study was to explore further the functions of konjac glucomannan (KGM) in starch-based foods. Experiments were carried out using the mixed amylose/amylopectin/KGM system as a model. High-speed differential scanning calorimetry (hyper-DSC) with the support of high-performance size exclusion chromatography (HPSEC) equipped with multi-angle laser light scattering (MALLS) and differential refractive index (RI), X-ray diffractometry (XRD) and viscosimetry was used to investigate the effects of KGM on glass transition temperatures (T(g) s) of mixtures with different amylose/amylopectin ratios. Hyper-DSC results showed that the T(g) s of amylose, amylopection and their mixtures decreased with increasing concentration of KGM. Based on the molecular characteristics of KGM, HPSEC-MALLS-RI, viscosimetry and XRD results showed that the molar masses of KGM ranged from 1.023 × 10(6) to 1.329 × 10(6) g mol(-1) ; the root mean square (RMS) radii were distributed from 110.5 to 129.6 nm, and M(w) /M(n) was 1.017. KGM was a linear molecule with random-coil conformation in solution and the crystallinity was 0.00%. It is suggested that the addition of KGM has plasticizing effects on the structures of amylose and amylopectin, which can increase free volume and molecular movement of amylose and amylopectin chains, resulting in a decrease in their T(g) s. Copyright © 2010 Society of Chemical Industry.

  18. Phase transitions to dipolar clusters and charge density waves in high T{sub c} superconductors

    Energy Technology Data Exchange (ETDEWEB)

    Saarela, M., E-mail: Mikko.Saarela@oulu.fi [Department of Physics, University of Oulu, P.O. Box 3000, FIN-90014 (Finland); Kusmartsev, F.V. [Department of Physics, Loughborough University, LE11 3TU (United Kingdom)

    2017-02-15

    We show that doping of hole charge carriers leads to formation of electric dipolar clusters in cuprates. They are created by many-body interactions between the dopant ion outside and holes inside the CuO planes. Because of the two-fold degeneracy holes in the CuO plane cluster into four-particles resonance valence bond plaquettes bound with dopant ions. Such dipoles may order into charge-density waves (CDW) or stripes or form a disordered state depending on doping and temperature. The lowest energy of the ordered system corresponds to a local anti-ferroelectric ordering. The mobility of individual disordered dipoles is very low at low temperatures and they prefer first to bind into dipole-dipole pairs. Electromagnetic radiation interacts strongly with electric dipoles and when the sample is subjected to it the mobility changes significantly. This leads to a fractal growth of dipolar clusters. The existence of electric dipoles and CDW induce two phase transitions with increasing temperature, melting of the ordered state and disappearance of the dipolar state. Ferroelectricity at low doping is a natural consequence of such dipole moments. We develop a theory based on two-level systems and dipole-dipole interaction to explain the behavior of the polarization as a function of temperature and electric field.

  19. Quantum critical properties of a metallic spin-density-wave transition

    Science.gov (United States)

    Gerlach, Max H.; Schattner, Yoni; Berg, Erez; Trebst, Simon

    2017-01-01

    We report on numerically exact determinantal quantum Monte Carlo simulations of the onset of spin-density-wave (SDW) order in itinerant electron systems captured by a sign-problem-free two-dimensional lattice model. Extensive measurements of the SDW correlations in the vicinity of the phase transition reveal that the critical dynamics of the bosonic order parameter are well described by a dynamical critical exponent z =2 , consistent with Hertz-Millis theory, but are found to follow a finite-temperature dependence that does not fit the predicted behavior of the same theory. The presence of critical SDW fluctuations is found to have a strong impact on the fermionic quasiparticles, giving rise to a dome-shaped superconducting phase near the quantum critical point. In the superconducting state we find a gap function that has an opposite sign between the two bands of the model and is nearly constant along the Fermi surface of each band. Above the superconducting Tc, our numerical simulations reveal a nearly temperature and frequency independent self-energy causing a strong suppression of the low-energy quasiparticle weight in the vicinity of the hot spots on the Fermi surface. This indicates a clear breakdown of Fermi liquid theory around these points.

  20. AC-field-induced quantum phase transitions in density of states

    Science.gov (United States)

    Yang, Kai-Hua; Liu, Kai-Di; Wang, Huai-Yu; Qin, Chang-Dong

    2016-02-01

    We investigate the joint effects of the intralead electron interaction and an external alternating gate voltage on the time-averaged local density of states (DOSs) of a quantum dot coupled to two Luttinger-liquid leads in the Kondo regime. A rich dependence of the DOSs on the driving amplitude and intralead interaction is demonstrated. We show that the feature is quite different for different interaction strengths in the presence of the ac field. It is shown that the photon-assisted transport processes cause an additional splitting of the Kondo peak or dip, which exhibits photon-assisted single-channel (1CK) or two-channel Kondo (2CK) physics behavior. The phase transition between photon-assisted 1CK and 2CK physics occurs when the interaction strength is moderately strong. The inelastic channels associated with photon-assisted electron tunneling can dominate electron transport for weak interaction when the ac amplitude is greater than the frequency by one order of magnitude. In the limit of strong interaction the DOSs scale as a power-law behavior which is strongly affected by the ac field.