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Sample records for glass transition phenomena

  1. Numerical simulation of spin-glass transition phenomena (invited)

    NASA Astrophysics Data System (ADS)

    Walstedt, R. E.; Walker, L. R.

    1982-11-01

    Results are presented from a continuing investigation of spin-glass transition effects by numerical simulation. The model is one of classical unit vectors randomly distributed on an fcc lattice, with RKKY exchange coupling and nearest-neighbor dipolar coupling in an approximate representation of dilute Mn in Cu. Results for system energy and for dipolar energy as a function of temperature show no resolvable features at the freezing temperature TG* in accord with the high-precision specific heat data of Fogle, Boyer, Phillips, and Van Curen. Additional details of shattered susceptibility behavior in the vicinity of the ground-state transition are presented. Further data on freezing temperatures as a function of dipolar coupling strength D show a trend toward macroscopic behavior (i.e., TG* independent of D) with a sample of 4928 spins. Finally, a moderately sharp onset of freezing transverse to an applied magnetic field is found, as predicted by the mean-field calculations of Toulouse and Gabay. As expected, this transition is unrelated to transverse susceptibilities.

  2. Are polymers standard glass-forming systems? The role of intramolecular barriers on the glass-transition phenomena of glass-forming polymers

    NASA Astrophysics Data System (ADS)

    Colmenero, J.

    2015-03-01

    Traditionally, polymer melts have been considered archetypal glass-formers. This has been mainly due to the fact that these systems can easily be obtained as glasses by cooling from the melt, even at low cooling rates. However, the macromolecules, i.e. the structural units of polymer systems in general, are rather different from the standard molecules. They are long objects (‘chains’) made by repetition of a given chemical motif (monomer) and have intra-macromolecular barriers that limit their flexibility. The influence of these properties on, for instance, the glass-transition temperature of polymers, is a topic that has been widely studied by the polymer community almost from the early times of polymer science. However, in the framework of the glass-community, the relevant influence of intra-macromolecular barriers and chain connectivity on glass-transition phenomena of polymers has started to be recognized only recently. The aim of this review is to give an overview and to critically revise the results reported on this topic over the last years. From these results, it seems to be evident that there are two different mechanisms involved in the dynamic arrest in glass-forming polymers: (i) the intermolecular packing effects, which dominate the dynamic arrest of low molecular weight glass-forming systems; and (ii) the effect of intra-macromolecular barriers combined with chain connectivity. It has also been shown that the mode coupling theory (MCT) is a suitable theoretical framework to discuss these questions. The values found for polymers for the central MCT parameter—the so-called λ-exponent—are of the order of 0.9, clearly higher than the standard values (λ ≈ 0.7) found in systems where the dynamic arrest is mainly driven by packing effects (‘standard’ glass-formers). Within the MCT, this is a signature of the presence of two competing mechanisms of dynamic arrest, as it has been observed in short-ranged attractive colloids or two component

  3. Are polymers standard glass-forming systems? The role of intramolecular barriers on the glass-transition phenomena of glass-forming polymers.

    PubMed

    Colmenero, J

    2015-03-18

    Traditionally, polymer melts have been considered archetypal glass-formers. This has been mainly due to the fact that these systems can easily be obtained as glasses by cooling from the melt, even at low cooling rates. However, the macromolecules, i.e. the structural units of polymer systems in general, are rather different from the standard molecules. They are long objects ('chains') made by repetition of a given chemical motif (monomer) and have intra-macromolecular barriers that limit their flexibility. The influence of these properties on, for instance, the glass-transition temperature of polymers, is a topic that has been widely studied by the polymer community almost from the early times of polymer science. However, in the framework of the glass-community, the relevant influence of intra-macromolecular barriers and chain connectivity on glass-transition phenomena of polymers has started to be recognized only recently. The aim of this review is to give an overview and to critically revise the results reported on this topic over the last years. From these results, it seems to be evident that there are two different mechanisms involved in the dynamic arrest in glass-forming polymers: (i) the intermolecular packing effects, which dominate the dynamic arrest of low molecular weight glass-forming systems; and (ii) the effect of intra-macromolecular barriers combined with chain connectivity. It has also been shown that the mode coupling theory (MCT) is a suitable theoretical framework to discuss these questions. The values found for polymers for the central MCT parameter--the so-called λ-exponent--are of the order of 0.9, clearly higher than the standard values (λ ≈ 0.7) found in systems where the dynamic arrest is mainly driven by packing effects ('standard' glass-formers). Within the MCT, this is a signature of the presence of two competing mechanisms of dynamic arrest, as it has been observed in short-ranged attractive colloids or two component mixtures with

  4. Glass transition(s) of ionomers

    SciTech Connect

    Weiss, R.A.

    1994-09-01

    Ionomers are predominantly nonpolar polymers that contain a small amount of bonded salt groups. Microphase separation of ion-rich microdomains occurs as a consequence of the thermodynamic incompatibility of the salt groups and the polymer matrix and associative interactions between salt groups. Associations of the salt groups usually increase the glass transition of the continuous matrix phase, presumably as a consequence of the inhibition of chain mobility that accompanies physical crosslinking. The central question raised in this paper is whether the dispersed ion-rich microphase exhibits a glass transition. Although no glass transition for the microphase is detected by calorimetry, a dynamic mechanical relaxation is commonly observed above the T{sub g} of the matrix phase. This transition has some of the attributes of a glass transition, but it is not clear what is the actual relaxation process that is measured. This paper discusses the effect of the ionic groups on the matrix glass transition, the origin of the high-temperature dynamic mechanical transition, and the effects of the addition of plasticizers on the T{sub g} of the matrix and the higher temperature mechanical relaxation.

  5. Theories of glass formation and glass transition

    SciTech Connect

    Langer, James S.

    2014-03-19

    This key-issues review is a plea for a new focus on simpler and more realistic models of glass-forming fluids. It seems to me that we have too often been led astray by sophisticated mathematical models that beautifully capture some of the most intriguing features of glassy behavior, but are too unrealistic to provide bases for predictive theories. As illustrations of what I mean, the first part of this article is devoted to brief summaries of imaginative, sensible, but disparate and often contradictory ideas for solving glass problems. Almost all of these ideas remain alive today, with their own enthusiastic advocates. I then describe numerical simulations, mostly by H Tanaka and coworkers, in which it appears that very simple, polydisperse systems of hard disks and spheres develop long range, Ising-like, bond-orientational order as they approach glass transitions. Finally, a summary of my recent proposal that topologically ordered clusters of particles, in disordered environments, tend to become aligned with each other as if they were two-state systems, and thus produce the observed Ising-like behavior. Neither Tanaka’s results nor my proposed interpretation of them fit comfortably within any of the currently popular glass theories.

  6. Gauge theory of glass transition

    NASA Astrophysics Data System (ADS)

    Vasin, Mikhail

    2011-05-01

    A new analytical approach for the description of the glass transition in a frustrated system is suggested. The theory is based on the non-equilibrium dynamics technique, and takes into account the interaction of the local order field with the massive gauge field, which describes frustration-induced plastic deformation. The glass transition is regarded as a phase transition interrupted because of the premature critical slowing-down of one of the degrees of freedom caused by the frustrations. It is shown that freezing of the system appears when the correlation length and relaxation time of the gauge field diverge. The Vogel-Fulcher-Tammann relation for the transition kinetics and the critical exponent for the nonlinear susceptibility, 2.5\\lesssim \\gamma \\leq 3 , are derived in the framework of the suggested approach. An expression for the temperature dependence of the heat capacity near to the glass transition is derived. This dependence is qualitatively in good agreement with experimental data. The presented theory reproduces the characteristic form of the langphiphirangt correlation function dependence on time, and explains the boson peak appearance on this curve. In addition, the function of the glass transition temperature value with cooling rate is derived; this dependence fully conforms with known experimental data.

  7. Isoconversion Analysis of the Glass Transition

    NASA Astrophysics Data System (ADS)

    Badrinarayanan, Prashanth; Zheng, Wei; Simon, Sindee

    2007-03-01

    At temperatures below their glass transition temperatures (Tgs), glass forming materials deviate from equilibrium density and form a glass. The kinetic nature of the glass transition process is manifested in the cooling rate dependence of the glass transition temperature and by structural relaxation below Tg. Various facets of the glass transition kinetics have been well described by phenomenological models of the glass transition, such as the TNM and KAHR model. An important yet frequently questioned assumption in these models is that the apparent activation energy, which describes the temperature dependence of the relaxation time, does not vary during the glass transition process. Some recent reports suggest that the activation energy varies significantly during the glass transition process. In this work we apply an isoconversion analysis to data in the glass transition region which was obtained on cooling from capillary dilatometry and differential scanning calorimetry (DSC) in order to determine whether the apparent activation energy increases as the glassy state is approached.

  8. Physical phenomena in containerless glass processing

    NASA Technical Reports Server (NTRS)

    Subramanian, R. S.; Cole, R.; Annamalai, P.; Jayaraj, K.; Kondos, P.; Mcneil, T. J.; Shankar, N.

    1982-01-01

    Experiments were conducted on bubble migration in rotating liquid bodies contained in a sphere. Experiments were initiated on the migration of a drop in a slightly less dense continuous phase contained in a rotating sphere. A refined apparatus for the study of thermocapillar flow in a glass melt was built, and data were acquired on surface velocities in the melt. Similar data also were obtained from an ambient temperature fluid model. The data were analyzed and correlated with the aid of theory. Data were obtained on flow velocities in a pendant drop heated from above. The motion in this system was driven principally by thermocapillarity. An apparatus was designed for the study of volatilization from a glass melt.

  9. Colloquium: Water's controversial glass transitions

    NASA Astrophysics Data System (ADS)

    Amann-Winkel, Katrin; Böhmer, Roland; Fujara, Franz; Gainaru, Catalin; Geil, Burkhard; Loerting, Thomas

    2016-01-01

    Water is the most common and, judged from its numerous anomalous properties, the weirdest of all known liquids and the complexity of its pressure-temperature map is unsurpassed. A major obstacle on the way to a full understanding of water's structure and dynamics is the hard-to-explore territory within this map, colloquially named the no man's land. Many experiments suggest that just before stepping across its low-temperature border, amorphous ices undergo glass-to-liquid transitions while other interpretations emphasize the importance of underlying disordered (nano)crystalline states. Prospects for reconciling the conflicting views regarding the nature of water's glass transitions are discussed.

  10. Polyamorphic transitions in network glasses and glass-forming liquids

    NASA Astrophysics Data System (ADS)

    Kieffer, John

    2006-03-01

    Over the past two decades, we have witnessed increasing evidence for the occurrence of polyamorphism, i.e., the existence of more than one thermodynamically and structurally distinct non-crystalline state of a given substance. This concept is manifest predominantly through the transitions between different polyamorphic states, as we are still not able to unequivocally describe a given amorphous structure. However, if substantiated, the concept of polyamorphism should facilitate such a description, since it implies that polyamorphic states are uniquely defined and a distinctive structural character must exist for each state. We have observed polyamorphic transitions in a number of glass-forming systems, e.g., when probing their high-frequency visco-elastic response as a function of temperature,[1] or when compacting such systems at high pressures. We have carried out molecular dynamics simulations to reveal explanations for the phenomena observed in experiments.[2] In this presentation we discuss reversible and irreversible transitions in silica glass, their relation to the anomalous thermo-mechanical properties of this material, and the effects of permanent densification on structure and properties. We present an unusual transition in boron oxide glass, which is continuous upon compression and discontinuous upon decompression.[3] We show how the manifestations of polyamorphic transitions and their are related to structural transformations in the crystalline counterparts of these materials, and how this can even lead to the discovery of previously unknown metastable crystalline phases. [1] J. Kieffer, J.E. Masnik, O. Nickolayev, and J.D. Bass, Phys. Rev. B 58, 694 (1998). [2] L. Huang, and J. Kieffer, Phys. Rev. B 69, 224203 and 224204 (2004). [3] J.D. Nicholas, S.V. Sinogeikin, J. Kieffer, and J.D. Bass, Phys. Rev. Letters 92, 215701 (2004).

  11. Assessing transitional phenomena with the transitional object memory probe.

    PubMed

    Fowler, C; Hilsenroth, M J; Handler, L

    1998-01-01

    Winnicott's concept of transitional relatedness has captured the interest of psychoanalysts because it provides an understanding of the dialectical process occurring between inner and outer reality, and by extension, between analyst and analysand. Clinical observations related to transitional phenomena have led the authors to develop a projective early memory probe that assesses transitional phenomena. The transitional object early memory probe was tested both for its empirical validity and for its clinical utility in psychodynamic psychotherapy. Construct validity was assessed by comparing memory scores to the Rorschach Transitional Object Scale, as well as to therapist ratings of patient behaviors. Results demonstrated moderate correlations between early memory scores and Rorschach scale scores. Equally important was the finding that early memory scores were significantly correlated with therapist ratings of key behavioral patterns in therapy. A case vignette highlights the clinical application of the transitional object probe in assessing the capacity for transitional relatedness. In this case, the data gleaned from the patient's memories provided the therapist with a sharper focus on their role in the patient's growing capacity for more vital and creative contact with reality. PMID:9810109

  12. Glass Transitions in Polymer Nanocomposites

    NASA Astrophysics Data System (ADS)

    Meng, Dong; Kumar, Sanat

    2014-03-01

    For polymers are under geometric confinement, it is generally believed that the glass transition temperature (Tg) increases with favorable interfacial interactions. Experiments and simulations have reported that Tg increases almost proportionally to the attractive polymer-surface interactions. However, recent studies have reported the contradictory finding that the Tg shift is rather modest and insensitive to the strength of interfacial attractions. In this study, we investigate the glass transition in polymer nanocomposites using molecular dynamics simulations. With attractive polymer-nanoparticle (NP) interactions, we find that Tg is increased by ~ 3% at moderate loadings and that the shift stays almost unchanged when the polymer-NP attractions are further increased by one order of magnitude. Both are in agreement with the recent experiments at comparable NP loadings. We show that this is because the strongly adsorbed polymer segments do not participate in the glass transition. In other words, strong polymer-NP attractions create immobile polymer ``coatings'' around NPs that shield them from direct contact with the mobile polymers.

  13. Transition phenomena in unstably stratified turbulent flows.

    PubMed

    Bukai, M; Eidelman, A; Elperin, T; Kleeorin, N; Rogachevskii, I; Sapir-Katiraie, I

    2011-03-01

    We study experimentally and theoretically the transition phenomena caused by external forcing from Rayleigh-Bénard convection with large-scale circulation (LSC) to the limiting regime of unstably stratified turbulent flow without LSC, where the temperature field behaves like a passive scalar. In the experiments we use the Rayleigh-Bénard apparatus with an additional source of turbulence produced by two oscillating grids located near the sidewalls of the chamber. When the frequency of the grid oscillations is larger than 2 Hz, the LSC in turbulent convection is destroyed, and the destruction of the LSC is accompanied by a strong change of the mean temperature distribution. However, in all regimes of the unstably stratified turbulent flow the ratio [(ℓ{x}∇{x}T)²+(ℓ{y}∇{y}T)² + (ℓ{z}∇{z}T)²]/<θ²> varies slightly (even in the range of parameters where the behavior of the temperature field is different from that of the passive scalar). Here ℓ{i} are the integral scales of turbulence along the x,y,z directions, and T and θ are the mean and fluctuating parts of the fluid temperature. At all frequencies of the grid oscillations we have detected long-term nonlinear oscillations of the mean temperature. The theoretical predictions based on the budget equations for turbulent kinetic energy, turbulent temperature fluctuations, and turbulent heat flux, are in agreement with the experimental results. PMID:21517582

  14. Pressure dependence of glass transition temperature of elastomeric glasses

    NASA Astrophysics Data System (ADS)

    Pae, K. D.; Tang, C.-L.; Shin, E.-S.

    1984-11-01

    The pressure dependence of the glass transition temperature Tg of two elastomers, Solithane 113 and 3,3-bis(azidomethyl)oxetane/tetrahydrofuran (BAMO/THF) has been determined, employing high-pressure differential thermal analysis (HP-DTA) and dielectric techniques, up to 8.5 kbar. The glasses of the elastomers were named the specific (or Pi glass) or the general glass depending on how the glasses were formed. A Pi glass was formed by lowering temperature under a constant pressure (Pi) and the pressure dependency of the Pi glass was determined after changing pressure only in the glassy state. The general glass consists of a series of specific glasses but the Tg is determined only at pressures under which the glass is formed. The Tg for both glasses increased with increasing pressure. However, the Tg for the Pi glass appears to level off at very high pressures while the Tg does not level off for the general glass. Thermodynamic analysis was made to show that for many general glasses dTg/dP=Δβ/(1+n)Δα holds, in which n=1 for Solithane and many other glasses. It is also shown that a modified Gibbs and DiMarzio theory can be used effectively to predict the observed experimental results.

  15. Glass transition and stable glass formation of tetrachloromethane

    NASA Astrophysics Data System (ADS)

    Chua, Y. Z.; Tylinski, M.; Tatsumi, S.; Ediger, M. D.; Schick, C.

    2016-06-01

    Physical vapor deposition (PVD) has been used to prepare organic glasses with very high kinetic stability and it has been suggested that molecular anisotropy is a prerequisite for stable glass formation. Here we use PVD to prepare glasses of tetrachloromethane, a simple organic molecule with a nearly isotropic molecular structure. In situ AC nanocalorimetry was used to characterize the vapor-deposited glasses. Glasses of high kinetic stability were produced by deposition near 0.8 Tg. The isothermal transformation of the vapor-deposited glasses into the supercooled liquid state gave further evidence that tetrachloromethane forms glasses with high kinetic stability, with the transformation time exceeding the structural relaxation time of the supercooled liquid by a factor of 103. The glass transition temperature of liquid-cooled tetrachloromethane is determined as Tg ≈ 78 K, which is different from previously reported values. The frequency dependence of the glass transition was also determined and the fragility was estimated as m ≈ 118. The successful formation of PVD glasses of tetrachloromethane which have high kinetic stability argues that molecular asymmetry is not a prerequisite for stable glass formation.

  16. Glass transition and stable glass formation of tetrachloromethane.

    PubMed

    Chua, Y Z; Tylinski, M; Tatsumi, S; Ediger, M D; Schick, C

    2016-06-28

    Physical vapor deposition (PVD) has been used to prepare organic glasses with very high kinetic stability and it has been suggested that molecular anisotropy is a prerequisite for stable glass formation. Here we use PVD to prepare glasses of tetrachloromethane, a simple organic molecule with a nearly isotropic molecular structure. In situ AC nanocalorimetry was used to characterize the vapor-deposited glasses. Glasses of high kinetic stability were produced by deposition near 0.8 Tg. The isothermal transformation of the vapor-deposited glasses into the supercooled liquid state gave further evidence that tetrachloromethane forms glasses with high kinetic stability, with the transformation time exceeding the structural relaxation time of the supercooled liquid by a factor of 10(3). The glass transition temperature of liquid-cooled tetrachloromethane is determined as Tg ≈ 78 K, which is different from previously reported values. The frequency dependence of the glass transition was also determined and the fragility was estimated as m ≈ 118. The successful formation of PVD glasses of tetrachloromethane which have high kinetic stability argues that molecular asymmetry is not a prerequisite for stable glass formation. PMID:27369523

  17. Electron anions and the glass transition temperature.

    PubMed

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

    2016-09-01

    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. The 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 unique avenue in rational materials design. PMID:27559083

  18. Mechanical failure and glass transition in metallic glasses

    SciTech Connect

    Egami, Takeshi

    2011-01-01

    The current majority view on the phenomenon of mechanical failure in metallic glasses appears to be that it is caused by the activity of some structural defects, such as free-volumes or shear transformation zones, and the concentration of such defects is small, only of the order of 1%. However, the recent results compel us to revise this view. Through molecular dynamics simulation it has been shown that mechanical failure is the stress-induced glass transition. According to our theory the concentration of the liquid-like sites (defects) is well over 20% at the glass transition. We suggest that the defect concentration in metallic glasses is actually very high, and percolation of such defects causes atomic avalanche and mechanical failure. In this article we discuss the glass transition, mechanical failure and viscosity from such a point of view.

  19. Excitation Chains at the Glass Transition

    SciTech Connect

    Langer, J. S.

    2006-09-15

    The excitation-chain theory of the glass transition, proposed in an earlier publication, predicts diverging, super-Arrhenius relaxation times and, via a similarly diverging length scale, suggests a way of understanding the relations between dynamic and thermodynamic properties of glass-forming liquids. I argue here that critically large excitation chains play a role roughly analogous to that played by critical clusters in the droplet model of vapor condensation. Unlike a first-order condensation point in a vapor, the glass transition is not a conventional phase transformation, and may not be a thermodynamic transition at all.

  20. Understanding the glass transition in GeSbTe materials

    NASA Astrophysics Data System (ADS)

    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.

  1. Chemically induced transition phenomena in polyurethanes as seen from generalized mode Grüneisen parameters.

    PubMed

    Müller, U; Philipp, M; Bactavatchalou, R; Sanctuary, R; Baller, J; Zielinski, B; Possart, W; Alnot, P; Krüger, J K

    2008-05-21

    Many phenomenological properties of reactive polymers like polyurethanes increase or decrease continuously in the course of the curing process before saturating at the end of the chemical reaction. This holds true for instance for the mass density, the refractive index, the chemical turnover and the hypersonic properties. The reason for this monotone behaviour is that the chemical reaction behaves like a continuous succession of irreversible phase transitions. These transitions are superposed by the sol-gel transition and possibly by the chemically induced glass transition, with the drawback that the latter two highlighted transitions are often hidden by the underlying curing process. In this work we propose generalized mode Grüneisen parameters as an alternative probe for elucidating the polymerization process itself and the closely related transition phenomena. As a model system we use polyurethane composed of a diisocyanate and varying ratios of difunctional and trifunctional alcohols. PMID:21694282

  2. Kauzmann's paradox and the glass transition.

    PubMed

    Speedy, Robin J

    2003-09-01

    Kauzmann showed that the entropy of a liquid decreases rapidly on cooling towards the kinetic glass transition temperature and extrapolates to unreasonable values at lower temperature. The temperature where the extrapolated liquid entropy meets the crystal entropy is now called the Kauzmann temperature. Thermodynamics, with Planck's statement of the third law, shows that the entropy of a liquid cannot be less than the entropy of a glass with the same enthalpy. This is the thermodynamic condition violated by the Kauzmann extrapolation and it suggests a thermodynamic glass transition. Simulations show that, for the simple models studied and regardless of how the liquid entropy is extrapolated, the Kauzmann temperature cannot be reached because the entropy of glasses with the same enthalpy as the liquid is greater than that of the crystal. PMID:14499908

  3. Strain induced fragility transition in metallic glass

    PubMed Central

    Yu, Hai-Bin; Richert, Ranko; Maaß, Robert; Samwer, Konrad

    2015-01-01

    Relaxation dynamics are the central topic in glassy physics. Recently, there is an emerging view that mechanical strain plays a similar role as temperature in altering the relaxation dynamics. Here, we report that mechanical strain in a model metallic glass modulates the relaxation dynamics in unexpected ways. We find that a large strain amplitude makes a fragile liquid become stronger, reduces dynamical heterogeneity at the glass transition and broadens the loss spectra asymmetrically, in addition to speeding up the relaxation dynamics. These findings demonstrate the distinctive roles of strain compared with temperature on the relaxation dynamics and indicate that dynamical heterogeneity inherently relates to the fragility of glass-forming materials. PMID:25981888

  4. Application of Glass Transition in Food Processing.

    PubMed

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

    2016-04-25

    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. PMID:25118113

  5. Investigation of Glass Transition Temperature of Binary Tellurite Glasses

    SciTech Connect

    Chippy, L.; Unnithan, C. Harikuttan; Jayakumar, S.

    2011-10-20

    Five series of binary Tellurite glass samples containing Sb{sub 2}O{sub 4}, WO{sub 3}, Fe{sub 2}O{sub 3}, Na{sub 2}O and ZnO{sub 2} are studied in terms of the variation of glass transition temperature (T{sub g}). It is seen that Tg increases as Tellurite concentration decreases in the case of glasses containing metal oxides Sb{sub 2}O{sub 4} WO{sub 3}, and Fe{sub 2}O{sub 3} while T{sub g} shows a decreasing trend with that of Na{sub 2}O and ZnO and the corresponding changes in the network structure are accounted to possible extent. The structural variations are analyzed using the concept of electronegativity.

  6. Bulk and interfacial glass transitions of water.

    PubMed

    Bhattacharya, Deepanjan; Payne, Candace N; Sadtchenko, Vlad

    2011-06-16

    Fast scanning calorimetry (FSC) was employed to investigate glass softening dynamics in bulk-like and ultrathin glassy water films. Bulk-like water samples were prepared by vapor-deposition on the surface of a tungsten filament near 140 K where vapor-deposition results in low enthalpy glassy water films. The vapor-deposition approach was also used to grow multiple nanoscale (approximately 50 nm thick) water films alternated with benzene and methanoic films of similar dimensions. When heated from cryogenic temperatures, the ultrathin water films underwent a well manifested glass softening transition at temperatures 20 K below the onset of crystallization. However, no such transition was observed in bulk-like samples prior to their crystallization. These results indicate that thin-film water demonstrates glass softening dynamics that are dramatically distinct from those of the bulk phase. We attribute these differences to water's interfacial glass transition, which occurs at temperatures tens of degrees lower than that in the bulk. Implications of these findings for past studies of glass softening dynamics in various glassy water samples are discussed. PMID:21401034

  7. Superconducting Metallic Glass Transition-Edge-Sensors

    NASA Technical Reports Server (NTRS)

    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.

  8. Critical Phenomena of the Disorder Driven Localization-Delocalization Transition

    SciTech Connect

    Marc Ruhlander

    2002-12-31

    Metal-to-insulator transitions are generally linked to two phenomena: electron-electron correlations and disorder. Although real systems are usually responding to a mixture of both, they can be classified as undergoing a Mott-transition, if the former process dominates, or an Anderson-transition, if the latter dominates. High-T{sub c} superconductors, e.g., are a candidate for the first class. Materials in which disorder drives the metal-to-insulator transition include doped semiconductors and amorphous materials. After briefly reviewing the previous research on transport in disordered materials and the disorder-induced metal-to-insulator transition, a summary of the model and the methods used in subsequent chapters is given.

  9. Water’s second glass transition

    PubMed Central

    Amann-Winkel, Katrin; Gainaru, Catalin; Handle, Philip H.; Seidl, Markus; Nelson, Helge; Böhmer, Roland

    2013-01-01

    The glassy states of water are of common interest as the majority of H2O in space is in the glassy state and especially because a proper description of this phenomenon is considered to be the key to our understanding why liquid water shows exceptional properties, different from all other liquids. The occurrence of water’s calorimetric glass transition of low-density amorphous ice at 136 K has been discussed controversially for many years because its calorimetric signature is very feeble. Here, we report that high-density amorphous ice at ambient pressure shows a distinct calorimetric glass transitions at 116 K and present evidence that this second glass transition involves liquid-like translational mobility of water molecules. This “double Tg scenario” is related to the coexistence of two liquid phases. The calorimetric signature of the second glass transition is much less feeble, with a heat capacity increase at Tg,2 about five times as large as at Tg,1. By using broadband-dielectric spectroscopy we resolve loss peaks yielding relaxation times near 100 s at 126 K for low-density amorphous ice and at 110 K for high-density amorphous ice as signatures of these two distinct glass transitions. Temperature-dependent dielectric data and heating-rate–dependent calorimetric data allow us to construct the relaxation map for the two distinct phases of water and to extract fragility indices m = 14 for the low-density and m = 20–25 for the high-density liquid. Thus, low-density liquid is classified as the strongest of all liquids known (“superstrong”), and also high-density liquid is classified as a strong liquid. PMID:24101518

  10. Mechanisms of Rhyolitic Glass Hydration Below the Glass Transition

    SciTech Connect

    Anovitz, Lawrence {Larry} M; Cole, David R; Fayek, Mostafa

    2008-01-01

    Although a great deal is known about the interaction between water and rhyolitic glasses and melts at temperatures above the glass transition, the nature of this interaction at lower temperatures is much more obscure. Comparisons between high- and low-temperature diffusion studies suggest that several factors play important roles under lower-temperature conditions that are not significant at higher temperatures. Water concentrations in rhyolitic glasses hydrated at low temperatures are significantly greater than in those hydrated at high temperatures and low pressures. Surface concentrations, which equilibrate quickly with the surrounding environment at high temperature, change far more slowly as temperature decreases, and may not equilibrate at room temperature for hundreds or thousands of years. Temperature extrapolations of high- and low-temperature diffusion data are not consistent, suggesting that a change in mechanism occurs. These differences may be due to the inability of "self-stress," caused by the in-diffusing species, to relax at lower temperature. Preliminary calculations suggest that the level of stress caused by glass-water interaction may be greater than the tensile strength of the glass. On a microstuctural scale, extrapolations of high-temperature Fourier transform infrared spectroscopy (FTIR) data to lower temperatures suggests that there should be little or no hydroxyl present in glasses hydrated at low temperature. Comparisons of low-temperature hydration results among SiO2, obsidian, and albite compositions show distinct differences, and features are present in the spectra that do not occur at high temperature. Analysis of H2O and D2O diffusion also suggest that mechanistic differences occur between low- and high-temperature diffusive processes.

  11. Two glass transitions in miscible polymer blends?

    SciTech Connect

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

    2014-06-28

    In contrast to mixtures of two small molecule fluids, miscible binary polymer blends often exhibit two structural relaxation times and two glass transition temperatures. Qualitative explanations postulate phenomenological models of local concentration enhancements due to chain connectivity in ideal, fully miscible systems. We develop a quantitative theory that explains qualitative trends in the dynamics of real miscible polymer blends which are never ideal mixtures. The theory is a synthesis of the lattice cluster theory of blend thermodynamics, the generalized entropy theory for glass-formation in polymer materials, and the Kirkwood-Buff theory for concentration fluctuations in binary mixtures.

  12. Theories of glass formation and the glass transition

    NASA Astrophysics Data System (ADS)

    Langer, J. S.

    2014-04-01

    This key-issues review is a plea for a new focus on simpler and more realistic models of glass-forming fluids. It seems to me that we have too often been led astray by sophisticated mathematical models that beautifully capture some of the most intriguing features of glassy behavior, but are too unrealistic to provide bases for predictive theories. As illustrations of what I mean, the first part of this article is devoted to brief summaries of imaginative, sensible, but disparate and often contradictory ideas for solving glass problems. Almost all of these ideas remain alive today, with their own enthusiastic advocates. I then describe numerical simulations, mostly by H Tanaka and coworkers, in which it appears that very simple, polydisperse systems of hard disks and spheres develop long range, Ising-like, bond-orientational order as they approach glass transitions. Finally, I summarize my recent proposal that topologically ordered clusters of particles, in disordered environments, tend to become aligned with each other as if they were two-state systems, and thus produce the observed Ising-like behavior. Neither Tanaka's results nor my proposed interpretation of them fit comfortably within any of the currently popular glass theories.

  13. Dielectric determination of the glass transition temperature (T sub g)

    NASA Technical Reports Server (NTRS)

    Ries, Heidi R.

    1990-01-01

    The objective is to determine the glass transition temperature of a polymer using a dielectric dissipation technique. A peak in the dissipation factor versus temperature curve is expected near the glass transition temperature T sub g. It should be noted that the glass transition is gradual rather than abrupt, so that the glass transition temperature T sub g is not clearly identifiable. In this case, the glass transition temperature is defined to be the temperature at the intersection point of the tangent lines to the dissipation factor versus temperature curve above and below the transition region, as illustrated.

  14. Glass transition temperature and topological constraints of sodium borophosphate glass-forming liquids

    NASA Astrophysics Data System (ADS)

    Jiang, Qi; Zeng, Huidan; Liu, Zhao; Ren, Jing; Chen, Guorong; Wang, Zhaofeng; Sun, Luyi; Zhao, Donghui

    2013-09-01

    Sodium borophosphate glasses exhibit intriguing mixed network former effect, with the nonlinear compositional dependence of their glass transition temperature as one of the most typical examples. In this paper, we establish the widely applicable topological constraint model of sodium borophosphate mixed network former glasses to explain the relationship between the internal structure and nonlinear changes of glass transition temperature. The application of glass topology network was discussed in detail in terms of the unified methodology for the quantitative distribution of each coordinated boron and phosphorus units and glass transition temperature dependence of atomic constraints. An accurate prediction of composition scaling of the glass transition temperature was obtained based on topological constraint model.

  15. Structural signatures evidenced in dynamic crossover phenomena in metallic glass-forming liquids

    NASA Astrophysics Data System (ADS)

    Hu, Y. C.; Li, F. X.; Li, M. Z.; Bai, H. Y.; Wang, W. H.

    2016-05-01

    Molecular dynamics simulations were performed to investigate dynamic evolution in metallic glass-forming liquids during quenching from high temperature above melting point down to supercooled region. Two crossover temperatures TA and TS (TA > TS) are identified, and their physical meanings are clarified. TA and TS are found to be not only the sign of dynamic crossover phenomena but also the manifestation of two key structure correlation lengths ξ s . As temperature decreases below TA, ξ s goes beyond the nearest-neighbor distance, resulting in the Arrhenius-to-non-Arrhenius transition of structural relaxation time and the failure of Stokes-Einstein (SE) relation. As TS is traversed, the increase rate of ξ s reaches the maximum, leading to the simultaneous appearance of dynamical heterogeneity and fractional SE relation. It is further found that structure correlation increases much faster than dynamic correlation, playing a role of structural precursor for dynamic evolution in liquids. Thus, a structural link is established for deeper understanding dynamic crossover phenomena.

  16. Mutarotational kinetics and glass transition of lactose

    NASA Astrophysics Data System (ADS)

    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.

  17. Scaling and universality in glass transition.

    PubMed

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

    2016-01-01

    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 〈q(t)〉 and the dynamical susceptibility 〈q(2)(t)〉 - 〈q(t)〉(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. PMID:27221056

  18. Scaling and universality in glass transition

    PubMed Central

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

    2016-01-01

    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 〈q(t)〉 and the dynamical susceptibility 〈q2(t)〉 − 〈q(t)〉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. PMID:27221056

  19. Scaling and universality in glass transition

    NASA Astrophysics Data System (ADS)

    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.

  20. Probing the Glass Transition from Structural and Vibrational Properties of Zero-Temperature Glasses

    NASA Astrophysics Data System (ADS)

    Wang, Lijin; Xu, Ning

    2014-02-01

    We find that the density dependence of the glass transition temperature of Lennard-Jones (LJ) and Weeks-Chandler-Andersen (WCA) systems can be predicted from properties of the zero-temperature (T=0) glasses. Below a crossover density ρs, LJ and WCA glasses show different structures, leading to different vibrational properties and consequently making LJ glasses more stable with higher glass transition temperatures than WCA ones. Above ρs, structural and vibrational quantities of the T =0 glasses show scaling collapse. From scaling relations and dimensional analysis, we predict a density scaling of the glass transition temperature, in excellent agreement with simulation results. We also propose an empirical expression of the glass transition temperature using structural and vibrational properties of the T=0 glasses, which works well over a wide range of densities.

  1. Phenomena of solid state grain boundaries phase transition in technology

    NASA Astrophysics Data System (ADS)

    Minaev, Y. A.

    2015-03-01

    The results of study the phenomenon, discovered by author (1971), of the phase transition of grain boundary by the formation of two-dimensional liquid or quasi-liquid films have been done. The described phenomena of the first order phase transition (two-dimensional melting) at temperatures 0.6 - 0.9 TS0 (of the solid state melting point) is a fundamental property of solid crystalline materials, which has allowed to revise radically scientific representations about a solid state of substance. Using the mathematical tools of the film thermodynamics it has been obtained the generalized equation of Clausius - Clapeyron type for two-dimensional phase transition. The generalized equation has been used for calculating grain boundary phase transition temperature TSf of any metal, which value lies in the range of (0.55…0.86) TS0. Based on these works conclusions the develop strategies for effective forming of coatings (by thermo-chemical processing) on surface layers of functional alloys and hard metals have been made. The short overview of the results of some graded alloys characterization has been done.

  2. Phenomena of solid state grain boundaries phase transition in technology

    SciTech Connect

    Minaev, Y. A.

    2015-03-30

    The results of study the phenomenon, discovered by author (1971), of the phase transition of grain boundary by the formation of two-dimensional liquid or quasi-liquid films have been done. The described phenomena of the first order phase transition (two-dimensional melting) at temperatures 0.6 – 0.9 T{sub S0} (of the solid state melting point) is a fundamental property of solid crystalline materials, which has allowed to revise radically scientific representations about a solid state of substance. Using the mathematical tools of the film thermodynamics it has been obtained the generalized equation of Clausius - Clapeyron type for two-dimensional phase transition. The generalized equation has been used for calculating grain boundary phase transition temperature T{sub Sf} of any metal, which value lies in the range of (0.55…0.86) T{sub S0}. Based on these works conclusions the develop strategies for effective forming of coatings (by thermo-chemical processing) on surface layers of functional alloys and hard metals have been made. The short overview of the results of some graded alloys characterization has been done.

  3. Glass/Jamming Transition in Colloidal Aggregation

    NASA Technical Reports Server (NTRS)

    Segre, Philip N.; Prasad, Vikram; Weitz, David A.; Rose, M. Franklin (Technical Monitor)

    2000-01-01

    We have studied colloidal aggregation in a model colloid plus polymer system with short-range attractive interactions. By varying the colloid concentration and the strength of the attraction, we explored regions where the equilibrium phase is expected to consist of colloidal crystallites in coexistance with colloidal gas (i.e. monomers). This occurs for moderate values of the potential depth, U approximately equal to 2-5 kT. Crystallization was not always observed. Rather, over an extended sub-region two new metastable phases appear, one fluid-like and one solid-like. These were examined in detail with light scattering and microscopy techniques. Both phases consist of a near uniform distribution of small irregular shaped clusters of colloidal particles. The dynamical and structural characteristics of the ergodic-nonergodic transition between the two phases share much in common with the colloidal hard sphere glass transition.

  4. Ionic conductivity and glass transition of phosphoric acids

    SciTech Connect

    Wang, Yangyang; Lane, Nathan A; Sun, Che-Nan; Fan, Fei; Zawodzinski, Thomas; Sokolov, Alexei P

    2013-01-01

    Here we report the low-temperature dielectric and viscoelastic properties of phosphoric acids in the range of H2O:P2O5 1.5 5. Both dielectric and viscosity measurements allow us to determine the glass-transition temperatures of phosphoric acids. The obtained glass-transition temperatures are in good agreement with previous differential scanning calorimetric measurements. Moreover, our analysis reveals moderate decoupling of ionic conductivity from structural relaxation in the vicinity of the glass transition.

  5. Ionic Ckonductivity and Glass Transition of Phosphoric Acids

    SciTech Connect

    Wang, Yangyang; Lane, Nathan A; Sun, Che-Nan; Fan, Fei; Zawodzinski, Thomas; Sokolov, Alexei P

    2013-01-01

    Here we report the low-temperature dielectric and viscoelastic properties of phosphoric acids in the range of H2O:P2O5 1.5 5. Both dielectric and viscosity measurements allow us to determine the glass-transition temperatures of phosphoric acids. The obtained glass-transition temperatures are in good agreement with previous differential scanning calorimetric measurements. Moreover, our analysis reveals moderate decoupling of ionic conductivity from structural relaxation in the vicinity of the glass transition.

  6. PREFACE: Fourh Workshop on Non-Equilibrium Phenomena in Supercooled Fluids, Glasses and Amorphous Materials

    NASA Astrophysics Data System (ADS)

    Andreozzi, Laura; Giordano, Marco; Leporini, Dino; Tosi, Mario

    2007-04-01

    round-table discussion sessions were organized to discuss issues that have special impact on our current understanding (or lack of it) of the dynamics of glass transition: 'Low-energy excitations and relaxations in glasses' and 'An assessment of current theories: interconnections and relevance to experiments'. We are very grateful to M A Ramos and R Bömer, and to P G Debenedetti and H Z Cummins for organizing and leading these two activities. Two very active and profitable poster sessions collected contributions on the themes of relaxation processes, cooperativity in polymers and mixtures, polyamorphism and water, biomaterials, relaxation, aging phenomena in thin films, confined and complex systems, and theoretical aspect, energy landscape and molecular dynamics, low temperature, glass and PT procedures, tracer dynamics, heterogeneity and relaxation in glass formers We acknowledge the generous support given to the workshop by our institutions, and in particular by Scuola Normale Superiore. The organization of the events in its beautiful rooms and corridors, as well as the lunches and coffee breaks held in its courtyard, especially favoured meetings and discussions between the participants. Several public and private Institutions have also supported our efforts and we would like to thank them warmly: they are the 'Soft Matter' Center of Rome, the INFN Section in Pisa, the CNR/INFM Polylab, and Ital Scientifica, TA Instruments, Novocontrol Technologies, Up Group, Isole e Olena. Finally, we express our gratitude to all those individuals—we mention here in particular Dr Ciro Autiero, Dr Massimo Faetti, Dr Fabio Zulli, Ms Patrizia Pucci, and Ms Caterina D'Elia—who have given their work and time to the making and running of the Workshop.

  7. Approaching the Glass Transition from Various Directions

    NASA Astrophysics Data System (ADS)

    Lipson, Jane

    2015-03-01

    In recent years a significant amount of experimental work has appeared on glassy systems, both polymeric and small molecule. However, this rich explosion in data has not been met with a concomitant leap in fundamental understanding. We have developed a number of approaches to elucidate some of the underlying mechanisms of behaviour in bulk and confined glassy systems. Using our Limited Mobility (LM) coarse-grained simulation model we have characterized the dynamic heterogeneity associated with approaching the glass transition, explored interfacial behaviour when layering materials of differing mobility, and analyzed the effect of a free surface on a supported thin film. Approaching related problems from a different direction we have modified a simple thermodynamic description of the bulk to account for missing interactions at a film surface, and substrate interactions in the case of supported films. Characterizing the systems via bulk data alone, we find our film-averaged predictions for the effects of confinement agree well with experimental data on several freestanding and supported polymer films. That work deals with confined systems; a fundamental understanding of bulk glass transitions also remains incomplete. Most recently we have been applying our Locally Correlated Lattice (LCL) equation of state model, which has met with success in modeling polymer melt and mixture behaviour, to reveal hints of the underlying glassy nature of a bulk polymer sample, even while above its transition temperature (Tg). Correlations between Tg and a variety of equilibrium bulk quantities have lead us to make connections not only with a substantive amount of experimental data on a wide range of polymers, but also with other models of glassy polymeric systems. This talk will comprise an efficient summary of past progress from these different directions, and will then focus on our most recent results and current understanding. This work has been supported by NSF-DMR and GAANN.

  8. Dynamics and thermodynamics of the glass transition

    SciTech Connect

    Langer, J.S.

    2006-04-15

    The principal theme of this paper is that anomalously slow, super-Arrhenius relaxations in glassy materials may be activated processes involving chains of molecular displacements. As pointed out in a preceding paper with Lemaitre, the entropy of critically long excitation chains can enable them to grow without bound, thus activating stable thermal fluctuations in the local density or molecular coordination of the material. I argue here that the intrinsic molecular-scale disorder in a glass plays an essential role in determining the activation rate for such chains, and show that a simple disorder-related correction to the earlier theory recovers the Vogel-Fulcher law in three dimensions. A key feature of this theory is that the spatial extent of critically long excitation chains diverges at the Vogel-Fulcher temperature. I speculate that this diverging length scale implies that, as the temperature decreases, increasingly large regions of the system become frozen and do not contribute to the configurational entropy, and thus ergodicity is partially broken in the super-Arrhenius region above the Kauzmann temperature T{sub K}. This partially broken ergodicity seems to explain the vanishing entropy at T{sub K} and other observed relations between dynamics and thermodynamics at the glass transition.

  9. Quantitative field theory of the glass transition

    PubMed Central

    Franz, Silvio; Jacquin, Hugo; Parisi, Giorgio; Urbani, Pierfrancesco; Zamponi, Francesco

    2012-01-01

    We develop a full microscopic replica field theory of the dynamical transition in glasses. By studying the soft modes that appear at the dynamical temperature, we obtain an effective theory for the critical fluctuations. This analysis leads to several results: we give expressions for the mean field critical exponents, and we analytically study the critical behavior of a set of four-points correlation functions, from which we can extract the dynamical correlation length. Finally, we can obtain a Ginzburg criterion that states the range of validity of our analysis. We compute all these quantities within the hypernetted chain approximation for the Gibbs free energy, and we find results that are consistent with numerical simulations. PMID:23112202

  10. Supercooled water and the kinetic glass transition

    NASA Astrophysics Data System (ADS)

    Sciortino, F.; Gallo, P.; Tartaglia, P.; Chen, S.-H.

    1996-12-01

    We present a molecular-dynamics study of the self-dynamics of water molecules in deeply supercooled liquid states. We find that the decay of single-particle dynamics correlation functions is characterized by a fast initial relaxation toward a plateau and by a region of self-similar dynamics, followed at late times by a stretched exponential decay. We interpret such results in the framework of the mode-coupling theory for supercooled liquids. We relate the apparent anomalies of the transport coefficients in water on lowering the temperature to the formation of cages and to the associated slow dynamics resulting from the presence of long-lived molecular cages. The so-called critical Angell temperature in supercooled water could thus be interpreted as kinetic glass transition temperature, relaxing the need of a thermodynamic singularity for the explanation of the anomalies of liquid water.

  11. An ideal glass transition in supercooled water?

    NASA Astrophysics Data System (ADS)

    Sciortino, F.; Chen, S. H.; Gallo, P.; Tartaglia, P.

    Analyzing recent molecular dynamics simulations in deeply supercooled liquid states, we have found that the single particle dynamics in water can be interpreted in terms of Mode Coupling Theory, in its so-called ideal formulation. In this paper we review such evidence and discuss the relevance of this finding for the debated thermodynamic behavior of supercooled water. The experimental apparent power-law behavior of the transport coefficients in water, diverging or going to zero at the so-called Angell temperature could indeed be interpreted as a kinetic, as distinct from thermodynamic, phenomena. This finding removes the need of a thermodynamic singularity for the explanation of the anomalies of liquid water. We also comment on the development of a significant harmonic dynamics on cooling the liquid, which could indicate a transition from a fragile to a strong behavior in liquid water.

  12. PREFACE: Dynamic crossover phenomena in water and other glass-forming liquids Dynamic crossover phenomena in water and other glass-forming liquids

    NASA Astrophysics Data System (ADS)

    Chen, Sow-Hsin; Baglioni, Piero

    2012-02-01

    protein hydration water Francesco Mallamace, Carmelo Corsaro, Piero Baglioni, Emiliano Fratini and Sow-Hsin Chen Common features in the microscopic dynamics of hydration water on organic and inorganic surfacesE Mamontov, H O'Neill, Q Zhang, W Wang and D J Wesolowski Water dynamics as affected by interaction with biomolecules and change of thermodynamic state: a neutron scattering studyA Orecchini, A Paciaroni, C Petrillo, F Sebastiani, A De Francesco and F Sacchetti Temperature dependence of structure and density for D2O confined in MCM-41-SWilliam A Kamitakahara, Antonio Faraone, Kao-Hsiang Liu and Chung-Yuan Mou Density profile of water confined in cylindrical pores in MCM-41 silicaAlan K Soper Dynamic crossover in hydration water of curing cement paste: the effect of superplasticizerHua Li, Wei-Shan Chiang, Emiliano Fratini, Francesca Ridi, Francesco Bausi, Piero Baglioni, Madhu Tyagi and Sow-Hsin Chen Water confined in MCM-41: a mode coupling theory analysisP Gallo, M Rovere and S-H Chen Computer simulations of dynamic crossover phenomena in nanoconfined waterG B Suffritti, P Demontis, J Gulín-Gonźlez and M Masia Hydrophobic nanoconfinement suppresses fluctuations in supercooled waterE G Strekalova, M G Mazza, H E Stanley and G Franzese Other glass-forming liquids Quasi-elastic neutron scattering studies of the slow dynamics of supercooled and glassy aspirinYang Zhang, Madhusudan Tyagi, Eugene Mamontov and Sow-Hsin Chen Colloids Phase diagram of trivalent and pentavalent patchy particlesFlavio Romano, Eduardo Sanz, Piero Tartaglia and Francesco Sciortino Distinguishing the monomer to cluster phase transition in concentrated lysozyme solutions by studying the temperature dependence of the short-time dynamicsPéter Falus, Lionel Porcar, Emiliano Fratini, Wei-Ren Chen, Antonio Faraone, Kunlun Hong, Piero Baglioni and Yun Liu Contrast variation in spin-echo small angle neutron scatteringXin Li, Bin Wu, Yun Liu, Roger Pynn, Chwen-Yang Shew, Gregory S Smith, Kenneth W

  13. Modern aspects of the kinetic theory of glass transition

    NASA Astrophysics Data System (ADS)

    Tropin, T. V.; Schmelzer, J. W.; Aksenov, V. L.

    2016-01-01

    This paper reviews glass transition kinetics models that are developed to describe the formation of structural (for example, covalent and metallic) glasses, as well as to account for the transition of a polymer to a solid glassy state. As the two approaches most frequently used over the last decade to model the glass transition, the Tool–Narayanaswamy–Moynihan model and the Adam–Gibbs theory of glass transition are described together with examples of their applications. Also discussed are entropy-based approaches that rely on irreversible thermodynamics methods originated in the work of De Donder, Mandelstam, and Leontovich. The actual problems that arise in applying these methods and the prospects of their development are discussed. A brief overview of statistical glass transition models is given, including the mode-coupling and energy-landscape theories.

  14. Does Brillouin light scattering probe the primary glass transition process at temperatures well above glass transition?

    NASA Astrophysics Data System (ADS)

    Voudouris, P.; Gomopoulos, N.; Le Grand, A.; Hadjichristidis, N.; Floudas, G.; Ediger, M. D.; Fytas, G.

    2010-02-01

    The primary α-relaxation time (τα) for molecular and polymeric glass formers probed by dielectric spectroscopy and two light scattering techniques (depolarized light scattering and photon correlation spectroscopy) relates to the decay of the torsional autocorrelation function computed by molecular dynamics simulation. It is well known that Brillouin light scattering spectroscopy (BLS) operating in gigahertz frequencies probes a fast (10-100 ps) relaxation of the longitudinal modulus M∗. The characteristic relaxation time, irrespective of the fitting procedure, is faster than the α-relaxation which obeys the non-Arrhenius Vogel-Fulcher-Tammann equation. Albeit, this has been noticed, it remains a puzzling finding in glass forming systems. The available knowledge is based only on temperature dependent BLS experiments performed, however, at a single wave vector (frequency). Using a new BLS spectrometer, we studied the phonon dispersion at gigahertz frequencies in molecular [o-terphenyl (OTP)] and polymeric [polyisoprene (PI) and polypropylene (PP)] glass formers. We found that the hypersonic dispersion does relate to the glass transition dynamics but the disparity between the BLS-relaxation times and τα is system dependent. In PI and PP, the former is more than one order of magnitude faster than τα, whereas the two relaxation times become comparable in the case of OTP. The difference between the two relaxation times appears to relate to the "breadth" of the relaxation time distribution function. In OTP the α-relaxation process assumes a virtually single exponential decay at high temperatures well above the glass transition temperature, in clear contrast with the case of the amorphous bulk polymers.

  15. Does Brillouin light scattering probe the primary glass transition process at temperatures well above glass transition?

    PubMed

    Voudouris, P; Gomopoulos, N; Le Grand, A; Hadjichristidis, N; Floudas, G; Ediger, M D; Fytas, G

    2010-02-21

    The primary alpha-relaxation time (tau(alpha)) for molecular and polymeric glass formers probed by dielectric spectroscopy and two light scattering techniques (depolarized light scattering and photon correlation spectroscopy) relates to the decay of the torsional autocorrelation function computed by molecular dynamics simulation. It is well known that Brillouin light scattering spectroscopy (BLS) operating in gigahertz frequencies probes a fast (10-100 ps) relaxation of the longitudinal modulus M*. The characteristic relaxation time, irrespective of the fitting procedure, is faster than the alpha-relaxation which obeys the non-Arrhenius Vogel-Fulcher-Tammann equation. Albeit, this has been noticed, it remains a puzzling finding in glass forming systems. The available knowledge is based only on temperature dependent BLS experiments performed, however, at a single wave vector (frequency). Using a new BLS spectrometer, we studied the phonon dispersion at gigahertz frequencies in molecular [o-terphenyl (OTP)] and polymeric [polyisoprene (PI) and polypropylene (PP)] glass formers. We found that the hypersonic dispersion does relate to the glass transition dynamics but the disparity between the BLS-relaxation times and tau(alpha) is system dependent. In PI and PP, the former is more than one order of magnitude faster than tau(alpha), whereas the two relaxation times become comparable in the case of OTP. The difference between the two relaxation times appears to relate to the "breadth" of the relaxation time distribution function. In OTP the alpha-relaxation process assumes a virtually single exponential decay at high temperatures well above the glass transition temperature, in clear contrast with the case of the amorphous bulk polymers. PMID:20170250

  16. PREFACE: Dynamic crossover phenomena in water and other glass-forming liquids Dynamic crossover phenomena in water and other glass-forming liquids

    NASA Astrophysics Data System (ADS)

    Chen, Sow-Hsin; Baglioni, Piero

    2012-02-01

    This special section has been inspired by the workshop on Dynamic Crossover Phenomena in Water and Other Glass-Forming Liquids, held during November 11-13, 2010 at Pensione Bencistà, Fiesole, Italy, a well-preserved 14th century Italian villa tucked high in the hills overlooking Florence. The meeting, an assembly of world renowned scientists, was organized as a special occasion to celebrate the 75th birthday of Professor Sow-Hsin Chen of MIT, a pioneer in several aspects of complex fluids and soft matter physics. The workshop covered a large variety of experimental and theoretical research topics of current interest related to dynamic crossover phenomena in water and, more generally, in other glass-forming liquids. The 30 invited speakers/lecturers and approximately 60 participants were a select group of prominent physicists and chemists from the USA, Europe, Asia and Mexico, who are actively working in the field. Some highlights of this special issue include the following works. Professor Yamaguchi's group and their collaborators present a neutron spin echo study of the coherent intermediate scattering function of heavy water confined in cylindrical pores of MCM-41-C10 silica material in the temperature range 190-298 K. They clearly show that a fragile-to-strong (FTS) dynamic crossover occurs at about 225 K. They attribute the FTS dynamic crossover to the formation of a tetrahedral-like structure, which is preserved in the bulk-like water confined to the central part of the cylindrical pores. Mamontov and Kolesnikov et al study the collective excitations in an aqueous solution of lithium chloride over a temperature range of 205-270 K using neutron and x-ray Rayleigh-Brillouin (coherent) scattering. They detect both the low-frequency and the high-frequency sounds known to exist in pure bulk water above the melting temperature. They also perform neutron (incoherent) and x-ray (coherent) elastic intensity scan measurements. Clear evidence of the crossover in the

  17. The glass transition in high-density amorphous ice

    PubMed Central

    Loerting, Thomas; Fuentes-Landete, Violeta; Handle, Philip H.; Seidl, Markus; Amann-Winkel, Katrin; Gainaru, Catalin; Böhmer, Roland

    2015-01-01

    There has been a long controversy regarding the glass transition in low-density amorphous ice (LDA). The central question is whether or not it transforms to an ultraviscous liquid state above 136 K at ambient pressure prior to crystallization. Currently, the most widespread interpretation of the experimental findings is in terms of a transformation to a superstrong liquid above 136 K. In the last decade some work has also been devoted to the study of the glass transition in high-density amorphous ice (HDA) which is in the focus of the present review. At ambient pressure HDA is metastable against both ice I and LDA, whereas at > 0.2 GPa HDA is no longer metastable against LDA, but merely against high-pressure forms of crystalline ice. The first experimental observation interpreted as the glass transition of HDA was made using in situ methods by Mishima, who reported a glass transition temperature Tg of 160 K at 0.40 GPa. Soon thereafter Andersson and Inaba reported a much lower glass transition temperature of 122 K at 1.0 GPa. Based on the pressure dependence of HDA's Tg measured in Innsbruck, we suggest that they were in fact probing the distinct glass transition of very high-density amorphous ice (VHDA). Very recently the glass transition in HDA was also observed at ambient pressure at 116 K. That is, LDA and HDA show two distinct glass transitions, clearly separated by about 20 K at ambient pressure. In summary, this suggests that three glass transition lines can be defined in the p–T plane for LDA, HDA, and VHDA. PMID:25641986

  18. Theoretical study of production of unique glasses in space. [kinetic relationships describing nucleation and crystallization phenomena

    NASA Technical Reports Server (NTRS)

    Larsen, D. C.; Sievert, J. L.

    1975-01-01

    The potential of producing the glassy form of selected materials in the weightless, containerless nature of space processing is examined through the development of kinetic relationships describing nucleation and crystallization phenomena. Transformation kinetics are applied to a well-characterized system (SiO2), an excellent glass former (B2O3), and a poor glass former (Al2O3) by conventional earth processing methods. Viscosity and entropy of fusion are shown to be the primary materials parameters controlling the glass forming tendency. For multicomponent systems diffusion-controlled kinetics and heterogeneous nucleation effects are considered. An analytical empirical approach is used to analyze the mullite system. Results are consistent with experimentally observed data and indicate the promise of mullite as a future space processing candidate.

  19. The deformation units in metallic glasses revealed by stress-induced localized glass transition

    NASA Astrophysics Data System (ADS)

    Huo, L. S.; Ma, J.; Ke, H. B.; Bai, H. Y.; Zhao, D. Q.; Wang, W. H.

    2012-06-01

    We report that even in quasi-static cyclic compressions in the apparent elastic regimes of the bulk metallic glasses, the precisely measured stress-strain curve presents a mechanical hysteresis loop, which is commonly perceived to occur only in high-frequency dynamic tests. A phenomenological viscoelastic model is established to explain the hysteresis loop and demonstrate the evolutions of the viscous zones in metallic glasses during the cyclic compression. The declining of the viscosity of the viscous zones to at least 1 × 1012 Pa s when stress applied indicates that stress-induced localized glass to supercooled liquid transition occurs. We show that the deformation units of metallic glasses are evolved from the intrinsic heterogeneous defects in metallic glasses under stress and the evolution is a manifestation of the stress-induced localized glass transition. Our study might provide a new insight into the atomic-scale mechanisms of plastic deformation of metallic glasses.

  20. Estimation of the critical glass transition rate and the inorganic glass thickness

    NASA Astrophysics Data System (ADS)

    Belousov, O. K.

    2009-12-01

    Procedures are described for calculating the components of a new equation obtained to estimate critical glass transition rate R c . Reported data on R c are used to calculate critical shear frequency ν t, g( m), and a technique of its calculation using absolute entropy and elastic constants is presented. Procedures for calculating the energy of defect formation in amorphous substances H ν and for estimating glass transition temperature T g are described. It is shown that the ratio H ν / q (where q = N A k BΔ T m-g , N A is Avogadro’s number, k B is the Boltzmann constant, and Δ T m-g is the difference between the melting and glass transition temperatures) can be used to estimate critical glass transition rate R c and critical glass thickness h c .

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

    PubMed Central

    Xu, Limei; Buldyrev, Sergey V.; Giovambattista, Nicolas; Stanley, H. Eugene

    2010-01-01

    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. PMID:21614201

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

    ERIC Educational Resources Information Center

    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)

  3. Thermodynamic consequences of the kinetic nature of the glass transition

    PubMed Central

    Koperwas, Kajetan; Grzybowski, Andrzej; Tripathy, Satya N.; Masiewicz, Elzbieta; Paluch, Marian

    2015-01-01

    In this paper, we consider the glass transition as a kinetic process and establish one universal equation for the pressure coefficient of the glass transition temperature, dTg/dp, which is a thermodynamic characteristic of this process. Our findings challenge the common previous expectations concerning key characteristics of the transformation from the liquid to the glassy state, because it suggests that without employing an additional condition, met in the glass transition, derivation of the two independent equations for dTg/dp is not possible. Hence, the relation among the thermodynamic coefficients, which could be equivalent to the well-known Prigogine-Defay ratio for the process under consideration, cannot be obtained. Besides, by comparing the predictions of our universal equation for dTg/dp and Ehrenfest equations, we find the aforementioned supplementary restriction, which must be met to use the Prigogine-Defay ratio for the glass transition. PMID:26657017

  4. Thermodynamic glass transition in a spin glass without time-reversal symmetry

    PubMed Central

    Baños, Raquel Alvarez; Cruz, Andres; Fernandez, Luis Antonio; Gil-Narvion, Jose Miguel; Gordillo-Guerrero, Antonio; Guidetti, Marco; Iñiguez, David; Maiorano, Andrea; Marinari, Enzo; Martin-Mayor, Victor; Monforte-Garcia, Jorge; Muñoz Sudupe, Antonio; Navarro, Denis; Parisi, Giorgio; Perez-Gaviro, Sergio; Ruiz-Lorenzo, Juan Jesus; Schifano, Sebastiano Fabio; Seoane, Beatriz; Tarancon, Alfonso; Tellez, Pedro; Tripiccione, Raffaele; Yllanes, David

    2012-01-01

    Spin glasses are a longstanding model for the sluggish dynamics that appear at the glass transition. However, spin glasses differ from structural glasses in a crucial feature: they enjoy a time reversal symmetry. This symmetry can be broken by applying an external magnetic field, but embarrassingly little is known about the critical behavior of a spin glass in a field. In this context, the space dimension is crucial. Simulations are easier to interpret in a large number of dimensions, but one must work below the upper critical dimension (i.e., in d < 6) in order for results to have relevance for experiments. Here we show conclusive evidence for the presence of a phase transition in a four-dimensional spin glass in a field. Two ingredients were crucial for this achievement: massive numerical simulations were carried out on the Janus special-purpose computer, and a new and powerful finite-size scaling method. PMID:22493229

  5. Glass-crystal transition in silver-iodide-doped silver selenomolybdate glasses

    NASA Astrophysics Data System (ADS)

    Deb, B.; Ghosh, A.

    2013-12-01

    In this paper, we have studied the isothermal and non-isothermal glass-crystal transition in AgI-doped silver selenomolybdate glasses using differential scanning calorimetry. We have observed a strong dependence of AgI on the glass-crystal transition of these glasses. The activation energy for the crystallization and the dimensionality of the crystal growth for the isothermal and non-isothermal crystallization processes have been determined. The dimensionality of the crystal growth depends strongly on the AgI content and intriguingly shows different behavior when compared for isothermal and non-isothermal cases. For the present glass system the John-Mehl-Avrami model describes well the isothermal crystallization kinetics, while the Sestak-Berggren model is more suitable to describe the non-isothermal crystallization kinetics for glass-crystal transformation.

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

    NASA Astrophysics Data System (ADS)

    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.

  7. Strain glass state as the boundary of two phase transitions.

    PubMed

    Zhou, Zhijian; Cui, Jian; Ren, Xiaobing

    2015-01-01

    A strain glass state was found to be located between B2-B19' (cubic to monoclinic) phase transition and B2-R (cubic to rhombohedral) phase transition in Ti49Ni51 alloys after aging process. After a short time aging, strong strain glass transition was observed, because the size of the precipitates is small, which means the strain field induced by the precipitates is isotropic and point-defect-like, and the distribution of the precipitates is random. After a long time aging, the average size of the precipitates increases. The strong strain field induced by the precipitates around them forces the symmetry of the matrix materials to conform to the symmetry of the crystalline structure of the precipitates, which results in the new phase transition. The experiment shows that there exists no well-defined boundary in the evolution from the strain glass transition to the new phase transition. Due to its generality, this glass mediated phase transition divergence scheme can be applied to other proper material systems to induce a more important new phase transition path, which can be useful in the field of phase transition engineering. PMID:26307500

  8. Strain glass state as the boundary of two phase transitions

    NASA Astrophysics Data System (ADS)

    Zhou, Zhijian; Cui, Jian; Ren, Xiaobing

    2015-08-01

    A strain glass state was found to be located between B2-B19’ (cubic to monoclinic) phase transition and B2-R (cubic to rhombohedral) phase transition in Ti49Ni51 alloys after aging process. After a short time aging, strong strain glass transition was observed, because the size of the precipitates is small, which means the strain field induced by the precipitates is isotropic and point-defect-like, and the distribution of the precipitates is random. After a long time aging, the average size of the precipitates increases. The strong strain field induced by the precipitates around them forces the symmetry of the matrix materials to conform to the symmetry of the crystalline structure of the precipitates, which results in the new phase transition. The experiment shows that there exists no well-defined boundary in the evolution from the strain glass transition to the new phase transition. Due to its generality, this glass mediated phase transition divergence scheme can be applied to other proper material systems to induce a more important new phase transition path, which can be useful in the field of phase transition engineering.

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

    NASA Astrophysics Data System (ADS)

    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.

  10. Temperature range of the liquid-glass transition

    NASA Astrophysics Data System (ADS)

    Sanditov, D. S.; Darmaev, M. V.; Sanditov, B. D.

    2016-02-01

    It has been shown that the currently used method for calculating the temperature range of δ T g in the glass transition equation qτ g = δ T g as the difference δ T g = ( T 12- T 13) results in overestimated values, which is explained by the assumption of a constant activation energy of glass transition in deriving the calculation equation ( T 12 and T 13 are the temperatures corresponding to the logarithmic viscosity values of logη = 12 and logη = 13). The methods for the evaluation of δ T g using the Williams-Landel-Ferry equation and the model of delocalized atoms are considered, the results of which are in satisfactory agreement with the product qτ g ( q is the cooling rate of the melt and τ g is the structural relaxation time at the glass transition temperature). The calculation of τ g for inorganic glasses and amorphous organic polymers is proposed.

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

    NASA Astrophysics Data System (ADS)

    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.

  12. Brittle to Ductile Transition in Densified Silica Glass

    PubMed Central

    Yuan, Fenglin; Huang, Liping

    2014-01-01

    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. PMID:24849328

  13. Thermodynamic properties of the lipid bilayer transition. Pseudocritical phenomena.

    PubMed Central

    Mitaku, S; Jippo, T; Kataoka, R

    1983-01-01

    Ultrasonic relaxation of multilamellar liposomes formed from dipalmitoylphosphatidylcholine was measured near the gel-to-liquid crystal transition by a differential ultrasonic resonator. The relaxation time and strength increased remarkably near the transition temperature, indicating a pseudocritical phenomenon. A quantitative analysis of the relaxation in terms of thermodynamic relationships between specific heat, thermal-expansion coefficient, and compressibility showed that more than 90% of the total endothermic heat of the transition arises from the latent heat. The temperature dependence of the ultrasonic relaxation parameters was also analyzed by the Landau theory; we obtain a small but finite difference, 0.6 degree C, between the pseudocritical temperature and the transition temperature. These results provide a quantitative description of both the first-order and second-order characters of the gel-to-liquid crystal transition. PMID:6688030

  14. Correlation between dynamic flow and thermodynamic glass transition in metallic glasses

    NASA Astrophysics Data System (ADS)

    Ke, H. B.; Wen, P.; Zhao, D. Q.; Wang, W. H.

    2010-06-01

    We report the values of steps of heat capacity (ΔCp) during the glass transition in a variety of metallic glasses (MGs). It is found that ΔCp is around 13.69 J mol-1 K-1 and almost invariable for the MGs. Based on the Eyring's theory [N. Hirai and H. Eyring, J. Polym. Sci. 37, 51 (1959)], the phenomenon corresponds to a critical reduced free volume value. This exhibits that the glass transition takes place when the reduced free volume approaches to ˜2.35% in the MG systems. The value, consistent with that of the yielding of MGs, confirms that temperature and stress are equivalent for fluidizing MGs. Our results give an implication to understanding the glass transition in MGs as a Lindemann-type melting behavior [F. A. Lindemann, Z. Phys. 11, 609 (1910)].

  15. Slowdown of Interhelical Motions Induces a Glass Transition in RNA

    PubMed Central

    Frank, Aaron T.; Zhang, Qi; Al-Hashimi, Hashim M.; Andricioaei, Ioan

    2015-01-01

    RNA function depends crucially on the details of its dynamics. The simplest RNA dynamical unit is a two-way interhelical junction. Here, for such a unit—the transactivation response RNA element—we present evidence from molecular dynamics simulations, supported by nuclear magnetic resonance relaxation experiments, for a dynamical transition near 230 K. This glass transition arises from the freezing out of collective interhelical motional modes. The motions, resolved with site-specificity, are dynamically heterogeneous and exhibit non-Arrhenius relaxation. The microscopic origin of the glass transition is a low-dimensional, slow manifold consisting largely of the Euler angles describing interhelical reorientation. Principal component analysis over a range of temperatures covering the glass transition shows that the abrupt slowdown of motion finds its explanation in a localization transition that traps probability density into several disconnected conformational pools over the low-dimensional energy landscape. Upon temperature increase, the probability density pools then flood a larger basin, akin to a lakes-to-sea transition. Simulations on transactivation response RNA are also used to backcalculate inelastic neutron scattering data that match previous inelastic neutron scattering measurements on larger and more complex RNA structures and which, upon normalization, give temperature-dependent fluctuation profiles that overlap onto a glass transition curve that is quasi-universal over a range of systems and techniques. PMID:26083927

  16. Slowdown of Interhelical Motions Induces a Glass Transition in RNA.

    PubMed

    Frank, Aaron T; Zhang, Qi; Al-Hashimi, Hashim M; Andricioaei, Ioan

    2015-06-16

    RNA function depends crucially on the details of its dynamics. The simplest RNA dynamical unit is a two-way interhelical junction. Here, for such a unit--the transactivation response RNA element--we present evidence from molecular dynamics simulations, supported by nuclear magnetic resonance relaxation experiments, for a dynamical transition near 230 K. This glass transition arises from the freezing out of collective interhelical motional modes. The motions, resolved with site-specificity, are dynamically heterogeneous and exhibit non-Arrhenius relaxation. The microscopic origin of the glass transition is a low-dimensional, slow manifold consisting largely of the Euler angles describing interhelical reorientation. Principal component analysis over a range of temperatures covering the glass transition shows that the abrupt slowdown of motion finds its explanation in a localization transition that traps probability density into several disconnected conformational pools over the low-dimensional energy landscape. Upon temperature increase, the probability density pools then flood a larger basin, akin to a lakes-to-sea transition. Simulations on transactivation response RNA are also used to backcalculate inelastic neutron scattering data that match previous inelastic neutron scattering measurements on larger and more complex RNA structures and which, upon normalization, give temperature-dependent fluctuation profiles that overlap onto a glass transition curve that is quasi-universal over a range of systems and techniques. PMID:26083927

  17. A simple method for tuning the glass transition process in inorganic phosphate glasses.

    PubMed

    Fulchiron, René; Belyamani, Imane; Otaigbe, Joshua U; Bounor-Legaré, Véronique

    2015-01-01

    The physical modification of glass transition temperature (T(g)) and properties of materials via blending is a common practice in industry and academia and has a large economic advantage. In this context, simple production of hitherto unattainable new inorganic glass blends from already existing glass compositions via blending raises much hope with the potential to provide new glasses with new and improved properties, that cannot be achieved with classical glass synthesis, for a plethora of applications such as computers screens, glass-to-metal seals, and storage materials for nuclear wastes. Here, we demonstrate that blends of the specific glass compositions studied are miscible in all proportions, an unreported phenomenon in hard condensed matter like glass. Interestingly, excellent agreement was found between the obtained data and calculated Tgs from theoretical equations (Supplementary information) for predicting the composition dependence of T(g) for miscible blends with weak but significant specific interactions between the blend components. That this blending method is at present not applied to inorganic glasses reflects the fact that water and chemically resistant phosphate glasses with relatively low T(g)s have become available only recently. PMID:25666949

  18. A simple method for tuning the glass transition process in inorganic phosphate glasses

    NASA Astrophysics Data System (ADS)

    Fulchiron, René; Belyamani, Imane; Otaigbe, Joshua U.; Bounor-Legaré, Véronique

    2015-02-01

    The physical modification of glass transition temperature (Tg) and properties of materials via blending is a common practice in industry and academia and has a large economic advantage. In this context, simple production of hitherto unattainable new inorganic glass blends from already existing glass compositions via blending raises much hope with the potential to provide new glasses with new and improved properties, that cannot be achieved with classical glass synthesis, for a plethora of applications such as computers screens, glass-to-metal seals, and storage materials for nuclear wastes. Here, we demonstrate that blends of the specific glass compositions studied are miscible in all proportions, an unreported phenomenon in hard condensed matter like glass. Interestingly, excellent agreement was found between the obtained data and calculated Tgs from theoretical equations (Supplementary information) for predicting the composition dependence of Tg for miscible blends with weak but significant specific interactions between the blend components. That this blending method is at present not applied to inorganic glasses reflects the fact that water and chemically resistant phosphate glasses with relatively low Tgs have become available only recently.

  19. Fluctuation model for structural relaxation and the glass transition

    SciTech Connect

    Moynihan, C.T.; Whang, J.H.

    1997-12-31

    The fluctuation or independently relaxing nanoregion model attributes the distribution of structural relaxation times in a glassforming melt to a physical distribution of nanoregions which vary in their properties. A quantitative test of this model is described, in which parameters derived from relaxational data on B{sub 2}O{sub 3} glass are shown to be capable of predicting the anomalous light scattering in the glass transition region. It is also shown that the local inhomogeneities which lead to the distribution of structural relaxation times make only a very minor contribution to the distribution of electrical relaxation times in ionically conducting glasses and melts.

  20. Numerical Studies of Phase Transition Phenomena in Microgravity

    NASA Technical Reports Server (NTRS)

    1997-01-01

    This work was aimed at developing and applying a new methodology for the efficient and accurate computation of problems involving several phases of matter. In particular, solidification processes typically involve melt/solid and sometimes melt//gas interfaces, whose location and shape is unknown a priori. This class of problems is called the free or moving boundary problem, and the numerical approaches for its solution to date are inaccurate, inefficient, and can not be readily extended to multi-dimensions or to time dependent phenomenon. Ongoing research on crystal growth at NASA and other institutions falls into the category of free boundary problems. It is exactly the accurate determination of the process dynamics and the shape and location of the interface between the phases which is responsible for the ultimate chemical segregation and the mechanical properties in the solid. This work developed the Triad Field Formalism approach for the computation of general multi-dimensional and time dependent free boundary problems. The particular subject addressed is solidification phenomena. All the relevant boundary conditions on the developing interface were exactly resolved. Several computer programs were developed during the course of this research, enabling us to determine for the first time the interplay among the various fields operating in tandem to produce the phenomena observed during solidification processes in weld pools and during crystal growth.

  1. Fluorinated epoxy resins with high glass transition temperatures

    NASA Technical Reports Server (NTRS)

    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.

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

    NASA Astrophysics Data System (ADS)

    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.

  3. Room temperature homogeneous flow in a bulk metallic glass with low glass transition temperature

    NASA Astrophysics Data System (ADS)

    Zhao, K.; Xia, X. X.; Bai, H. Y.; Zhao, D. Q.; Wang, W. H.

    2011-04-01

    We report a high entropy metallic glass of Zn20Ca20Sr20Yb20(Li0.55Mg0.45)20 via composition design that exhibiting remarkable homogeneous deformation without shear banding under stress at room temperature. The glass also shows properties such as low glass transition temperature (323 K) approaching room temperature, low density and high specific strength, good conductivity, polymerlike thermoplastic manufacturability, and ultralow elastic moduli comparable to that of bones. The alloy is thermally and chemically stable.

  4. Room temperature homogeneous flow in a bulk metallic glass with low glass transition temperature

    SciTech Connect

    Zhao, K.; Xia, X. X.; Bai, H. Y.; Zhao, D. Q.; Wang, W. H.

    2011-04-04

    We report a high entropy metallic glass of Zn{sub 20}Ca{sub 20}Sr{sub 20}Yb{sub 20}(Li{sub 0.55}Mg{sub 0.45}){sub 20} via composition design that exhibiting remarkable homogeneous deformation without shear banding under stress at room temperature. The glass also shows properties such as low glass transition temperature (323 K) approaching room temperature, low density and high specific strength, good conductivity, polymerlike thermoplastic manufacturability, and ultralow elastic moduli comparable to that of bones. The alloy is thermally and chemically stable.

  5. Configurational entropy of polar glass formers and the effect of electric field on glass transition.

    PubMed

    Matyushov, Dmitry V

    2016-07-21

    A model of low-temperature polar liquids is constructed that accounts for the configurational heat capacity, entropy, and the effect of a strong electric field on the glass transition. The model is based on the Padé-truncated perturbation expansions of the liquid state theory. Depending on parameters, it accommodates an ideal glass transition of vanishing configurational entropy and its avoidance, with a square-root divergent enumeration function at the point of its termination. A composite density-temperature parameter ρ(γ)/T, often used to represent combined pressure and temperature data, follows from the model. The theory is in good agreement with the experimental data for excess (over the crystal state) thermodynamics of molecular glass formers. We suggest that the Kauzmann entropy crisis might be a signature of vanishing configurational entropy of a subset of degrees of freedom, multipolar rotations in our model. This scenario has observable consequences: (i) a dynamical crossover of the relaxation time and (ii) the fragility index defined by the ratio of the excess heat capacity and excess entropy at the glass transition. The Kauzmann temperature of vanishing configurational entropy and the corresponding glass transition temperature shift upward when the electric field is applied. The temperature shift scales quadratically with the field strength. PMID:27448893

  6. Configurational entropy of polar glass formers and the effect of electric field on glass transition

    NASA Astrophysics Data System (ADS)

    Matyushov, Dmitry V.

    2016-07-01

    A model of low-temperature polar liquids is constructed that accounts for the configurational heat capacity, entropy, and the effect of a strong electric field on the glass transition. The model is based on the Padé-truncated perturbation expansions of the liquid state theory. Depending on parameters, it accommodates an ideal glass transition of vanishing configurational entropy and its avoidance, with a square-root divergent enumeration function at the point of its termination. A composite density-temperature parameter ργ/T, often used to represent combined pressure and temperature data, follows from the model. The theory is in good agreement with the experimental data for excess (over the crystal state) thermodynamics of molecular glass formers. We suggest that the Kauzmann entropy crisis might be a signature of vanishing configurational entropy of a subset of degrees of freedom, multipolar rotations in our model. This scenario has observable consequences: (i) a dynamical crossover of the relaxation time and (ii) the fragility index defined by the ratio of the excess heat capacity and excess entropy at the glass transition. The Kauzmann temperature of vanishing configurational entropy and the corresponding glass transition temperature shift upward when the electric field is applied. The temperature shift scales quadratically with the field strength.

  7. Apparent critical phenomena in the superionic phase transition of Cu2-xSe

    DOE PAGESBeta

    Kang, Stephen Dongmin; Danilkin, Sergey A.; Aydemir, Umut; Avdeev, Maxim; Studer, Andrew; Snyder, G. Jeffrey

    2016-01-11

    The superionic phase transition ofmore » $${\\mathrm{Cu}}_{2-x}\\mathrm{Se}$$ accompanies drastic changes in transport properties. The Seebeck coefficient increases sharply while the electrical conductivity and thermal diffusivity drops. Such behavior has previously been attributed to critical phenomena under the assumption of a continuous phase transition. However, applying Landau's criteria suggests that the transition should be first order. Using the phase diagram that is consistent with a first order transition, we show that the observed transport properties and heat capacity curves can be accounted for and modeled with good agreement. The apparent critical phenomena is shown to be a result of compositional degree-of-freedom. In conclusion, understanding of the phase transition allows to explain the enhancement in the thermoelectric figure-of-merit that is accompanied with the transition.« less

  8. EZ lidar dust transit phenomena observations in Seoul, Korea

    NASA Astrophysics Data System (ADS)

    Lolli, S.; Sauvage, L.; Loaec, S.

    2009-09-01

    Duststorms and sandstorms regularly devastate Northeast Asia and cause considerable damage to transportation system and public health; further, these events are conceived to be one of the very important indices for estimating the global warming and desertification. Previously, yellow sand events were considered natural phenomena that originate in deserts and arid areas. However, the greater scale and frequency of these events in recent years are considered to be the result of human activities such as overgrazing and over-cultivation. Japan, Korea, Cina and Mongolia are directly concerned to prevent and control these storms and have been able to some extent to provide forecasts and early warnings. In this framework, to improve the accuracy of forecasting , a compact and rugged eye safe lidar, the EZ LIDATM, developed together by Laboratoire des Sciences du Climat et l'Environnement (LSCE) (CEA-CNRS) and LEOSPHERE, France) to study and investigate structural and optical properties of clouds and aerosols, thanks to the strong know-how of CEA and CNRS in the field of air quality measurements and cloud observation and analysis, was deployed in Seoul, Korea in order to detect and study yellow sand events, thanks to its depolarization channel and scan capabilities. The preliminary results, showed in this paper, of this measurement campaign put in evidence that EZ Lidar, for its capabilities of operating unattended day and night under each atmospheric condition, is mature to be deployed in a global network to study long-range transport, crucial in the forecasting model.

  9. Galvanomagnetic phenomena in organic conductors under topological phase transition

    NASA Astrophysics Data System (ADS)

    Galbova, O.; Peschansky, V. G.; Stepanenko, D. I.

    2015-07-01

    The magnetoresistance of layered organic conductors with a multisheet Fermi surface (FS) is studied theoretically under conditions of the Lifshitz topological transition, where the FS topology may change in response to external effects acting on the conductor, such as pressure or doping with impurity atoms. Using as an example the Fermi surface consisting of a cylinder and two planes, which are slightly corrugated along the projection of the momentum pz=p n along the normal to the layers n, we analyze the magnetic-field dependence of the resistance and the Hall field in a strong external magnetic field H, where the cyclotron frequency ωc of the conduction electrons is much higher than their collision frequency 1/τ. In the immediate vicinity of the topological transition, where the distance between the different sheets of the FS becomes small, an electron can move from one sheet of the FS to another with the probability w due to the magnetic breakdown. In this case, a quadratic increase of the electric resistance across the layers with magnetic field, which occurs in the absence of the magnetic breakdown, is replaced by a linear dependence on H for w ≥γ=1 /ωcτ , and then reaches saturation for (1 -w )≤γ . The Hall field depends substantially on the probability of a magnetic breakdown, but in the case of ωcτ≫1 , its asymptote is independent of τ for all values of w. At w = 1, the quasi-planar sheets of the Fermi surface touch the corrugated cylinders, and under further perturbation acting on the conductor, there occurs a break of a flat sheet along the line of contact. As a result, separate sections of the flat FS sheet together with the cut halves of the corrugated cylinder form a new corrugated cylinder with the sign of charge carriers reversed. This is not the only scenario of the Lifshitz topological transition. Studies of the Hall effect will allow us to obtain further important information on the nature of changes in the topological structure of

  10. Effects of the host glass on optical transitions

    SciTech Connect

    Snitzer, E.

    1993-12-31

    All the glass lasers consist of various rare earths doped singly or in combinations in different glass bases. Because the transitions are between energy levels with the same f-electron configurations that are shielded by 5s and 5p electrons from the ligand field, the fluorescent lifetimes are of the order of a few milliseconds and the ligand field interaction is of the order of a few hundred cm{sup {minus}1}. Nevertheless, the host glass has a substantial influence because of the site symmetry, the presence of multiple sites and the quenching associated with the interaction between the rare earth and the phonon spectrum of the glass. The use of fiber lasers for oscillators, amplifiers, and superluminescent sources will be discussed. The ions of particular interest are Er, Pr, Nd, and Tm.

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

    NASA Astrophysics Data System (ADS)

    Jiang, M. Q.; Naderi, M.; Wang, Y. J.; Peterlechner, M.; Liu, X. F.; Zeng, F.; Jiang, F.; Dai, L. H.; Wilde, G.

    2015-12-01

    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.

  12. Deformation, Stress Relaxation, and Crystallization of Lithium Silicate Glass Fibers Below the Glass Transition Temperature

    NASA Technical Reports Server (NTRS)

    Ray, Chandra S.; Brow, Richard K.; Kim, Cheol W.; Reis, Signo T.

    2004-01-01

    The deformation and crystallization of Li(sub 2)O (center dot) 2SiO2 and Li(sub 2)O (center dot) 1.6SiO2 glass fibers subjected to a bending stress were measured as a function of time over the temperature range -50 to -150 C below the glass transition temperature (Tg). The glass fibers can be permanently deformed at temperatures about 100 C below T (sub)g, and they crystallize significantly at temperatures close to, but below T,, about 150 C lower than the onset temperature for crystallization for these glasses in the no-stress condition. The crystallization was found to occur only on the surface of the glass fibers with no detectable difference in the extent of crystallization in tensile and compressive stress regions. The relaxation mechanism for fiber deformation can be best described by a stretched exponential (Kohlrausch-Williams-Watt (KWW) approximation), rather than a single exponential model.The activation energy for stress relaxation, Es, for the glass fibers ranges between 175 and 195 kJ/mol, which is considerably smaller than the activation energy for viscous flow, E, (about 400 kJ/mol) near T, for these glasses at normal, stress-free condition. It is suspected that a viscosity relaxation mechanism could be responsible for permanent deformation and crystallization of the glass fibers below T,

  13. Glass transition and crystallization kinetics of a barium borosilicate glass by a non-isothermal method

    SciTech Connect

    Lopes, Andreia A. S.; Soares, Roque S.; Lima, Maria M. A.; Monteiro, Regina C. C.

    2014-01-28

    The glass transition and crystallization kinetics of a glass with a molar composition 60BaO-30B{sub 2}O{sub 3}-10SiO{sub 2} were investigated by differential scanning calorimetry (DSC) under non-isothermal conditions. DSC curves exhibited an endothermic peak associated with the glass transition and two partially overlapped exothermic peaks associated with the crystallization of the glass. The dependence of the glass transition temperature (T{sub g}) and of the maximum crystallization temperature (T{sub p}) on the heating rate was used to determine the activation energy associated with the glass transition (E{sub g}), the activation energy for crystallization (E{sub c}), and the Avrami exponent (n). X-ray diffraction (XRD) revealed that barium borate (β-BaB{sub 2}O{sub 4}) was the first crystalline phase to be formed followed by the formation of barium silicate (Ba{sub 5}Si{sub 8}O{sub 21}). The variations of activation energy for crystallization and of Avrami exponent with the fraction of crystallization (χ) were also examined. When the crystallization fraction (χ) increased from 0.1 to 0.9, the value of local activation energy (E{sub c}(χ)) decreased from 554 to 458 kJ/mol for the first exothermic peak and from 1104 to 831 kJ/mol for the second exothermic peak. The value determined for the Avrami exponent was near 2 indicating a similar one-dimensional crystallization mechanism for both crystalline phases. This was confirmed by the morphological studies performed by scanning electron microscopy (SEM) on glass samples heat-treated at the first and at the second crystallization temperatures.

  14. Polaronic Transport in Phosphate Glasses Containing Transition Metal Ions

    NASA Astrophysics Data System (ADS)

    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

  15. Brillouin Scattering Study of Liquid Glass Transition in Lithium Borate Glass

    NASA Astrophysics Data System (ADS)

    Ike, Yuji; Matsuda, Yu; Kojima, Seiji; Kodama, Masao

    2006-05-01

    Elastic properties of different compositions of lithium borate glasses xLi2O\\cdot(1-x)B2O3 (x=0.06--0.28) were investigated in the temperature range from 25 to 600 °C by Brillouin scattering spectroscopy. The composition dependence of the lithium borate glass system shows a stiffening tendency and a higher onset temperature of softening with increasing mole fraction of Li2O. We successfully observed the change in longitudinal elastic modulus in the vicinity of the glass transition temperature (Tg). The elastic moduli show a marked temperature dependence above the glass transition temperature Tg, while they show little change below Tg. These results strongly relate to the structural conversion of cross-linking borate units from triangular BO3 to tetrahedral BO4 units by the addition of Li2O. The increase in lithium oxide enhances the glass network integrity in the composition range of this study. A significant decrease in the elastic modulus above Tg can be attributed to the association of boroxol ring deformation and a change in the coordination number of boron atoms. These elastic properties were discussed in comparison with lithium silicate glass.

  16. Vacuum ellipsometry as a method for probing glass transition in thin polymer films

    NASA Astrophysics Data System (ADS)

    Efremov, Mikhail Yu.; Soofi, Shauheen S.; Kiyanova, Anna V.; Munoz, Claudio J.; Burgardt, Peter; Cerrina, Franco; Nealey, Paul F.

    2008-04-01

    A vacuum ellipsometer has been designed for probing the glass transition in thin supported polymer films. The device is based on the optics of a commercial spectroscopic phase-modulated ellipsometer. A custom-made vacuum chamber evacuated by oil-free pumps, variable temperature optical table, and computer-based data acquisition system was described. The performance of the tool has been demonstrated using 20-200nm thick poly(methyl methacrylate) and polystyrene films coated on silicon substrates at 10-6-10-8torr residual gas pressure. Both polymers show pronounced glass transitions. The difficulties in assigning in the glass transition temperature are discussed with respect to the experimental challenges of the measurements in thin polymer films. It is found that the experimental curves can be significantly affected by a residual gas. This effect manifests itself at lower temperatures as a decreased or even negative apparent thermal coefficient of expansion, and is related to the uptake and desorption of water by the samples during temperature scans. It is also found that an ionization gauge—the standard accessory of any high vacuum system—can cause a number of spurious phenomena including drift in the experimental data, roughening of the polymer surface, and film dewetting.

  17. Impact-induced glass transition in elastomeric coatings

    NASA Astrophysics Data System (ADS)

    Bogoslovov, R. B.; Roland, C. M.; Gamache, R. M.

    2007-05-01

    Polybutadiene (PB) has a low glass temperature Tg and exhibits rubbery behavior during mechanical perturbation. The corresponding PB-based polyurea (PU) has a higher Tg and fails in a brittle mode for high strain rates. However, unlike in glasses, this brittle failure is accompanied by large energy dissipation. Dielectric relaxation measurements demonstrate that whereas the PB segmental dynamics are faster than the strain rate during impact loading, for PU these motions are on the order of the strain rate, ˜105s-1. Consequently, impact induces a transition to the glassy state, with the accompanying response markedly different from that of a rubber.

  18. Isothermal glass transitions in supercooled and overcompressed liquids

    NASA Astrophysics Data System (ADS)

    Alba-Simionesco, C.

    1994-02-01

    We report the first calorimetric characterization of isothermal glass transitions obtained by changing the pressure at constant temperature. This isothermal glass transition is described in the case of m-fluoroaniline, a so-called fragile liquid. The method employed is based on Maxwell's equations and involves measurement of the heat of compression of a sample enclosed in a hydrostatic pressure cell under isothermal and reversible conditions. A discontinuity of the thermodynamic quantity αV, where α is the expansivity and V is the molar volume, defines the glass transition pressure Pg at which ergodicity is broken on the time scale of the experiments (300-1000 s) which depends on the pressure step employed. The step in αV is found initially to decrease rapidly with increasing pressure. The slope (∂Pg/∂T)τ seems smaller than that determined by the usual isobaric methods, implying some distinction in the degrees of freedom involved and associated differences in defining the values of Tg. Because of the high sensitivity and stability of the calorimeter, we can also observe annealing effects in the overcompressed glass at a pressure above Pg; the slow dynamic processes associated are called entropic relaxation because it is the entropy which is measured directly. An approximate relaxation function and a model for the compression data are discussed. Keeping in mind the overall pattern of ``strong and fragile'' liquid behavior, isothermal pressure variations appear to offer a useful tool to connect these extremes and may constrain the glass transition of a molecular liquid in a particular range of the P-T diagram. The concept of Kauzmann pressure PK is introduced, but it is noted that PK must become less well defined the further from ambient pressure it lies due to the decrease in ΔαV which is observed with increasing pressure.

  19. Experimental signatures of a nonequilibrium phase transition governing the yielding of a soft glass

    NASA Astrophysics Data System (ADS)

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

    2014-06-01

    We present direct experimental signatures of a nonequilibrium phase transition associated with the yield point of a prototypical soft solid—a binary colloidal glass. By simultaneously quantifying single-particle dynamics and bulk mechanical response, we identified the threshold for the onset of irreversibility with the yield strain. We extracted the relaxation time from the transient behavior of the loss modulus and found that it diverges in the vicinity of the yield strain. This critical slowing down is accompanied by a growing correlation length associated with the size of regions of high Debye-Waller factor, which are precursors to yield events in glasses. Our results affirm that the paradigm of nonequilibrium critical phenomena is instrumental in achieving a holistic understanding of yielding in soft solids.

  20. Instantaneous normal modes and the protein glass transition.

    PubMed

    Schulz, Roland; Krishnan, Marimuthu; Daidone, Isabella; Smith, Jeremy C

    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 approximately 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. PMID:19167298

  1. Instantaneous Normal Modes and the Protein Glass Transition

    SciTech Connect

    Schultz, Roland; Krishnan, Marimuthu; Daidone, Isabella; Smith, Jeremy C

    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.

  2. Leading-edge transition and relaminarization phenomena on a subsonic high-lift system

    NASA Technical Reports Server (NTRS)

    Van Dam, C. P.; Vijgen, P. M. H. W.; Yip, L. P.; Potter, R. C.

    1993-01-01

    Boundary-layer transition and relaminarization may have a critical effect on the flow development about multielement high-lift systems of subsonic transport aircraft with swept wings. The purpose of this paper is a study of transition phenomena in the leading-edge region of the various elements of a high-lift system. The flow phenomena studied include transition of the attachment-line flow, relaminarization, and crossflow instability. The calculations are based on pressure distributions measured in flight on the NASA Transport Systems Research Vehicle (Boeing 737-100) at a wing station where the flow approximated infinite swept wing conditions. The results indicate that significant regions of laminar flow can exist on all flap elements in flight. In future flight experiments the extent of these regions will be measured, and the transition mechanisms and the effect of laminar flow on the high-lift characteristics of the multi-element system will be further explored.

  3. Why is there no clear glass transition of confined water?

    NASA Astrophysics Data System (ADS)

    Swenson, Jan; Elamin, Khalid; Jansson, Helén; Kittaka, Shigeharu

    2013-10-01

    To overcome the problem of crystallization of supercooled bulk water and water rich solutions we have studied water-glycerol mixtures confined in 21 Å pores of the silica matrix MCM-41 C10. The results from the differential scanning calorimetry (DSC) measurements shows an almost concentration independent glass transition temperature, Tg, at about 176 K for water concentrations up to 80 wt%, suggesting that the confined water has no influence on Tg in this concentration range. Rather, the findings indicate that the water molecules in the solutions have a stronger preference to coordinate to the hydroxyl surface groups than the glycerol molecules, which results in a micro-phase separation of the two liquids. The water phase does not give any sign of a Tg and therefore the observed Tg should be associated with the glass transition of the glycerol phase. Finally, we discuss why the confined water does not exhibit any clear calorimetric Tg.

  4. Scaled down glass transition temperature in confined polymer nanofibers.

    PubMed

    Wang, Hongxia; Chang, Tongxin; Li, Xiaohui; Zhang, Weidong; Hu, Zhijun; Jonas, Alain M

    2016-08-11

    Arrays of polymer nanostructures have been widely used in many novel devices and nanofabrication methods. The glass transition temperature, which is a key parameter influencing the long-term stability of polymer nanostructures, has not yet been systematically studied and well understood. Here we study this technological and fundamental issue with polymers of different values of molar mass M confined in nanocylinders of a varying diameter D. The glass transition temperature Tg loses its dependence on the molar mass for D ≲ 100 nm, a range in which the relative depression of Tg varies as D(-0.44). For higher cylinder diameters, Tg progressively recovers its dependence on the molar mass. This is quantitatively reproduced by a model based on an equilibrium interfacial excess of free volume, which needs to be created unless provided by the chain ends. Our findings suggest that the structural perturbations during nanofabrication may strongly affect the long-term stability of arrays of polymer nanostructures. PMID:27476991

  5. Predicting Glass Transition Temperatures of Polyarylethersulphones Using QSPR Methods

    PubMed Central

    Hamerton, Ian; Howlin, Brendan J.; Kamyszek, Grzegorz

    2012-01-01

    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. PMID:22719884

  6. Ductile-to-brittle transition in spallation of metallic glasses

    SciTech Connect

    Huang, X.; Ling, Z.; Dai, L. H.

    2014-10-14

    In this paper, the spallation behavior of a binary metallic glass Cu{sub 50}Zr{sub 50} is investigated with molecular dynamics simulations. With increasing the impact velocity, micro-voids induced by tensile pulses become smaller and more concentrated. The phenomenon suggests a ductile-to-brittle transition during the spallation process. Further investigation indicates that the transition is controlled by the interaction between void nucleation and growth, which can be regarded as a competition between tension transformation zones (TTZs) and shear transformation zones (STZs) at atomic scale. As impact velocities become higher, the stress amplitude and temperature rise in the spall region increase and micro-structures of the material become more unstable. Therefore, TTZs are prone to activation in metallic glasses, leading to a brittle behavior during the spallation process.

  7. Optical transitions of Er3+ ions in fluorozirconate glass

    NASA Astrophysics Data System (ADS)

    Shinn, M. D.; Sibley, W. A.; Drexhage, M. G.; Brown, R. N.

    1983-06-01

    Optical-absorption, -emission, and -excitation spectra are presented for Er3+ ions in fluorozirconate glass. Measured oscillator strengths of the transitions between J manifolds at 300 and 15 K are compared with calculated electric and magnetic dipole oscillator strengths. Radiative rates for five luminescing states were calculated. The nonradiative rates from these excited states were determined by calculating the difference between the measured rates and the calculated radiative rates. The low-temperature nonradiative rates are in agreement with the phenomenological energy-gap law followed by rare-earth ions in a number of crystals and glasses. The temperature dependence of the lifetimes was analyzed using the Huang-Rhys theory of multiphonon emission. Values for the 4I112 radiative and nonradiative rates obtained by the above methods are compared with those obtained applying the method Flaherty and DiBartolo used to study MnF2: Er3+. The multiphonon emission rates in fluorozirconate glass are much lower than the rates for the same levels of Er3+ in oxide glasses. Measurements of the bandwidths of the ground and excited states of Er3+ and the nearly exponential decay of the emissions indicate a relatively narrow distribution of site symmetries compared to oxide glasses.

  8. L to H mode transitions and associated phenomena in divertor tokamaks

    SciTech Connect

    Punjabi, A. )

    1990-09-01

    This is the final report for the research project titled L to H Mode Transitions and Associated Phenomena in Divertor Tokamaks.'' The period covered by this project is the fiscal year 1990. This report covers the development of Advanced Two Chamber Model.

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

    PubMed Central

    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

  10. Correlated Percolation Models of Jamming and Glass Transitions

    NASA Astrophysics Data System (ADS)

    Jeng, Monwhea; Schwarz, Jennifer

    2007-03-01

    Toninelli, Biroli, and Fisher recently introduced a model of correlated percolation called the Knight model, which they claimed to prove underwent a dynamical glass transition. This transition had novel properties, with a discontinuous jump in the order parameter, but with diverging time scales and correlation lengths. We show that their proof misidentified the critical point, so that these properties are currently unproven for this model. However, we show that these novel properties can in fact be proven for suitably modified models of correlated percolation, with qualitatively similar culling rules. We discuss the features of the models necessary for a rigorous proof to be possible. We also discuss properties of models such as the force balance model and the original Knight model, which appear to undergo novel transitions despite the lack of a rigorous proof of such a transition.

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

    NASA Astrophysics Data System (ADS)

    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.

  12. Determination of the glass transition temperature of cyclodextrin polymers.

    PubMed

    Tabary, Nicolas; Garcia-Fernandez, Maria Jose; Danède, Florence; Descamps, Marc; Martel, Bernard; Willart, Jean-François

    2016-09-01

    The aim of this work was to determine the main physical characteristics of β-cyclodextrin polymers, well known for improving complexation capacities and providing enhanced and sustained release of a large panel of drugs. Two polymers were investigated: a polymer of β-cyclodextrin (polyβ-CD) and a polymer of partially methylated (DS=0.57) β-cyclodextrin (polyMe-β-CD). The physical characterizations were performed by powder X-ray diffraction and differential scanning calorimetry. The results indicate that these polymers are amorphous and that their glass transition is located above the thermal degradation point of the materials preventing their direct observation and thus their full characterization. We could however estimate the virtual glass transition temperatures by mixing the polymers with different plasticizers (trehalose and mannitol) which decreases Tg sufficiently to make the glass transition observable. Extrapolation to zero plasticizer concentration then yield the following Tg values: Tg (polyMe-β-CD)=317°C±5°C and Tg (polyβ-CD)=418°C±6°C. PMID:27185128

  13. Glass transition of dense fluids of hard and compressible spheres.

    PubMed

    Berthier, Ludovic; Witten, Thomas A

    2009-08-01

    We use computer simulations to study the glass transition of dense fluids made of polydisperse repulsive spheres. For hard particles, we vary the volume fraction, phi , and use compressible particles to explore finite temperatures, T>0 . In the hard sphere limit, our dynamic data show evidence of an avoided mode-coupling singularity near phi(MCT) is approximately 0.592; they are consistent with a divergence of equilibrium relaxation times occurring at phi(0) is approximately 0.635, but they leave open the existence of a finite temperature singularity for compressible spheres at volume fraction phi>phi(0). Using direct measurements and a scaling procedure, we estimate the equilibrium equation of state for the hard sphere metastable fluid up to phi(0), where pressure remains finite, suggesting that phi(0) corresponds to an ideal glass transition. We use nonequilibrium protocols to explore glassy states above phi(0) and establish the existence of multiple equations of state for the unequilibrated glass of hard spheres, all diverging at different densities in the range phi in [0.642, 0.664]. Glassiness thus results in the existence of a continuum of densities where jamming transitions can occur. PMID:19792128

  14. Glass transition dynamics of stacked thin polymer films

    NASA Astrophysics Data System (ADS)

    Fukao, Koji; Terasawa, Takehide; Oda, Yuto; Nakamura, Kenji; Tahara, Daisuke

    2011-10-01

    The glass transition dynamics of stacked thin films of polystyrene and poly(2-chlorostyrene) were investigated using differential scanning calorimetry and dielectric relaxation spectroscopy. The glass transition temperature Tg of as-stacked thin polystyrene films has a strong depression from that of the bulk samples. However, after annealing at high temperatures above Tg, the stacked thin films exhibit glass transition at a temperature almost equal to the Tg of the bulk system. The α-process dynamics of stacked thin films of poly(2-chlorostyrene) show a time evolution from single-thin-film-like dynamics to bulk-like dynamics during the isothermal annealing process. The relaxation rate of the α process becomes smaller with increase in the annealing time. The time scale for the evolution of the α dynamics during the annealing process is very long compared with that for the reptation dynamics. At the same time, the temperature dependence of the relaxation time for the α process changes from Arrhenius-like to Vogel-Fulcher-Tammann dependence with increase of the annealing time. The fragility index increases and the distribution of the α-relaxation times becomes smaller with increase in the annealing time for isothermal annealing. The observed change in the α process is discussed with respect to the interfacial interaction between the thin layers of stacked thin polymer films.

  15. Liquid-glass transition in charge-stabilized colloidal dispersions

    NASA Astrophysics Data System (ADS)

    Lai, S. K.; Wang, G. F.; Peng, W. P.

    2000-06-01

    We model the inter-colloidal interactions in a charge-stabilized colloidal dispersion by a hard-core Yukawa potential φ(r)=σ0γ exp(-κr)/r, r>σ0 and apply the rescaled mean spherical approximation to calculate its static structure factor. In conjunction with the idealized mode-coupling theory, we determine the loci of the liquid-glass transition phase boundary for a salt-free suspension of charged colloids evaluated at different counter-ion environment (characterized by the κ) in terms of the macro-ion parameters: volume fraction ɛ, charge Z0 and size σ0. The calculated parametric phase diagrams are quite general since the results, with slight and straightforward modification, can be utilized to study the glass transition in a more realistic colloidal solution such as an aqueous monodisperse suspension of polystyrene charged spheres with an added electrolyte. Confining our discussion, then, to the simplest salt-free colloidal liquids, we extract from our analysis of the calculated liquid-glass transition boundaries some succinct features. Specifically, we show in this work that given a range of interaction Vkgr=κσ0<~3.8, there is a possibility of observing the liquid⇋glass⇋liquid⇋glass(LGLG) re-entrant phenomenon in restrictive regions of the phase diagram ɛ-σ0 or ɛ-Z0 for a monodisperse charge-stabilized solution. However, as the σ0 increases above a critical size, the LGLG re-entrant behavior vanishes. To delve into this re-entrant phenomenon, we compare, for a given Vkgr, the glassy Debye-Waller factor, static structure factor and their spatial counterparts for two cases-nnone for lower-Z0 colloids at a high ɛ and the other for higher-Z0 colloids at a low ɛ. For the former, the glassification is basically driven by the geometric restriction while that, for the latter, it is mainly induced by the Coulomb force. We conclude from this comparison that under the same screening environment both the excluded volume and the electrostatic effects are

  16. Brittle-to-Ductile Transition in Metallic Glass Nanowires.

    PubMed

    Şopu, D; Foroughi, A; Stoica, M; Eckert, J

    2016-07-13

    When reducing the size of metallic glass samples down to the nanoscale regime, experimental studies on the plasticity under uniaxial tension show a wide range of failure modes ranging from brittle to ductile ones. Simulations on the deformation behavior of nanoscaled metallic glasses report an unusual extended strain softening and are not able to reproduce the brittle-like fracture deformation as found in experiments. Using large-scale molecular dynamics simulations we provide an atomistic understanding of the deformation mechanisms of metallic glass nanowires and differentiate the extrinsic size effects and aspect ratio contribution to plasticity. A model for predicting the critical nanowire aspect ratio for the ductile-to-brittle transition is developed. Furthermore, the structure of brittle nanowires can be tuned to a softer phase characterized by a defective short-range order and an excess free volume upon systematic structural rejuvenation, leading to enhanced tensile ductility. The presented results shed light on the fundamental deformation mechanisms of nanoscaled metallic glasses and demarcate ductile and catastrophic failure. PMID:27248329

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

    NASA Astrophysics Data System (ADS)

    Stavrou, E.; Tsiantos, C.; Tsopouridou, R. D.; Kripotou, S.; Kontos, A. G.; Raptis, C.; Capoen, B.; Bouazaoui, M.; Turrell, S.; Khatir, S.

    2010-05-01

    Raman scattering and differential scanning calorimetry (DSC) measurements have been carried out on four mixed tellurium-zinc oxide (TeO2)1 - x(ZnO)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 Tg has been determined for each glass, showing a monotonous decrease of Tg 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 Td very close to the respective Tg 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 Tg 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 Tg and confirms the correlation between the BP and the MRO of glasses.

  18. The old problems of glass and the glass transition, and the many new twists.

    PubMed Central

    Angell, C A

    1995-01-01

    In this paper I review the ways in which the glassy state is obtained both in nature and in materials science and highlight a "new twist"--the recent recognition of polymorphism within the glassy state. The formation of glass by continuous cooling (viscous slowdown) is then examined, the strong/fragile liquids classification is reviewed, and a new twist-the possibility that the slowdown is a result of an avoided critical point-is noted. The three canonical characteristics of relaxing liquids are correlated through the fragility. As a further new twist, the conversion of strong liquids to fragile liquids by pressure-induced coordination number increases is demonstrated. It is then shown that, for comparable systems, it is possible to have the same conversion accomplished via a first-order transition within the liquid state during quenching. This occurs in the systems in which "polyamorphism" (polymorphism in the glassy state) is observed, and the whole phenomenology is accounted for by Poole's bond-modified van der Waals model. The sudden loss of some liquid degrees of freedom through such weak first-order transitions is then related to the polyamorphic transition between native and denatured hydrated proteins, since the latter are also glass-forming systems--water-plasticized, hydrogen bond-cross-linked chain polymers (and single molecule glass formers). The circle is closed with a final new twist by noting that a short time scale phenomenon much studied by protein physicists-namely, the onset of a sharp change in d/dT ( is the Debye-Waller factor)--is general for glass-forming liquids, including computer-simulated strong and fragile ionic liquids, and is closely correlated with the experimental glass transition temperature. The latter thus originates in strong anharmonicity in certain components of the vibrational density of states, which permits the system to access the multiple minima of its configuration space. The connection between the anharmonicity

  19. Nonequilibrium and nonhomogeneous phenomena around a first-order quantum phase transition

    NASA Astrophysics Data System (ADS)

    Del Re, Lorenzo; Fabrizio, Michele; Tosatti, Erio

    2016-03-01

    We consider nonequilibrium phenomena in a very simple model that displays a zero-temperature first-order phase transition. The quantum Ising model with a four-spin exchange is adopted as a general representative of first-order quantum phase transitions that belong to the Ising universality class, such as for instance the order-disorder ferroelectric transitions, and possibly first-order T =0 Mott transitions. In particular, we address quantum quenches in the exactly solvable limit of infinite connectivity and show that, within the coexistence region around the transition, the system can remain trapped in a metastable phase, as long as it is spatially homogeneous so that nucleation can be ignored. Motivated by the physics of nucleation, we then study in the same model static but inhomogeneous phenomena that take place at surfaces and interfaces. The first-order nature implies that both phases remain locally stable across the transition, and with that the possibility of a metastable wetting layer showing up at the surface of the stable phase, even at T =0 . We use mean-field theory plus quantum fluctuations in the harmonic approximation to study quantum surface wetting.

  20. The length and time scales of water's glass transitions

    NASA Astrophysics Data System (ADS)

    Limmer, David T.

    2014-06-01

    Using a general model for the equilibrium dynamics of supercooled liquids, I compute from molecular properties the emergent length and time scales that govern the nonequilibrium relaxation behavior of amorphous ice prepared by rapid cooling. Upon cooling, the liquid water falls out of equilibrium whereby the temperature dependence of its relaxation time is predicted to change from super-Arrhenius to Arrhenius. A consequence of this crossover is that the location of the apparent glass transition temperature depends logarithmically on cooling rate. Accompanying vitrification is the emergence of a dynamical length-scale, the size of which depends on the cooling rate and varies between angstroms and tens of nanometers. While this protocol dependence clarifies a number of previous experimental observations for amorphous ice, the arguments are general and can be extended to other glass forming liquids.

  1. Plastic Instability in Amorphous Selenium near its Glass Transition Temperature

    SciTech Connect

    Su, Caijun; Lamanna Jr, James; Gao, Yanfei; Oliver, Warren C.; Pharr, George M

    2010-01-01

    Deformation behavior of amorphous selenium near its glass transition temperature (31 C) has been investigated by uniaxial compression and nanoindentation creep tests. Cylindrical specimens compressed at high temperatures and low strain rates deform into drum-like shape, while tests at low temperatures and high strain rates lead to fragmentation. These results agree nicely with the stress exponent and kinetic activation parameters extracted from the nanoindentation creep tests by using a similarity analysis. The dependence of deformation modes on temperature and strain rate is understood as a consequence of material instability and strain localization in the rate-dependent solids.

  2. Measurement of the volatility and glass transition temperatures of glasses produced during the DWPF startup test program

    SciTech Connect

    Marra, J.C.; Harbour, J.R.

    1995-10-18

    The Defense Waste Processing Facility (DWPF) will immobilize high-level radioactive waste currently stored in underground tanks at the Savannah River Site by incorporating the waste into a glass matrix. The molten waste glass will be poured into stainless steel canisters which will be welded shut to produce the final waste form. One specification requires that any volatiles produced as a result of accidentally heating the waste glass to the glass transition temperature be identified. Glass samples from five melter campaigns, run as part of the DWPF Startup Test Program, were analyzed to determine glass transition temperatures and to examine the volatilization (by weight loss). Glass transition temperatures (T{sub g}) for the glasses, determined by differential scanning calorimetry (DSC), ranged between 445 C and 474 C. Thermogravimetric analysis (TGA) scans showed that no overall weight loss occurred in any of the glass samples when heated to 500 C. Therefore, no volatility will occur in the final glass product when heated up to 500 C.

  3. Viscosity, glass transition and activation energy of solid cis-polyisoprene and trans-polyisoprene blends

    NASA Astrophysics Data System (ADS)

    Baboo, Mahesh; Sharma, Kananbala; Saxena, N. S.

    2011-11-01

    Blends of cis-polyisoprene (CPI) and trans-polyisoprene (TPI) have been prepared by solution casting to study viscosity, glass transition temperature and activation energy for the glass transition. The viscosity of blends having different weight ratios has been obtained through a single experiment measuring storage and loss modulus using the dynamic mechanical analyser technique. The glass transition temperature is determined through the temperature at which the minimum of temperature derivative curve of viscosity falls. The activation energy of glass transition and fragility index have been obtained by employing the Vogel-Fulchar-Tammann (VFT) equation by assuming non-Arrhenius behaviour of viscosity of polymer blends. Results indicate that both glass transition and activation energy for the glass transition are influenced by composition and crosslink density of the blend.

  4. Thermal conductivity of Glycerol's liquid, glass, and crystal states, glass-liquid-glass transition, and crystallization at high pressures

    NASA Astrophysics Data System (ADS)

    Andersson, Ove; Johari, G. P.

    2016-02-01

    To investigate the effects of local density fluctuations on phonon propagation in a hydrogen bonded structure, we studied the thermal conductivity κ of the crystal, liquid, and glassy states of pure glycerol as a function of the temperature, T, and the pressure, p. We find that the following: (i) κcrystal is 3.6-times the κliquid value at 140 K at 0.1 MPa and 2.2-times at 290 K, and it varies with T according to 138 × T-0.95; (ii) the ratio κliquid (p)/κliquid (0.1 MPa) is 1.45 GPa-1 at 280 K, which, unexpectedly, is about the same as κcrystal (p)/κcrystal (0.1 MPa) of 1.42 GPa-1 at 298 K; (iii) κglass is relatively insensitive to T but sensitive to the applied p (1.38 GPa-1 at 150 K); (iv) κglass-T plots show an enhanced, pressure-dependent peak-like feature, which is due to the glass to liquid transition on heating; (v) continuous heating cold-crystallizes ultraviscous glycerol under pressure, at a higher T when p is high; and (vi) glycerol formed by cooling at a high p and then measured at a low p has a significantly higher κ than the glass formed by cooling at a low p. On heating at a fixed low p, its κ decreases before its glass-liquid transition range at that p is reached. We attribute this effect to thermally assisted loss of the configurational and vibrational instabilities of a glass formed at high p and recovered at low p, which is different from the usual glass-aging effect. While the heat capacity, entropy, and volume of glycerol crystal are less than those for its glass and liquid, κcrystal of glycerol, like its elastic modulus and refractive index, is higher. We discuss these findings in terms of the role of fluctuations in local density and structure, and the relations between κ and the thermodynamic quantities.

  5. Heat capacity, glass transition temperature, size of cooperatively rearranging regions, and network connectivity of sodium silicate and alkali borate glasses

    SciTech Connect

    Borisova, N.V.; Ushakov, V.M.; Shultz, M.M.

    1994-07-01

    The radius of cooperatively rearranging domains at the glass transition in sodium silicate glasses and the number of bridging oxygen atoms in these domains are assessed within the framework of the kinetic theory of thermal fluctuations. The tendencies of the heat capacity, T{sub g}, and the cooperative rearrangement scale with the alkali oxide concentration in sodium silicate and alkali borate glasses are compared. The points of similarity and distinctions between them are revealed.

  6. Glass transition of charged particles in two-dimensional confinement.

    PubMed

    Yazdi, Anoosheh; Heinen, Marco; Ivlev, Alexei; Löwen, Hartmut; Sperl, Matthias

    2015-05-01

    The glass transition of mesoscopic charged particles in two-dimensional confinement is studied by mode-coupling theory. We consider two types of effective interactions between the particles, corresponding to two different models for the distribution of surrounding ions that are integrated out in coarse-grained descriptions. In the first model, a planar monolayer of charged particles is immersed in an unbounded isotropic bath of ions, giving rise to an isotropically screened Debye-Hückel (Yukawa)-type effective interaction. The second, experimentally more relevant system is a monolayer of negatively charged particles that levitate atop a flat horizontal electrode, as frequently encountered in laboratory experiments with complex (dusty) plasmas. A steady plasma current toward the electrode gives rise to an anisotropic effective interaction potential between the particles, with an algebraically long-ranged in-plane decay. In a comprehensive parameter scan that covers the typical range of experimentally accessible plasma conditions, we calculate and compare the mode-coupling predictions for the glass transition in both kinds of systems. PMID:26066171

  7. Glass transition of ionic liquids under high pressure

    NASA Astrophysics Data System (ADS)

    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.

  8. Thermal Properties of Amorphous Selenium over the Glass- Transition Range

    NASA Astrophysics Data System (ADS)

    Ismail, Mukhtar Veliev

    1997-02-01

    In has been shown that the heat capacity (Cp), coefficients of heat conductivity, (l) and thermal expansion, (a), for the amorphous selenium are dependent on the temperature of the transition from glass-forming state into a high elasticity condition. On this transition these quantities are increased by ACp=3,47 kal/deg\\cdotmol, D l=0,32\\cdot 10-3 cal/sec\\cdot deg., da=0,79\\cdot 10-5 deg-1. These increments are due to the contribution by the increased concentration of holes. Contribution of holes in the glass-forming region was calculated using the formulae by Hirai and Eyring for 1 mol of "heads", which is equal to Cp=3,06 kal/deg\\cdotmol. The "hole" theory for liquids is used as a strating point in the calculation of the l and a. The obtained resuls are: l =0,28\\cdot 10-3 kal/cm\\cdotsec\\cdotdeg. a=0,73\\cdot 10-5 deg-1. These quantities for Cp, l and a are in satisfactory agreement with experimental data.

  9. Glass transition and relaxation processes of nanocomposite polymer electrolytes.

    PubMed

    Money, Benson K; Hariharan, K; Swenson, Jan

    2012-07-01

    This study focus on the effect of δ-Al(2)O(3) nanofillers on the dc-conductivity, glass transition, and dielectric relaxations in the polymer electrolyte (PEO)(4):LiClO(4). The results show that there are three dielectric relaxation processes, α, β, and γ, in the systems, although the structural α-relaxation is hidden in the strong conductivity contribution and could therefore not be directly observed. However, by comparing an enhanced dc-conductivity, by approximately 2 orders of magnitude with 4 wt % δ-Al(2)O(3) added, with a decrease in calorimetric glass transition temperature, we are able to conclude that the dc-conductivity is directly coupled to the hidden α-relaxation, even in the presence of nanofillers (at least in the case of δ-Al(2)O(3) nanofillers at concentrations up to 4 wt %). This filler induced speeding up of the segmental polymer dynamics, i.e., the α-relaxation, can be explained by the nonattractive nature of the polymer-filler interactions, which enhance the "free volume" and mobility of polymer segments in the vicinity of filler surfaces. PMID:22686254

  10. Measurement of the glass transition temperature of elastomer systems

    SciTech Connect

    Sircar, A.K.; Chartoff, R.P.

    1994-09-01

    The glass transition temperature of polymers depends on both the experimental procedures and the experimental techniques used for its evaluation. However, the value of the published data is often diminished because these details are omitted. Examples are cited to show how the magnitude of differential scanning calorimetry (DSC) T{sub g} depends on the T{sub g} location and different calibration methods. Some comments are also made about thermomechanical analysis (TMA) and dynamic mechanical analysis (DMA) methods, although these are treated only briefly. The factors that are unique to elastomer glass transition temperatures are: (1) the difficulties of calibration of the instruments at subambient temperature, (2) increase of T{sub g} by the extent of vulcanization and filler loading, (3) differences due to microstructure and microphase separation, and (4) the availability of different grades of the same elastomer with different composition or added components, which alter their T{sub g}. Thus, the literature value of T{sub g} should include not only the calibration and procedure for the experiment, but also the exact name and description of the elastomer with the number index, the recipe used, and the cure conditions.

  11. Structure of glasses containing transition metal ions. Progress report, February 1, 1979-January 31, 1980

    SciTech Connect

    White, W B; Furukawa, T; Tsong, I S.T.; Fox, K; Herman, J S; Houser, C; Nelson, C

    1980-02-01

    New normal coordinate calculations were used to relate the vibrational frequencies of silicate glasses to Si-O force constants. These appear to account for the observed frequency shifts with degree of silica polymerization. Raman spectroscopy has been used to elucidate the structure of sodium borosilicate glasses and of sodium aluminosilicate glasses. Structures of compositionally complex glasses can be understood if spectra are measured on many glasses spaced at small compositional intervals. Optical absorption spectra were used to investigate the structural setting of iron in alkali silicate glasses. Research on the alkali-hydrogen exchange in alkali silicate glasses was completed and additional work on ternary glasses is under way. A series of appendices present completed work on the structural investigations of alkali borosilicate glasses, on the structural setting of transition metal ions in glasses, and on the diffusion of hydrogen in alkali silicate glasses.

  12. Glass transitions and viscoelastic properties of carbopol and noveon compacts.

    PubMed

    Gómez-Carracedo, A; Alvarez-Lorenzo, C; Gómez-Amoza, J L; Concheiro, A

    2004-04-15

    Glass transitions of five varieties of Carbopol (acrylic acid polymers cross-linked with allyl sucrose or allyl pentaerythritol) and two varieties of Noveon (calcium salts of acrylic acid polymer cross-linked with divinylglycol) differing in cross-linking density and nature and content in residual solvents, were analysed (as compressed probes) by differential scanning calorimetry (DSC), modulated temperature differential scanning calorimetry (MTDSC), and oscillatory rheometry. All carbopol compacts showed a main glass transition, at a temperature between 130 and 140 degrees C, Tg, independently of their cross-linking degree and molecular weight. Additionally two batches of Carbopol 971P, which had greater contents in residual solvents, also presented a secondary transition at 65-70 degrees C. Sorption of water during storage of carbopol compacts at different relative humidity environments caused the Tg to strongly decrease. Compacts stored at 97.5% relative humidity have Tg below 0 degrees C and behave, at room temperature, as flexible hydrogels. The Gordon-Taylor/Kelley-Bueche equation only fit the dependence of Tg on water content well for carbopol compacts containing less than 15% water. The plasticizing effect of water was clearly evidenced in the considerable decrease in the storage and loss moduli of the compacts. Although the energy associated to the glass transitions of carbopol polymers, 0.40-0.50 Jg(-1) degrees C(-1), is high enough to be clearly detected by DSC, in some cases the evaporation of residual solvents may make it difficult to observe the Tg. This inconvenience is overcome using MTDSC or oscillatory rheometry. The decrease in Tg of carbopol caused by water sorption when compacts were stored at 97.5% R.H. explains why their loss (G") and storage (G') moduli at room temperature decreased four orders of magnitude. In contrast, in noveon varieties, calcium ions act as ionic cross-linkers of the carboxylic groups, providing rigid networks with much

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

    PubMed

    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. PMID:26286280

  14. Interplay of the Glass Transition and the Liquid-Liquid Phase Transition in Water

    PubMed Central

    Giovambattista, Nicolas; Loerting, Thomas; Lukanov, Boris R.; Starr, Francis W.

    2012-01-01

    Water has multiple glassy states, often called amorphous ices. Low-density (LDA) and high-density (HDA) amorphous ice are separated by a dramatic, first-order like phase transition. It has been argued that the LDA-HDA transformation connects to a first-order liquid-liquid phase transition (LLPT) above the glass transition temperature Tg. Direct experimental evidence of the LLPT is challenging to obtain, since the LLPT occurs at conditions where water rapidly crystallizes. In this work, we explore the implications of a LLPT on the pressure dependence of Tg(P) for LDA and HDA by performing computer simulations of two water models – one with a LLPT, and one without. In the absence of a LLPT, Tg(P) for all glasses nearly coincide. When there is a LLPT, different glasses exhibit dramatically different Tg(P) which are directly linked with the LLPT. Available experimental data for Tg(P) are only consistent with the scenario including a LLPT. PMID:22550566

  15. Two-dimensional electronic spectroscopy signatures of the glass transition

    DOE PAGESBeta

    Lewis, K. L. .. M.; Myers, J. A.; Fuller, F.; Tekavec, P. F.; Ogilvie, J. P.

    2010-01-01

    Two-dimensional electronic spectroscopy is a sensitive probe of solvation dynamics. Using a pump–probe geometry with a pulse shaper [ Optics Express 15 (2007), 16681-16689; Optics Express 16 (2008), 17420-17428], we present temperature dependent 2D spectra of laser dyes dissolved in glass-forming solvents. At low waiting times, the system has not yet relaxed, resulting in a spectrum that is elongated along the diagonal. At longer times, the system loses its memory of the initial excitation frequency, and the 2D spectrum rounds out. As the temperature is lowered, the time scale of this relaxation grows, and the elongation persists for longermore » waiting times. This can be measured in the ratio of the diagonal width to the anti-diagonal width; the behavior of this ratio is representative of the frequency–frequency correlation function [ Optics Letters 31 (2006), 3354–3356]. Near the glass transition temperature, the relaxation behavior changes. Understanding this change is important for interpreting temperature-dependent dynamics of biological systems.« less

  16. Anomalously large isotope effect in the glass transition of water

    DOE PAGESBeta

    Gainaru, Catalin; Agapov, Alexander L.; Fuentes-Landete, Violeta; Amann-Winkel, Katrin; Nelson, Helge; Köster, Karsten W.; Kolesnikov, Alexander I.; Novikov, Vladimir N.; Richert, Ranko; Böhmer, Roland; et al

    2014-11-24

    Here we present the discovery of an unusually large isotope effect in the structural relaxation and the glass transition temperature Tg of water. Dielectric relaxation spectroscopy of low-density as well as of vapor deposited amorphous water reveal Tg differences of 10±2K between H2O and D2O, sharply contrasting with other hydrogen bonded liquids for which H/D exchange increases Tg by typically less than 1K. We show that the large isotope effect and the unusual variation of relaxation times in water at low temperatures can be explained in terms of quantum effects. Thus, our findings shed new light on water's peculiar low-temperaturemore » dynamics and the possible role of quantum effects in its structural relaxation, and possibly in dynamics of other low molecular weight liquids.« less

  17. Moisture adsorption isotherms and glass transition temperature of pectin.

    PubMed

    Basu, Santanu; Shivhare, U S; Muley, S

    2013-06-01

    The moisture adsorption isotherms of low methoxyl pectin were determined at 30-70°C and water activity ranging from 0.11 to 0.94. The moisture adsorption isotherms revealed that the equilibrium moisture content increased with water activity. Increase in temperature, in general, resulted in decreased equilibrium moisture content. However in some cases, equilibrium moisture content values increased with temperature at higher water activities. Selected sorption models (GAB, Halsey, Henderson, Oswin, modified Oswin) were tested for describing the adsorption isotherms. Parameters of each sorption models were determined by nonlinear regression analysis. Oswin model gave the best fit for pectin sorption behaviour. Isosteric heat of sorption decreased with increase in moisture content and varied between 14.607 and 0.552 kJ/mol. Glass transition temperature decreased with increase in moisture content of pectin. PMID:24425957

  18. Influence of entanglements on glass transition temperature of polystyrene

    NASA Astrophysics Data System (ADS)

    Ougizawa, Toshiaki; Kinugasa, Yoshinori

    2013-03-01

    Chain entanglement is essential behavior of polymeric molecules and it seems to affect many physical properties such as not only viscosity of melt state but also glass transition temperature (Tg). But we have not attained the quantitative estimation because the entanglement density is considered as an intrinsic value of the polymer at melt state depending on the chemical structure. Freeze-drying method is known as one of the few ways to make different entanglement density sample from dilute solution. In this study, the influence of entanglements on Tg of polystyrene obtained by the freeze-dried method was estimated quantitatively. The freeze-dried samples showed Tg depression with decreasing the concentration of precursor solution due to the lower entanglement density and their depressed Tg would be saturated when the almost no intermolecular entanglement was formed. The molecular weight dependence of the maximum value of Tg depression was discussed.

  19. Simultaneous Determination of Glass Transition Temperatures of Several Polymers

    PubMed Central

    He, Jiang; Liu, Wei; Huang, Yao-Xiong

    2016-01-01

    Aims A simple and easy optical method is proposed for the determination of glass transition temperature (Tg) of polymers. Methods & Results Tg was determined using the technique of microsphere imaging to monitor the variation of the refractive index of polymer microsphere as a function of temperature. It was demonstrated that the method can eliminate most thermal lag and has sensitivity about six fold higher than the conventional method in Tg determination. So the determined Tg is more accurate and varies less with cooling/heating rate than that obtained by conventional methods. The most attractive character of the method is that it can simultaneously determine the Tg of several polymers in a single experiment, so it can greatly save experimental time and heating energy. Conclusion The method is not only applicable for polymer microspheres, but also for the materials with arbitrary shapes. Therefore, it is expected to be broadly applied to different fundamental researches and practical applications of polymers. PMID:26985670

  20. Anomalously large isotope effect in the glass transition of water

    SciTech Connect

    Gainaru, Catalin; Agapov, Alexander L.; Fuentes-Landete, Violeta; Amann-Winkel, Katrin; Nelson, Helge; Köster, Karsten W.; Kolesnikov, Alexander I.; Novikov, Vladimir N.; Richert, Ranko; Böhmer, Roland; Loerting, Thomas; Sokolov, Alexei P.

    2014-11-24

    Here we present the discovery of an unusually large isotope effect in the structural relaxation and the glass transition temperature Tg of water. Dielectric relaxation spectroscopy of low-density as well as of vapor deposited amorphous water reveal Tg differences of 10±2K between H2O and D2O, sharply contrasting with other hydrogen bonded liquids for which H/D exchange increases Tg by typically less than 1K. We show that the large isotope effect and the unusual variation of relaxation times in water at low temperatures can be explained in terms of quantum effects. Thus, our findings shed new light on water's peculiar low-temperature dynamics and the possible role of quantum effects in its structural relaxation, and possibly in dynamics of other low molecular weight liquids.

  1. Changes in the Atomic Structure through Glass Transition Observed by X-Ray Scattering

    SciTech Connect

    Egami, Takeshi

    2012-01-01

    The glass transition involves a minor change in the internal energy, and yet the physical and mechanical properties of a glass change dramatically. In order to determine the evolution of the atomic structure through the glass transition, we employed in-situ synchrotron X-ray scattering measurements as a function of temperature on a model material: Zr-Cu-Al metallic glass. We found that the thermal expansion at the atomic level is smaller than the macroscopic thermal expansion, and significantly increases above the glass transition temperature. The observed changes in the pair-distribution function (PDF) are explained in terms of the fluctuations in the local atomic volume and their change through the glass transition.

  2. The structural origin of the hard-sphere glass transition in granular packing

    PubMed Central

    Xia, Chengjie; Li, Jindong; Cao, Yixin; Kou, Binquan; Xiao, Xianghui; Fezzaa, Kamel; Xiao, Tiqiao; Wang, Yujie

    2015-01-01

    Glass transition is accompanied by a rapid growth of the structural relaxation time and a concomitant decrease of configurational entropy. It remains unclear whether the transition has a thermodynamic origin, and whether the dynamic arrest is associated with the growth of a certain static order. Using granular packing as a model hard-sphere glass, we show the glass transition as a thermodynamic phase transition with a ‘hidden' polytetrahedral order. This polytetrahedral order is spatially correlated with the slow dynamics. It is geometrically frustrated and has a peculiar fractal dimension. Additionally, as the packing fraction increases, its growth follows an entropy-driven nucleation process, similar to that of the random first-order transition theory. Our study essentially identifies a long-sought-after structural glass order in hard-sphere glasses. PMID:26412008

  3. The structural origin of the hard-sphere glass transition in granular packing

    DOE PAGESBeta

    Xia, Chengjie; Li, Jindong; Cao, Yixin; Kou, Binquan; Xiao, Xianghui; Fezzaa, Kamel; Xiao, Tiqiao; Wang, Yujie

    2015-09-28

    Glass transition is accompanied by a rapid growth of the structural relaxation time and a concomitant decrease of configurational entropy. It remains unclear whether the transition has a thermodynamic origin, and whether the dynamic arrest is associated with the growth of a certain static order. Using granular packing as a model hard-sphere glass, we show the glass transition as a thermodynamic phase transition with a ‘hidden’ polytetrahedral order. This polytetrahedral order is spatially correlated with the slow dynamics. It is geometrically frustrated and has a peculiar fractal dimension. Additionally, as the packing fraction increases, its growth follows an entropy-driven nucleationmore » process, similar to that of the random first-order transition theory. In conclusion, our study essentially identifies a long-sought-after structural glass order in hard-sphere glasses.« less

  4. The structural origin of the hard-sphere glass transition in granular packing

    SciTech Connect

    Xia, Chengjie; Li, Jindong; Cao, Yixin; Kou, Binquan; Xiao, Xianghui; Fezzaa, Kamel; Xiao, Tiqiao; Wang, Yujie

    2015-09-28

    Glass transition is accompanied by a rapid growth of the structural relaxation time and a concomitant decrease of configurational entropy. It remains unclear whether the transition has a thermodynamic origin, and whether the dynamic arrest is associated with the growth of a certain static order. Using granular packing as a model hard-sphere glass, we show the glass transition as a thermodynamic phase transition with a ‘hidden’ polytetrahedral order. This polytetrahedral order is spatially correlated with the slow dynamics. It is geometrically frustrated and has a peculiar fractal dimension. Additionally, as the packing fraction increases, its growth follows an entropy-driven nucleation process, similar to that of the random first-order transition theory. In conclusion, our study essentially identifies a long-sought-after structural glass order in hard-sphere glasses.

  5. The structural origin of the hard-sphere glass transition in granular packing

    NASA Astrophysics Data System (ADS)

    Xia, Chengjie; Li, Jindong; Cao, Yixin; Kou, Binquan; Xiao, Xianghui; Fezzaa, Kamel; Xiao, Tiqiao; Wang, Yujie

    2015-09-01

    Glass transition is accompanied by a rapid growth of the structural relaxation time and a concomitant decrease of configurational entropy. It remains unclear whether the transition has a thermodynamic origin, and whether the dynamic arrest is associated with the growth of a certain static order. Using granular packing as a model hard-sphere glass, we show the glass transition as a thermodynamic phase transition with a `hidden' polytetrahedral order. This polytetrahedral order is spatially correlated with the slow dynamics. It is geometrically frustrated and has a peculiar fractal dimension. Additionally, as the packing fraction increases, its growth follows an entropy-driven nucleation process, similar to that of the random first-order transition theory. Our study essentially identifies a long-sought-after structural glass order in hard-sphere glasses.

  6. The structural origin of the hard-sphere glass transition in granular packing.

    PubMed

    Xia, Chengjie; Li, Jindong; Cao, Yixin; Kou, Binquan; Xiao, Xianghui; Fezzaa, Kamel; Xiao, Tiqiao; Wang, Yujie

    2015-01-01

    Glass transition is accompanied by a rapid growth of the structural relaxation time and a concomitant decrease of configurational entropy. It remains unclear whether the transition has a thermodynamic origin, and whether the dynamic arrest is associated with the growth of a certain static order. Using granular packing as a model hard-sphere glass, we show the glass transition as a thermodynamic phase transition with a 'hidden' polytetrahedral order. This polytetrahedral order is spatially correlated with the slow dynamics. It is geometrically frustrated and has a peculiar fractal dimension. Additionally, as the packing fraction increases, its growth follows an entropy-driven nucleation process, similar to that of the random first-order transition theory. Our study essentially identifies a long-sought-after structural glass order in hard-sphere glasses. PMID:26412008

  7. Evidence for a second-order phase transition to a low-entropy glass

    NASA Astrophysics Data System (ADS)

    Royall, C. Patrick; Turci, Francesco; Speck, Thomas

    The physics underlying the glass transition is a major outstanding. Central its solution is whether there is some kind of thermodynamic transition to a ``ideal glass'', a disordered state with extremely low entropy, or whether in principle a liquid may be supercooled to arbitrary low temperature. Among the challenges that lie in tackling the glass transition are the immense timescales involved. Computer simulation, which might otherwise be able to pick up hints of a thermodynamic transition is limited by the small time-window over which a liquid can be equilibrated. Here we address this challenge using trajectory sampling in a system undergoing a first order nonequilibrium phase transition to a glassy state rich in low-energy geometric motifs. Extrapolation to equilibrium indicates that the transition would occur at a similar temperature at which the ideal glass transition is expected from extrapolation of dynamic and thermodynamic measurements. We further reweight nonequilibrium data to equilibrium leading to configurations representative of extremely low temperature, which indicate a transition to a low energy state at the ideal glass transition temperature. We thus interpret the ideal glass transition as the lower critical endpoint of this nonequilibrium transition.

  8. The Glass Transition at Silica/PMMA Nanocomposite Interfaces

    NASA Astrophysics Data System (ADS)

    Ozisik, Rahmi; Parker, Katelyn; Schneider, Ryan T.; Siegel, Richard W.; Cabanelas, Juan Carlos; Serrano, Berna; Antonelli, Claire; Baselga, Juan

    2011-03-01

    Local glass transition temperatures (Tg) have been measured in the interfaces of solution blended silica/poly(methyl methacrylate) (PMMA) nanocomposites using florescence spectroscopy and compared with Tg measured by differential scanning calorimetry (DSC). It was found that the two types of measurements yielded significantly different information. Combinations of silanes and poly(propylene glycol)- based molecular spacers bound to fluorophores were covalently linked to the surface of the nanoparticles, allowing for variation of the fluorophore response with respect to the distance from the nanofiller surface. Increases in the bulk Tg from the neat PMMA value were found upon the addition of nanofillers, but were independent of the nanofiller concentration when the filler concentration was above 2% by weight. Furthermore, as the size of the grafted molecular spacer was increased, Tg values were found to decrease and approach Tg of the neat PMMA. Owing to variable conformations of the spacers, an effective distribution of fluorophore-silica distances exists, which influences the fluorophores' response to the transition. Supported by NSF (CMMI-0500324) and CICYT (MAT 2007-63722).

  9. Mid-gap phenomena in chalcogenide glasses and barrier-cluster-heating model

    NASA Astrophysics Data System (ADS)

    Banik, Ivan; Kubliha, Marián; Lukovičová, Jozefa; Pavlendová, Gabriela

    2015-12-01

    The physical mechanism of photoluminescence spectrum formation of chalcogenide glasses (CHG) belongs to the important unsolved problems in physics of non-crystalline materials. Photoluminescence is an important means of the electron spectrum investigation. PL spectrum in CHG is produced mostly in the middle of the band gap, and its profile is normal - Gaussian. Several features of PL spectra in CHG is still a great mystery. The aim of the paper is to make reader acquainted with the new insight into the problem. In this article we also deal with the issue of clarifying the nature of mid-gap absorption. From the experiments it is known that after excitation of the glass As2S3 (or As2Se3) with primary radiation from Urbach-tail region the glass will be able to absorb the photons of low energy (IR) radiation from mid-gap region of spectra. This low photon absorption without action of the primary excitation radiation of the higher photon energy is impossible. Mid-gap absorption yields boost in the photoluminescence. The paper gives the reader the new insights into some, until now, unexplained effects and contexts in chalcogenide glasses from the position of barrier-cluster-heating model.

  10. Mid-gap phenomena in chalcogenide glasses and barrier-cluster-heating model

    SciTech Connect

    Banik, Ivan Kubliha, Marián; Lukovičová, Jozefa; Pavlendová, Gabriela

    2015-12-07

    The physical mechanism of photoluminescence spectrum formation of chalcogenide glasses (CHG) belongs to the important unsolved problems in physics of non-crystalline materials. Photoluminescence is an important means of the electron spectrum investigation. PL spectrum in CHG is produced mostly in the middle of the band gap, and its profile is normal - Gaussian. Several features of PL spectra in CHG is still a great mystery. The aim of the paper is to make reader acquainted with the new insight into the problem. In this article we also deal with the issue of clarifying the nature of mid-gap absorption. From the experiments it is known that after excitation of the glass As{sub 2}S{sub 3} (or As{sub 2}Se{sub 3}) with primary radiation from Urbach-tail region the glass will be able to absorb the photons of low energy (IR) radiation from mid-gap region of spectra. This low photon absorption without action of the primary excitation radiation of the higher photon energy is impossible. Mid-gap absorption yields boost in the photoluminescence. The paper gives the reader the new insights into some, until now, unexplained effects and contexts in chalcogenide glasses from the position of barrier-cluster-heating model.

  11. Structural Phase Transitions and Metallized Phenomena in Arsenic Telluride under High Pressure.

    PubMed

    Zhao, Jinggeng; Yang, Liuxiang; Yu, Zhenhai; Wang, Yong; Li, Chunyu; Yang, Ke; Liu, Zhiguo; Wang, Yi

    2016-04-18

    In this study, first-principle calculations, in situ angle-dispersive X-ray diffraction, and in situ electrical resistance measurements were performed on arsenic telluride (As2Te3) under high pressure. Structural phase transitions and metallized phenomena were observed from the calculated and experimental results. Upon compression, α-As2Te3 transforms into phases α' and α″ at ∼5.09 and ∼13.2 GPa, respectively, with two isostructural phase transitions. From 13.2 GPa, As2Te3 starts to transform into phase γ, with one first-order monoclinic to monoclinic crystal structural phase transition. According to the first-principle calculations and electrical resistance measurements, the structural phase transitions in the compression process induce the transformation from an insulator (phase α) across a semimetal (phase α') into a metal (phases α″ and γ). The evolution of the structure and transport property upon compression on As2Te3 is helpful for understanding the properties of other A2B3-type compounds under high pressure. PMID:27035163

  12. Crossover phenomena of percolation transition in evolution networks with hybrid attachment.

    PubMed

    Chen, Xiaolong; Yang, Chun; Zhong, Linfeng; Tang, Ming

    2016-08-01

    A first-order percolation transition, called explosive percolation, was recently discovered in evolution networks with random edge selection under a certain restriction. For many real world networks, the mechanism of preferential attachment plays a significant role in the formation of heterogeneous structures, but the network percolation in evolution process with preferential attachment has not yet been concerned. We propose a tunable network percolation model by introducing a hybrid mechanism of edge selection into the Bohman-Frieze-Wormald model, in which a parameter adjusts the relative weights between random and preferential selections. A large number of simulations indicate that there exist crossover phenomena of percolation transition by adjusting the parameter in the evolution processes. When the strategy of selecting a candidate edge is dominated by random selection, a single discontinuous percolation transition occurs. When a candidate edge is selected more preferentially based on nodes degree, the size of the largest component undergoes multiple discontinuous jumps, which exhibits a peculiar difference from the network percolation of random selection with a certain restriction. Besides, the percolation transition becomes continuous when the candidate edge is selected completely preferentially. PMID:27586610

  13. Glass-transition properties of Yukawa potentials: from charged point particles to hard spheres.

    PubMed

    Yazdi, Anoosheh; Ivlev, Alexei; Khrapak, Sergey; Thomas, Hubertus; Morfill, Gregor E; Löwen, Hartmut; Wysocki, Adam; Sperl, Matthias

    2014-06-01

    The glass transition is investigated in three dimensions for single and double Yukawa potentials for the full range of control parameters. For vanishing screening parameter, the limit of the one-component plasma is obtained; for large screening parameters and high coupling strengths, the glass-transition properties cross over to the hard-sphere system. Between the two limits, the entire transition diagram can be described by analytical functions. Unlike other potentials, the glass-transition and melting lines for Yukawa potentials are found to follow shifted but otherwise identical curves in control-parameter space. PMID:25019902

  14. Spatial glass transition temperature variations in polymer glass: application to a maltodextrin-water system.

    PubMed

    van Sleeuwen, Rutger M T; Zhang, Suying; Normand, Valéry

    2012-03-12

    A model was developed to predict spatial glass transition temperature (T(g)) distributions in glassy maltodextrin particles during transient moisture sorption. The simulation employed a numerical mass transfer model with a concentration dependent apparent diffusion coefficient (D(app)) measured using Dynamic Vapor Sorption. The mass average moisture content increase and the associated decrease in T(g) were successfully modeled over time. Large spatial T(g) variations were predicted in the particle, resulting in a temporary broadening of the T(g) region. Temperature modulated differential scanning calorimetry confirmed that the variation in T(g) in nonequilibrated samples was larger than in equilibrated samples. This experimental broadening was characterized by an almost doubling of the T(g) breadth compared to the start of the experiment. Upon reaching equilibrium, both the experimental and predicted T(g) breadth contracted back to their initial value. PMID:22268547

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

    PubMed

    Djemour, A; Sanctuary, R; Baller, J

    2015-04-01

    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. PMID:25689879

  16. Mechanical properties, glass transition temperature, and bond enthalpy trends of high metalloid Fe-based bulk metallic glasses

    SciTech Connect

    Gu, X. J.; Poon, S. Joseph; Shiflet, Gary J.; Widom, Michael

    2008-04-21

    Mechanical properties and glass transition temperatures (T{sub g}) of Fe-Cr-Mo-P-C-B bulk metallic glasses containing up to 27 at. % metalloids have been studied. The shear modulus (G) is found to decrease with increasing metalloid content and a maximum plastic strain of {approx}3% is obtained, despite the increase in the number of strong metal-metalloid bonds. Also, T{sub g} increases with the decrease in G, in contrast to usual behavior. By employing first-principles calculations, the results are discussed in light of atomic bonding and connectivity in the amorphous network. The findings are relevant to understanding ductility and glass transition of metallic glasses.

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

    NASA Astrophysics Data System (ADS)

    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.

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

    NASA Astrophysics Data System (ADS)

    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.

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

    NASA Astrophysics Data System (ADS)

    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.

  20. PHYSICAL PHENOMENA ACCOMPANYING THE GENERATION AND AMPLIFICATION OF LASER RADIATION: Highest efficiencies of neodymium glass lasers

    NASA Astrophysics Data System (ADS)

    Kuchma, I. G.; Levoshkin, A. V.; Murzin, A. G.; Prilezhaev, D. S.; Fromzel', V. A.

    1989-05-01

    An experimental study was made of the efficiency of transferring the excitation energy reaching different absorption bands of Nd3+ ions to the lasing channel of a phosphate glass laser. When the threshold pump power was exceeded by a factor of 1.1-5, the utilization (0.4-0.6) of the excitation energy was incomplete. One possible reason for this was shown to be a spectral inhomogeneity of the active medium.

  1. Faraday rotation measurements of time dependent magnetic phenomena in insulating spin glasses (invited)

    NASA Astrophysics Data System (ADS)

    Ferré, J.; Rajchenbach, J.; Maletta, H.

    1981-03-01

    We report here on a detailed study of the relaxation of the magnetization in an external field and of the remanent magnetization for the insulating spin glass: Eu0.4Sr0.6S. The Faraday rotation has allowed us to extend previous experiments near and just above the spin glass temperature Tfo = 1.55 K on a large time scale (10-6glass. The unusual field dependence of the TRM, always found in SG systems, i.e., the maximum in TRM versus H, results from an increase of the demagnetization rate with H, which can compensate the large initial magnetization at high fields. The isothermal remanent magnetization is analyzed from our knowledge of the time and field dependence of the in-field magnetization. The Tf(ν) variation and the TRM (H) behavior cannot be explained by a model of non interacting clusters and suggest a cooperative behavior, as for ferromagnets.

  2. Roles of water and solids composition in the control of glass transition and stickiness of milk powders.

    PubMed

    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. PMID:20629875

  3. Unraveling protein stabilization mechanisms: vitrification and water replacement in a glass transition temperature controlled system.

    PubMed

    Grasmeijer, N; Stankovic, M; de Waard, H; Frijlink, H W; Hinrichs, W L J

    2013-04-01

    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 vitrification or water replacement, both mechanisms could play a role and they should be considered simultaneously. A model protein, alkaline phosphatase, was incorporated in either inulin or trehalose by spray drying. To study the storage stability at different glass transition temperatures, a buffer which acts as a plasticizer, ammediol, was incorporated in the sugar glasses. At low glass transition temperatures (<50°C), the enzymatic activity of the protein strongly decreased during storage at 60°C. Protein stability increased when the glass transition temperature was raised considerably above the storage temperature. This increased stability could be attributed to vitrification. A further increase of the glass transition temperature did not further improve stability. In conclusion, vitrification plays a dominant role in stabilization at glass transition temperatures up to 10 to 20°C above storage temperature, depending on whether trehalose or inulin is used. On the other hand, the water replacement mechanism predominantly determines stability at higher glass transition temperatures. PMID:23360765

  4. Glass transitions in aqueous solutions of protein (bovine serum albumin).

    PubMed

    Shinyashiki, Naoki; Yamamoto, Wataru; Yokoyama, Ayame; Yoshinari, Takeo; Yagihara, Shin; Kita, Rio; Ngai, K L; Capaccioli, Simone

    2009-10-29

    Measurements by adiabatic calorimetry of heat capacities and enthalpy relaxation rates of a 20% (w/w) aqueous solution of bovine serum albumin (BSA) by Kawai, Suzuki, and Oguni [Biophys. J. 2006, 90, 3732] have found several enthalpy relaxations at long times indicating different processes undergoing glass transitions. In a quenched sample, one enthalpy relaxation at around 110 K and another over a wide temperature range (120-190 K) were observed. In a sample annealed at 200-240 K after quenching, three separated enthalpy relaxations at 110, 135, and above 180 K were observed. Dynamics of processes probed by adiabatic calorimetric data are limited to long times on the order of 10(3) s. A fuller understanding of the processes can be gained by probing the dynamics over a wider time/frequency range. Toward this goal, we performed broadband dielectric measurements of BSA-water mixtures at various BSA concentrations over a wide frequency range of thirteen decades from 2 mHz to 1.8 GHz at temperatures from 80 to 270 K. Three relevant relaxation processes were detected. For relaxation times equal to 100 s, the three processes are centered approximately at 110, 135, and 200 K, in good agreement with those observed by adiabatic calorimetry. We have made the following interpretation of the molecular origins of the three processes. The fastest relaxation process having relaxation time of 100 or 1000 s at ca. 110 K is due to the secondary relaxation of uncrystallized water (UCW) in the hydration shell. The intermediate relaxation process with 100 s relaxation time at ca. 135 K is due to ice. The slowest relaxation process having relaxation time of 100 s at ca. 200 K is interpreted to originate from local chain conformation fluctuations of protein slaved by water. Experimental evidence supporting these interpretations include the change of temperature dependence of the relaxation time of the UCW at approximately T(gBSA) approximately = 200 K, the glass transition temperature of

  5. Fractal network dimension determining the relation between the strength of bulk metallic glasses and the glass transition temperature

    NASA Astrophysics Data System (ADS)

    Klein, D. J.; March, N. H.; Alonso, J. A.

    2009-07-01

    [Ma et al., Nat. Mater. 8, 30 (2009)] have uncovered the fractal dimension Df=2.31 associated with the medium-range order in a variety of bulk metallic glasses, reflected in the first sharp diffraction peak q1 determined from neutron and x-ray measurements. Here, based on the proposal in this journal of [Yang et al., Appl. Phys. Lett. 88, 221911 (2006)], which related the strength σy of bulk metallic glasses to the glass transition temperature Tg, we show that the product q1Dfσy is linear in Tg.

  6. Optical transitions of Ho(3+) in oxyfluoride glasses and upconversion luminescence of Ho(3+)/Yb(3+)-codoped oxyfluoride glasses.

    PubMed

    Feng, Li; Wu, Yinsu

    2015-05-01

    Optical properties of Ho(3+)-doped SiO2-BaF2-ZnF2 glasses have been investigated on the basis of the Judd-Ofelt theory. Judd-Ofelt intensity parameters, radiative transition probabilities, fluorescence branching ratios and radiative lifetimes have been calculated for different glass compositions. Upconversion emissions were observed in Ho(3+)/Yb(3+)-codoped SiO2-BaF2-ZnF2 glasses under 980nm excitation. The effects of composition, concentration of the doping ions, and excitation pump power on the upconversion emissions were also systematically studied. PMID:25703369

  7. Dynamics of social contagions with heterogeneous adoption thresholds: crossover phenomena in phase transition

    NASA Astrophysics Data System (ADS)

    Wang, Wei; Tang, Ming; Shu, Panpan; Wang, Zhen

    2016-01-01

    Heterogeneous adoption thresholds exist widely in social contagions, such as behavior spreading, but were always neglected in previous studies. To this end, we introduce heterogeneous adoption threshold distribution into a non-Markovian spreading threshold model, in which an individual adopts a behavior only when the received cumulative pieces of behavioral information from neighbors exceeds his adoption threshold. In order to understand the effects of heterogeneous adoption thresholds quantitatively, an edge-based compartmental theory is developed. A two-state spreading threshold model is taken as an example, in which some individuals have a low adoption threshold (i.e., activists) while the remaining ones hold a relatively higher adoption threshold (i.e., bigots). We find a hierarchical characteristic in adopting behavior, i.e., activists first adopt the behavior and then stimulate bigots to adopt the behavior. Interestingly, two types of crossover phenomena in phase transition occur: for a relatively low adoption threshold of bigots, a change from first-order to second-order phase transition can be triggered by increasing the fraction of activists; for a relatively higher adoption threshold of bigots, a change from hybrid to second-order phase transition can be induced by varying the fraction of activists, decreasing mean degree or enhancing network heterogeneity. The theoretical predictions based on the suggested theory agree very well with the simulation results.

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

    PubMed

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

    2011-01-01

    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. PMID:24310595

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

    NASA Astrophysics Data System (ADS)

    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.

  10. Precise Measurements of the Density and Critical Phenomena Near Phase Transitions in Liquid Helium

    NASA Technical Reports Server (NTRS)

    Yeh, Nai-Chang

    1997-01-01

    The first-year progress for the project of precise measurements of the density and critical phenomena of helium near phase transitions is summarized below: (1) completion of a cryogenic sample probe for the proposed measurements, and the rehabilitation of a designated laboratory at Caltech for this project; (2) construction and testing of a superconducting niobium cavity; (3) acquisition of one phase-locked-loop system for high-resolution frequency control and read- out; (4) setting up high-resolution thermometry (HRT) for temperature readout and control; (5) developing new approaches for calibrating the coefficient between the resonant frequency shift (delta f) and the helium density (rho), as well as for measuring the effect of gravity on T(sub lambda) to a much better precision; (6) programming of the interface control of all instruments for automatic data acquisition; and (7) improving data analyses and fitting procedures.

  11. Ideal quantum glass transitions: Many-body localization without quenched disorder

    SciTech Connect

    Schiulaz, M.; Müller, M.

    2014-08-20

    We explore the possibility for translationally invariant quantum many-body systems to undergo a dynamical glass transition, at which ergodicity and translational invariance break down spontaneously, driven entirely by quantum effects. In contrast to analogous classical systems, where the existence of such an ideal glass transition remains a controversial issue, a genuine phase transition is predicted in the quantum regime. This ideal quantum glass transition can be regarded as a many-body localization transition due to self-generated disorder. Despite their lack of thermalization, these disorder-free quantum glasses do not possess an extensive set of local conserved operators, unlike what is conjectured for many-body localized systems with strong quenched disorder.

  12. High Glass Transition Temperature Renewable Polymers via Biginelli Multicomponent Polymerization.

    PubMed

    Boukis, Andreas C; Llevot, Audrey; Meier, Michael A R

    2016-04-01

    A novel and straightforward one-pot multicomponent polycondensation method was established in this work. The Biginelli reaction is a versatile multicomponent reaction of an aldehyde, a β-ketoester (acetoacetate) and urea, which can all be obtained from renewable resources, yielding diversely substituted 3,4-dihydropyrimidin-2(1H)-ones (DHMPs). In this study, renewable diacetoacetate monomers with different spacer chain lengths (C3, C6, C10, C20) were prepared via simple transesterification of renewable diols and commercial acetoacetates. The diacetoacetate monomers were then reacted with renewable dialdehydes, i.e., terephthalaldehyde and divanillin in a Biginelli type step-growth polymerization. The obtained DHMP polymers (polyDHMPs) displayed high molar masses, high glass transition temperatures (Tg) up to 203 °C and good thermal stability (Td5%) of 280 °C. The Tg of the polyDHMPs could be tuned by variation of the structure of the dialdehyde or the diacetoacetate component. PMID:26800511

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

    NASA Astrophysics Data System (ADS)

    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

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

    PubMed

    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

  15. Minimal cooling speed for glass transition in a simple solvable energy landscape model

    NASA Astrophysics Data System (ADS)

    Toledo-Marín, J. Quetzalcóatl; Castillo, Isaac Pérez; Naumis, Gerardo G.

    2016-06-01

    The minimal cooling speed required to form a glass is obtained for a simple solvable energy landscape model. The model, made from a two-level system modified to include the topology of the energy landscape, is able to capture either a glass transition or a crystallization depending on the cooling rate. In this setup, the minimal cooling speed to achieve glass formation is then found to be related with the crystallization relaxation time, energy barrier and with the thermal history. In particular, we obtain that the thermal history encodes small fluctuations around the equilibrium population which are exponentially amplified near the glass transition, which mathematically corresponds to the boundary layer of the master equation. The change in the glass transition temperature is also found as a function of the cooling rate. Finally, to verify our analytical results, a kinetic Monte Carlo simulation was implemented.

  16. Striking role of non-bridging oxygen on glass transition temperature of calcium aluminosilicate glass-formers

    SciTech Connect

    Bouhadja, M.; Jakse, N.; Pasturel, A.

    2014-06-21

    Molecular dynamics simulations are used to study the structural and dynamic properties of calcium aluminosilicate, (CaO-Al{sub 2}O{sub 3}){sub 1−x}(SiO{sub 2}){sub x}, glass formers along three joins, namely, R = 1, 1.57, and 3, in which the silica content x can vary from 0 to 1. For all compositions, we determined the glass-transition temperature, the abundances of the non-bridging oxygen, triclusters, and AlO{sub 5} structural units, as well as the fragility from the temperature evolution of the α-relaxation times. We clearly evidence the role played by the non-bridging oxygen linked either to Al atoms or Si atoms in the evolution of the glass-transition temperature as well as of the fragility as a function of silica content along the three joins.

  17. FAST TRACK COMMUNICATION: Characterization of frequency-dependent glass transition temperature by Vogel-Fulcher relationship

    NASA Astrophysics Data System (ADS)

    Bai, Yu; Jin, Li

    2008-08-01

    The complex mechanical modulus of polymer and polymer based composite materials showed a frequency-dependent behaviour during glass transition relaxation, which was historically modelled by the Arrhenius equation. However, this might not be true in a broad frequency domain based on the experience from the frequency dependence of the complex dielectric permittivity, which resulted from the same glass transition relaxation as for the complex mechanical modulus. Considering a good correspondence between dielectric and mechanical relaxation during glass transition, the Vogel-Fulcher relationship, previously proposed for the frequency dependence of dielectric permittivity, is introduced for that of the mechanical modulus; and the corresponding static glass transition temperature (Tf) was first determined for polymer and polymer based composite materials.

  18. On an anomalous kinetic in irradiated polymers around the glass transition temperature

    NASA Astrophysics Data System (ADS)

    Chipara, Mircea I.

    1997-08-01

    Anomalies occurring in irradiated polymers within the glass transition range, as reported by various authors are critically reviewed. A theoretical description for such processes, is developed within the free volume approximation. The discrepancies between the temperature at which such anomalies are noticed and the glass transition temperature have been ascribed to the fact that the volume of radiation-induced radicals is not equal with the segmental one. The agreement between experiment and theory is good.

  19. Using Rare Gas Permeation to Probe Methanol Diffusion near the Glass Transition Temperature

    NASA Astrophysics Data System (ADS)

    Matthiesen, Jesper; Smith, R. Scott; Kay, Bruce D.

    2009-12-01

    The permeation of rare-gas atoms through deeply supercooled metastable liquid methanol films is used to probe the diffusivity. The technique allows for measurement of supercooled liquid mobility at temperatures near the glass transition. The temperature dependence of the diffusivity is well described by a Vogel-Fulcher-Tamman equation. These new measurements and the temperature dependent kinetic parameters obtained from their analysis provide clear evidence that methanol is a fragile liquid near the glass transition.

  20. Using rare gas permeation to probe methanol diffusion near the glass transition temperature.

    PubMed

    Matthiesen, Jesper; Smith, R Scott; Kay, Bruce D

    2009-12-11

    The permeation of rare-gas atoms through deeply supercooled metastable liquid methanol films is used to probe the diffusivity. The technique allows for measurement of supercooled liquid mobility at temperatures near the glass transition. The temperature dependence of the diffusivity is well described by a Vogel-Fulcher-Tamman equation. These new measurements and the temperature dependent kinetic parameters obtained from their analysis provide clear evidence that methanol is a fragile liquid near the glass transition. PMID:20366212

  1. Kinetics of a bioactive compound (caffeine) mobility at the vicinity of the mechanical glass transition temperature induced by gelling polysaccharide.

    PubMed

    Jiang, Bin; Kasapis, Stefan

    2011-11-01

    An investigation of the diffusional mobility of a bioactive compound (caffeine) within the high-solid (80.0% w/w) matrices of glucose syrup and κ-carrageenan plus glucose syrup exhibiting distinct mechanical glass transition properties is reported. The experimental temperature range was from 20 to -60 °C, and the techniques of modulated differential scanning calorimetry, small deformation dynamic oscillation in shear, and UV spectrometry were employed. Calorimetric and mechanical measurements were complementary in recording the relaxation dynamics of high-solid matrices upon controlled heating. Predictions of the reaction rate theory and the combined WLF/free volume framework were further utilized to pinpoint the glass transition temperature (T(g)) of the two matrices in the softening dispersion. Independent of composition, calorimetry yielded similar T(g) predictions for both matrices at this level of solids. Mechanical experimentation, however, was able to detect the effect of adding gelling polysaccharide to glucose syrup as an accelerated pattern of vitrification leading to a higher value of T(g). Kinetic rates of caffeine diffusion within the experimental temperature range were taken with UV spectroscopy. These demonstrated the pronounced effect of the gelling κ-carrageenan/glucose syrup mixture to retard diffusion of the bioactive compound near the mechanical T(g). Modeling of the diffusional mobility of caffeine produced activation energy and fractional free-volume estimates, which were distinct from those of the carbohydrate matrix within the glass transition region. This result emphasizes the importance of molecular interactions between macromolecular matrix and small bioactive compound in glass-related relaxation phenomena. PMID:21936521

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

    NASA Astrophysics Data System (ADS)

    Xing, P. F.; Zhuang, Y. X.; Wang, W. H.; Gerward, L.; Jiang, J. Z.

    2002-04-01

    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 the Kissinger method. Results indicate that this glass crystallizes by a three-stage reaction: (1) phase separation and primary crystallization of glass, (2) formation of intermetallic compounds, and (3) decomposition of intermetallic compounds and crystallization of residual amorphous phase. The pressure 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/GPa in the range of 0 to 4.4 GPa, while the another crystallization temperature keeps almost unchanged in the applied pressure range. The results are attributed to the competing processes between the thermodynamic potential barrier and the diffusion activation energy under pressure.

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

    NASA Astrophysics Data System (ADS)

    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.

  4. Sharp semiconductor-to-metal transition of VO{sub 2} thin films on glass substrates

    SciTech Connect

    Jian, Jie; Chen, Aiping; Zhang, Wenrui; Wang, Haiyan

    2013-12-28

    Outstanding phase transition properties of vanadium dioxide (VO{sub 2}) thin films on amorphous glass were achieved and compared with the ones grown on c-cut sapphire and Si (111) substrates, all by pulsed laser deposition. The films on glass substrate exhibit a sharp semiconductor-to-metal transition (∼4.3 °C) at a near bulk transition temperature of ∼68.4 °C with an electrical resistance change as high as 3.2 × 10{sup 3} times. The excellent phase transition properties of the films on glass substrate are correlated with the large grain size and low defects density achieved. The phase transition properties of VO{sub 2} films on c-cut sapphire and Si (111) substrates were found to be limited by the high defect density.

  5. A toy MCT model for multiple glass transitions: Double swallow tail singularity

    NASA Astrophysics Data System (ADS)

    Ryzhov, V. N.; Tareyeva, E. E.

    2014-11-01

    We propose a toy model to describe in the frame of Mode Coupling Theory multiple glass transitions. The model is based on the postulated simple form for static structure factor as a sum of two delta-functions. This form makes it possible to solve the MCT equations in almost analytical way. The phase diagram is governed by two swallow tails resulting from two A4 singularities and includes liquid-glass transition and multiple glasses. The diagram has much in common with those of binary and quasibinary systems.

  6. Two-Step Glass Transition Induced by Attractive Interactions in Quasi-Two-Dimensional Suspensions of Ellipsoidal Particles

    NASA Astrophysics Data System (ADS)

    Mishra, Chandan K.; Rangarajan, Amritha; Ganapathy, Rajesh

    2013-05-01

    We study experimentally the glass transition dynamics in quasi-two-dimensional suspensions of colloidal ellipsoids, aspect ratio α=2.1, with repulsive as well as attractive interactions. For the purely repulsive case, we find that the orientational and translational glass transitions occur at the same area fraction. Strikingly, for intermediate depletion attraction strengths, we find that the orientational glass transition precedes the translational one. By quantifying structure and dynamics, we show that quasi-long-range ordering is promoted at these attraction strengths, which subsequently results in a two-step glass transition. Most interestingly, within experimental certainty, we observe reentrant glass dynamics only in the translational degrees of freedom.

  7. Pressure dependence of the glass transition and related properties of Solithane 113 elastomer

    NASA Astrophysics Data System (ADS)

    Questad, D. L.; Pae, K. D.; Newman, B. A.; Scheinbeim, J. I.

    1980-10-01

    Several studies have been carried out on a polyurethane elastomer (Solithane 113). At atmospheric pressure, dielectric methods were used to study ɛ″ over the temperature range from -180 to +20 °C. Three peaks in ɛ″ were observed: an α peak associated with the glass transition and two low temperatures peaks ( β and γ). Mechanical tests were peformed to osberve the effect of the pressure-induced glass transition Pg on the Young's modulus. The glass transition was studied of pressure from 1 bar to 6.5 k bar by observing the shift as a function of the dielectric α peak with pressure and also by volumetric methods. A densification of the glass and a resultant shift in the glass-transition temperature could be achieved by forming the glass at high pressures (Tg) as opposed to pressuring the glass formed at 1 bar (T*g). It was found that Δβ/Δα≳dTg /dP, but Δβ/Δα?dT*g /dP. At high pressures, dTg /dP reached a limiting value of 10.4 °C/kbar.

  8. Independently Relaxing Nanoscale Inhomogeneities as model for Structural Relaxation: Light Scattering around the Glass Transition Region.

    NASA Astrophysics Data System (ADS)

    Lee, Mierie; Schroeder, John; Saha, Susanta K.; Moynihan, Cornelius T.

    1996-03-01

    Recent observations of anomalous light scattering (Rayleigh, Brillouin, and Raman) in the glass transition region indicate that the apparent distribution of structural relaxation times corresponds to a physical distribution of nanoscale inhomogeneities (density fluctuation) with varying properties. A modified version of the Tool-Narayanaswamy model incorporating this feature has been developed. Parameters obtained by fitting heat capacity heating curves with this model are found to give an excellent prediction of the anomalous light scattering of B_2O3 glass in the transition region. Other examples from Halide glasses will also be discussed. The measurement of Boson peaks in glasses and their interpretation with respect to density fluctuations is presented. The range and degree of disorder in a glass is obtained in a quantitative sense from the behavior of the spectral form of the Boson peaks with temperature.

  9. The decoupling of the glass transitions in the two-component p-spin spherical model

    NASA Astrophysics Data System (ADS)

    Ikeda, Harukuni; Ikeda, Atsushi

    2016-07-01

    Binary mixtures of large and small particles with a disparate size ratio exhibit a rich phenomenology at their glass transition points. In order to gain insights on such systems, we introduce and study a two-component version of the p-spin spherical spin glass model. We employ the replica method to calculate the free energy and the phase diagram. We show that when the strengths of the interactions of each component are not widely separated, the model has only one glass phase characterized by the conventional one-step replica symmetry breaking. However when the strengths of the interactions are well separated, the model has three glass phases depending on the temperature and component ratio. One is the ‘single’ glass phase in which only the spins of one component are frozen while the spins of the other component remain mobile. This phase is characterized by the one-step replica symmetry breaking. The second is the ‘double’ glass phase obtained by cooling the single glass phase further, in which the spins of the remaining mobile component are also frozen. This phase is characterized by the two-step replica symmetry breaking. The third is also the ‘double’ glass phase, which, however, is formed by the simultaneous freezing of the spins of both components at the same temperatures and is characterized by the one-step replica symmetry breaking. We discuss the implications of these results for the glass transitions of binary mixtures.

  10. Calorimetric glass transition in a mean-field theory approach

    PubMed Central

    Mariani, Manuel Sebastian; Parisi, Giorgio; Rainone, Corrado

    2015-01-01

    The study of the properties of glass-forming liquids is difficult for many reasons. Analytic solutions of mean-field models are usually available only for systems embedded in a space with an unphysically high number of spatial dimensions; on the experimental and numerical side, the study of the properties of metastable glassy states requires thermalizing the system in the supercooled liquid phase, where the thermalization time may be extremely large. We consider here a hard-sphere mean-field model that is solvable in any number of spatial dimensions; moreover, we easily obtain thermalized configurations even in the glass phase. We study the 3D version of this model and we perform Monte Carlo simulations that mimic heating and cooling experiments performed on ultrastable glasses. The numerical findings are in good agreement with the analytical results and qualitatively capture the features of ultrastable glasses observed in experiments. PMID:25675523

  11. Direct Experimental Evidence of Growing Dynamical Facilitation on Approaching the Colloidal Glass Transition

    NASA Astrophysics Data System (ADS)

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

    2014-03-01

    The dramatic slowing down of dynamics with no apparent change in structure is perhaps the best-known and least understood feature of the glass transition in molecular, polymeric and colloidal liquids. Despite extensive research, the microscopic origin of this slowdown remains mysterious. In particular, it is unclear whether structural relaxation is governed by a growing length scale, as advocated by thermodynamic theories, or by the concerted motion of mobile defects termed excitations, a phenomenon known as dynamical facilitation. Here, by performing video microscopy on a binary colloidal glass-former, we show that dynamical facilitation unambiguously grows on approaching the glass transition. Interestingly, the spatial frequency of occurrence of excitations is anti-correlated with the distribution of local hexatic order, suggesting intriguing connections between structural evolution and relaxation dynamics on approaching the glass transition. SG thanks the Council for Scientifc and Industrial Research (CSIR), India, for a Shyama Prasad Mukherjee Fellowship.

  12. Molecular dynamics investigation of a density-driven glass transition in a liquid crystal system.

    PubMed

    Vieira, Pablo A; Lacks, Daniel J

    2004-08-22

    Molecular dynamics simulations are carried out to address the density-driven glass transition in a system of rodlike particles that interact with the Gay-Berne potential. Since crystallization occurs in this system on the time scale of the simulations, direct simulation of the glass transition is not possible. Instead, glasses with isotropic orientational order are heated to a temperature T, and the relaxation times by which nematic orientational order develops are determined. These relaxation times appear to diverge at a critical density rho(c); i.e., the system can equilibrate at rhorho(c) (at the temperature T). The relaxation times follow a power-law scaling as the critical density is approached, suggesting that this density-driven glass transition concurs with mode coupling theory. PMID:15303960

  13. Scaling of the hysteresis in the glass transition of glycerol with the temperature scanning rate

    NASA Astrophysics Data System (ADS)

    Wang, Yi-Zhen; Li, Ying; Zhang, Jin-Xiu

    2011-03-01

    By measuring the dependences of the temperature-dependent primary ("alpha") dielectric relaxation time behavior on the temperature scanning rate for the glass-forming glycerol, we study the scaling of hysteresis at the glass transition in glycerol. Based on the Vogel-Fulcher-Tammann (VFT) expression and the Angell's fragility concept, notable correlations of the systematic kinetic fragility, and of the hysteresis effect in the vitrification/fusion "alpha"-relaxation process of glycerol, with the temperature scanning rate, were reasonably analyzed and discussed. It was observed that the kinetic fragility m and the apparent glass-transition temperature hysteresis width Δ T_g^a, respectively, scaled the temperature scanning rate q as m ≈ αmq-γ and Δ T_g^a ≈ A0 + αqβ, at which the exponents, γ and β, were suggested to be characteristic of the resistance to the structure change or fragility change of the system during the glass transition. The observed scaling laws are quite similar to the scaling power law for the thermal hysteresis in the first-order phase transition (FOPT) of solids, providing a significant insight into the hysteresis effect in the glass transition of the glass-forming liquids.

  14. Percolation effects on entangled polymer rheology and the glass transition

    NASA Astrophysics Data System (ADS)

    Wool, Richard P.

    2012-07-01

    Current thinking on the fundamentals of entangled polymer melt rheology suggests that stress relaxation in the terminal zone occurs via Reptation, chain-end fluctuation and (convective) constraint release. This scenario is not correct. It is shown through a series of experiments with selectively deuterated model polymers that relaxation occurs through a percolation process which permits large clusters of entangled polymers to stress relax before their conformations are fully relaxed. The percolation model of entanglements (R.P. Wool, Macromolecules 26, 1564, 1993) makes unique predictions regarding the dynamics of polymer chains in the terminal relaxation zone. These include: (a) Reptating homopolymer chains with molecular weight M >> Mc appear to be non-Reptating as their ends and centers relax at the same rate in a Rouse-like manner during percolation. (b) The mechanical relaxation time τ(M) is related to the Reptation time Tr˜ M3 by τ(M) = Tr[(1-Mc/M)Me/Mc]2, which is the origin of the zero shear viscosity behaving as ηo˜M3.4 (c) The biggest surprise is that during stress relaxation, the random coil dimensions Rg(//) and Rg(⊥) are not fully relaxed when the stress and birefringence relax to zero. (d) Matrix molecular weight P effects on relaxation time τ(M) of the probe chain M are as follows: When the probe chain M>>P, the matrix P-chains percolate and Rouse-like dynamics is observed for the M-Reptating chains with τ(M) ˜ P1M2. (e) When the matrix P>>M, percolation does not occur for the M-chain and the relaxation time of the probe chain τ(M) ˜ PoM3 is in accord with DeGennes Reptation theory. These unusual results predicted by entanglement percolation are supported by extensive experimental data (NR, SANS, DSIMS, FTIR, BR) from selectively deuterated polystyrene chains HDH, DHD, HPS and DPS. These results clearly suggest that current notions of polymer rheology need to be reconsidered. Near Tg, a new perspective on the Glass Transition of amorphous

  15. Transition from glass to graphite in manufacture of composite aircraft structure

    NASA Technical Reports Server (NTRS)

    Buffum, H. E.; Thompson, V. S.

    1978-01-01

    The transition from fiberglass reinforced plastic composites to graphite reinforced plastic composites is described. Structural fiberglass design and manufacturing background are summarized. How this experience provides a technology base for moving into graphite composite secondary structure and then to composite primary structure is considered. The technical requirements that must be fulfilled in the transition from glass to graphite composite structure are also included.

  16. Bond orientational order in liquids: Towards a unified description of water-like anomalies, liquid-liquid transition, glass transition, and crystallization: Bond orientational order in liquids.

    PubMed

    Tanaka, Hajime

    2012-10-01

    There are at least three fundamental states of matter, depending upon temperature and pressure: gas, liquid, and solid (crystal). These states are separated by first-order phase transitions between them. In both gas and liquid phases a complete translational and rotational symmetry exist, whereas in a solid phase both symmetries are broken. In intermediate phases between liquid and solid, which include liquid crystal and plastic crystal phases, only one of the two symmetries is preserved. Among the fundamental states of matter, the liquid state is the most poorly understood. We argue that it is crucial for a better understanding of liquids to recognize that a liquid generally has the tendency to have a local structural order and its presence is intrinsic and universal to any liquid. Such structural ordering is a consequence of many-body correlations, more specifically, bond angle correlations, which we believe are crucial for the description of the liquid state. We show that this physical picture may naturally explain difficult unsolved problems associated with the liquid state, such as anomalies of water-type liquids (water, Si, Ge, ...), liquid-liquid transition, liquid-glass transition, crystallization and quasicrystal formation, in a unified manner. In other words, we need a new order parameter representing a low local free-energy configuration, which is a bond orientational order parameter in many cases, in addition to a density order parameter for the physical description of these phenomena. Here we review our two-order-parameter model of liquid and consider how transient local structural ordering is linked to all of the above-mentioned phenomena. The relationship between these phenomena is also discussed. PMID:23104614

  17. Glass Transition Temperature of Saccharide Aqueous Solutions Estimated with the Free Volume/Percolation Model.

    PubMed

    Constantin, Julian Gelman; Schneider, Matthias; Corti, Horacio R

    2016-06-01

    The glass transition temperature of trehalose, sucrose, glucose, and fructose aqueous solutions has been predicted as a function of the water content by using the free volume/percolation model (FVPM). This model only requires the molar volume of water in the liquid and supercooled regimes, the molar volumes of the hypothetical pure liquid sugars at temperatures below their pure glass transition temperatures, and the molar volumes of the mixtures at the glass transition temperature. The model is simplified by assuming that the excess thermal expansion coefficient is negligible for saccharide-water mixtures, and this ideal FVPM becomes identical to the Gordon-Taylor model. It was found that the behavior of the water molar volume in trehalose-water mixtures at low temperatures can be obtained by assuming that the FVPM holds for this mixture. The temperature dependence of the water molar volume in the supercooled region of interest seems to be compatible with the recent hypothesis on the existence of two structure of liquid water, being the high density liquid water the state of water in the sugar solutions. The idealized FVPM describes the measured glass transition temperature of sucrose, glucose, and fructose aqueous solutions, with much better accuracy than both the Gordon-Taylor model based on an empirical kGT constant dependent on the saccharide glass transition temperature and the Couchman-Karasz model using experimental heat capacity changes of the components at the glass transition temperature. Thus, FVPM seems to be an excellent tool to predict the glass transition temperature of other aqueous saccharides and polyols solutions by resorting to volumetric information easily available. PMID:27176640

  18. Vapor phase deposition of transition metal fluoride glasses

    NASA Astrophysics Data System (ADS)

    Boulard, Brigitte; Jacoboni, Charles

    1991-08-01

    Multicomponent fluoride glasses in the PbF2-ZnF2-GaF3 (PZG) vitreous ternary system have been prepared by vapor phase deposition. The thermal stability of the deposited glass was improved by adding stabilizing agents (AlF3, NaF, LiF, InF3). The thin films, deposited on different substrates (fluoride glass, fluoride single crystal, metal, and silica glass) have been characterized by x-ray diffraction. Differential scanning calorimetry (DSC) and secondary ion mass spectroscopy (SIMS). The quality of the film, adherence, and homogeneity was controlled by scanning electronic microscopy (SEM). The optical characteristics of the film and PZG glass are given: the visible-infrared (VIS-IR) window is 0.3-8 micrometers and the refractive index 1.59+/- 0.2 depends on the lead content. Mn2+ doped films (up to 3 mole % MnF2) are optically active: Mn2+ exhibits a broad luminescence band at 560-570 nm (orange). The achieved film thickness varies from 0.5 to 80 micrometers , and the refractive index gradient approaches the required geometry for planar waveguides (doping of the film with lanthanides is in progress).

  19. Discontinuous nature of the repulsive-to-attractive colloidal glass transition

    PubMed Central

    van de Laar, T.; Higler, R.; Schroën, K.; Sprakel, J.

    2016-01-01

    In purely repulsive colloidal systems a glass transition can be reached by increasing the particle volume fraction beyond a certain threshold. The resulting glassy state is governed by configurational cages which confine particles and restrict their motion. A colloidal glass may also be formed by inducing attractive interactions between the particles. When attraction is turned on in a repulsive colloidal glass a re-entrant solidification ensues. Initially, the repulsive glass melts as free volume in the system increases. As the attraction strength is increased further, this weakened configurational glass gives way to an attractive glass in which motion is hindered by the formation of physical bonds between neighboring particles. In this paper, we study the transition from repulsive-to-attractive glasses using three-dimensional imaging at the single-particle level. We show how the onset of cage weakening and bond formation is signalled by subtle changes in local structure. We then demonstrate the discontinuous nature of the solid-solid transition, which is marked by a critical onset at a threshold bonding energy. Finally, we highlight how the interplay between bonding and caging leads to complex and heterogeneous dynamics at the microscale. PMID:26940737

  20. Discontinuous nature of the repulsive-to-attractive colloidal glass transition.

    PubMed

    van de Laar, T; Higler, R; Schroën, K; Sprakel, J

    2016-01-01

    In purely repulsive colloidal systems a glass transition can be reached by increasing the particle volume fraction beyond a certain threshold. The resulting glassy state is governed by configurational cages which confine particles and restrict their motion. A colloidal glass may also be formed by inducing attractive interactions between the particles. When attraction is turned on in a repulsive colloidal glass a re-entrant solidification ensues. Initially, the repulsive glass melts as free volume in the system increases. As the attraction strength is increased further, this weakened configurational glass gives way to an attractive glass in which motion is hindered by the formation of physical bonds between neighboring particles. In this paper, we study the transition from repulsive-to-attractive glasses using three-dimensional imaging at the single-particle level. We show how the onset of cage weakening and bond formation is signalled by subtle changes in local structure. We then demonstrate the discontinuous nature of the solid-solid transition, which is marked by a critical onset at a threshold bonding energy. Finally, we highlight how the interplay between bonding and caging leads to complex and heterogeneous dynamics at the microscale. PMID:26940737

  1. Discontinuous nature of the repulsive-to-attractive colloidal glass transition

    NASA Astrophysics Data System (ADS)

    van de Laar, T.; Higler, R.; Schroën, K.; Sprakel, J.

    2016-03-01

    In purely repulsive colloidal systems a glass transition can be reached by increasing the particle volume fraction beyond a certain threshold. The resulting glassy state is governed by configurational cages which confine particles and restrict their motion. A colloidal glass may also be formed by inducing attractive interactions between the particles. When attraction is turned on in a repulsive colloidal glass a re-entrant solidification ensues. Initially, the repulsive glass melts as free volume in the system increases. As the attraction strength is increased further, this weakened configurational glass gives way to an attractive glass in which motion is hindered by the formation of physical bonds between neighboring particles. In this paper, we study the transition from repulsive-to-attractive glasses using three-dimensional imaging at the single-particle level. We show how the onset of cage weakening and bond formation is signalled by subtle changes in local structure. We then demonstrate the discontinuous nature of the solid-solid transition, which is marked by a critical onset at a threshold bonding energy. Finally, we highlight how the interplay between bonding and caging leads to complex and heterogeneous dynamics at the microscale.

  2. Effects of configurational changes on electrical resistivity during glass-liquid transition of two bulk metal-alloy glasses.

    PubMed

    Aji, D P B; Johari, G P

    2014-12-14

    Consequences of increase in structural fluctuations on heating Pd40Ni10Cu30P20 and Zr46.75Ti8.25Cu7.5Ni10Be27.5 through their glass to liquid transition range were investigated by measuring the electrical resistivity, ρ, an electron scattering property. The temperature coefficient of resistivity (TCR = (1/ρ) dρ/dT) of the liquid and glassy states is negative. The plots of their ρ against T in the Tg (glass to liquid transition) range show a gradual change in the slope similar to the change observed generally for the plots of the density, elastic modulus, and refractive index. As fluctuations in the melt structure involve fewer configurations on cooling, ρ increases. In the energy landscape description, the melt's structure explores fewer minima with decrease in T, vibrational frequencies increase, and electron scattering and ρ increase. Plots of (-dρ/dT) against T resemble the plot of the specific heat of other glasses and show a sub-Tg feature and a rapid rise at T near Tg. Analysis shows that the magnitude of negative TCR is dominated by change in the phonon characteristics, and configurational fluctuations make it more negative. The TCR of the liquid and glassy states seems qualitatively consistent with the variation in the structure factor in Ziman's model for pure liquid metals as extended by Nagel to metal alloys and used to explain the negative TCR of a two-component metal glass. PMID:25494761

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

    PubMed

    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 (∞). PMID:26646885

  4. Glass Transition in Thin Supported Polymer Films Probed by Temperature-Modulated Ellipsometry in Vacuum

    NASA Astrophysics Data System (ADS)

    Efremov, Mikhail; Nealey, Paul

    2010-03-01

    Glass transition in model glass-forming polymer coatings is probed by ellipsometry in vacuum. Novel temperature-modulated modification of the technique is used alongside with traditional linear temperature program [1]. Spin-cast 2 - 200 nm thick polystyrene (PS) and 10 - 200 nm thick poly(methyl methacrylate) (PMMA) films on silicon are studied. Measurements are performed at 10-6 - 10-8 torr residual gas pressure. Temperature modulation allows effective separation of reversible glass transition from accompanying irreversible processes. It is found that glass transition in both polymers demonstrates no appreciable dependence on film thickness for more than 20 nm thick coatings. The temperature of the transition (Tg) in thinnest PS films does depend on film thickness, but does not follow often accepted Tg(h)=Tg(∞)[1-(Ah)^δ] function (where h is film thickness, A and δ are constants). Effects of polymer molecular weight and substrate surface pre-treatment on glass transition will be discussed also.[4pt] [1]. M. Yu. Efremov, A. V. Kiyanova, and P. F. Nealey, Macromolecules, 41, 5978 (2008).

  5. Silver nanoparticles enhanced multichannel transition luminescence of Pr3+ in heavy metal germanium tellurite glasses

    NASA Astrophysics Data System (ADS)

    Du, Y. Y.; Chen, B. J.; Pun, E. Y. B.; Wang, Z. Q.; Zhao, X.; Lin, H.

    2015-01-01

    Enhanced luminescence of Pr3+ was observed in heavy metal germanium tellurite (NZPGT) glasses containing silver nanoparticles. Long-time annealing at 300 °C yield spherical and well-dispersed Ag nanoparticles with ~4 nm diameter as evidenced by transmission electron microscope (TEM). Multichannel transition luminescence intensity of Pr3+ in Ag nanoparticles embedded glasses grows by ~36% in comparison with the glasses without silver doping, which provides a new approach to improve energy conversion efficiency of GaAsAl solar cells. Hypersensitive probe Eu3+ reveals that electric field around rare-earth ions is remarkably enhanced due to the presence of Ag nanoparticles in the glass matrix, resulting in the luminescence intensification of Pr3+ in NZPGT glasses embedded with Ag nanoparticles.

  6. Structure of glasses containing transition metal ions. Progress report, February 1, 1980-January 31, 1981

    SciTech Connect

    White, W.B.; Fox, K.; Herman, J.S.; Houser, C.; Nelson, C.

    1981-01-01

    This research is concerned with the structure and properties of insulator glasses, particularly as these are modified by transition metal ions in solution. This progress report spans a one-year period and describes the status of the work two-thirds into the sixth contract year. Work on the host glasses has been concentrated on the alkali borosilicate, alkali aluminosilicate and alkali-gallia-silicate glasses. The main interest here is the structure setting for aluminum. The optical absorption spectra of nickel and iron in a variety of glasses have been examined. Utilization of luminescence in addition to optical absorption spectra has permitted the identification of several iron arrangements in glass. The investigation of diffusion processes, particularly hydrogen diffusion, by sputter-induced photon spectrometry (SIPS) has moved from qualitative demonstration to quantitative calculation.

  7. Coordination and valence state of transition metal ions in alkali-borate glasses

    NASA Astrophysics Data System (ADS)

    Terczyńska-Madej, A.; Cholewa-Kowalska, K.; Łączka, M.

    2011-10-01

    Borate glasses of the 20R 2O·80B 2O 3 type, where R = Li, Na and K, were colored by doping with transition metal ions (Co, Ni, Cr and Mn). The glasses were obtained by melting at the temperature of 1150 °C. For these glasses optical absorption in UV-VIS-NIR range were recorded. Analysis of the spectra allows to be determined the coordination and oxidation states of the doping transition metal ions. Changes of their coordination or oxidation are presented as a function of the optical basicity Λ after Duffy. Cobalt and nickel are present in examined borate glasses as divalent ions (Co 2+, Ni 2+) in octahedral coordination mainly, but the tetrahedral coordination state of cobalt is also possible. Chromium and manganese are present in the borate glasses in various oxidation state, though Cr 3+ and Mn 3+ ions in the octahedral coordination are probably dominant. A decrease of the electronegativity of the modifiers (Li → Na → K) and an increase of the glass matrix basicity cause a shift of the oxidation/reduction equilibrium towards higher valences of the transition metals (Cr 6+, Mn 3+).

  8. Use of glass transitions in carbohydrate excipient design for lyophilized protein formulations.

    PubMed

    Roughton, Brock C; Topp, E M; Camarda, Kyle V

    2012-01-10

    This work describes an effort to apply methods from process systems engineering to a pharmaceutical product design problem, with a novel application of statistical approaches to comparing solutions. A computational molecular design framework was employed to design carbohydrate molecules with high glass transition temperatures and low water content in the maximally freeze-concentrated matrix, with the objective of stabilizing lyophilized protein formulations. Quantitative structure-property relationships were developed for glass transition temperature of the anhydrous solute, glass transition temperature of the maximally concentrated solute, melting point of ice and Gordon-Taylor constant for carbohydrates. An optimization problem was formulated to design an excipient with optimal property values. Use of a stochastic optimization algorithm, Tabu search, provided several carbohydrate excipient candidates with statistically similar property values, as indicated by prediction intervals calculated for each property. PMID:24385675

  9. Shear banding of colloidal glasses: observation of a dynamic first-order transition.

    PubMed

    Chikkadi, V; Miedema, D M; Dang, M T; Nienhuis, B; Schall, P

    2014-11-14

    We demonstrate that application of an increasing shear field on a glass leads to an intriguing dynamic first-order transition in analogy with equilibrium transitions. By following the particle dynamics as a function of the driving field in a colloidal glass, we identify a critical shear rate upon which the diffusion time scale of the glass exhibits a sudden discontinuity. Using a new dynamic order parameter, we show that this discontinuity is analogous to a first-order transition, in which the applied stress acts as the conjugate field on the system's dynamic evolution. These results offer new perspectives to comprehend the generic shear-banding instability of a wide range of amorphous materials. PMID:25432056

  10. Liquid-liquid transition in a strong bulk metallic glass-forming liquid.

    PubMed

    Wei, Shuai; Yang, Fan; Bednarcik, Jozef; Kaban, Ivan; Shuleshova, Olga; Meyer, Andreas; Busch, Ralf

    2013-01-01

    Polymorphic phase transitions are common in crystalline solids. Recent studies suggest that phase transitions may also exist between two liquid forms with different entropy and structure. Such a liquid-liquid transition has been investigated in various substances including water, Al2O3-Y2O3 and network glass formers. However, the nature of liquid-liquid transition is debated due to experimental difficulties in avoiding crystallization and/or measuring at high temperatures/pressures. Here we report the thermodynamic and structural evidence of a temperature-induced weak first-order liquid-liquid transition in a bulk metallic glass-forming system Zr(41.2)Ti(13.8)Cu(12.5)Ni10Be(22.5) characterized by non- (or weak) directional bonds. Our experimental results suggest that the local structural changes during the transition induce the drastic viscosity changes without a detectable density anomaly. These changes are correlated with a heat capacity maximum in the liquid. Our findings support the hypothesis that the 'strong' kinetics (low fragility) of a liquid may arise from an underlying lambda transition above its glass transition. PMID:23817404

  11. Dynamical State Transition by Neuromodulation Due to Acetylcholine in Neural Network Model for Oscillatory Phenomena in Thalamus

    NASA Astrophysics Data System (ADS)

    Omori, Toshiaki; Horiguchi, Tsuyoshi

    2004-12-01

    We propose a two-layered neural network model for oscillatory phenomena in the thalamic system and investigate an effect of neuromodulation due to the acetylcholine on the oscillatory phenomena by numerical simulations. The proposed model consists of a layer of the thalamic reticular neurons and that of the cholinergic neurons. We introduce a dynamics of concentration of the acetylcholine which depends on a state of the cholinergic neurons, and assume that the conductance of the thalamic reticular neurons is dynamically regulated by the acetylcholine. From the results obtained by numerical simulations, we find that a dynamical transition between a bursting state and a resting state occurs successively in the layer of the thalamic reticular neurons due to the acetylcholine. Therefore it turns out that the neuromodulation due to the acetylcholine is important for the dynamical state transition in the thalamic system.

  12. Connection between the glass transition temperature Tg and the Arrhenius temperature TA in supercooled liquids

    NASA Astrophysics Data System (ADS)

    Novikov, V. N.

    2016-08-01

    At high temperatures the structural relaxation time in liquids has Arrhenius temperature dependence. At lowering temperature, temperature dependence changes to a super Arrhenius at some temperature TA. This temperature is an important point for the structural relaxation dynamics in supercooled liquids because it reflects the transition to collective relaxation. Here we derive a relation between TA, the glass transition temperature Tg and fragility. We show that the ratio Tg/TA increases with increasing fragility of a liquid. The derived relation is in agreement with the experimental data in a series of molecular, hydrogen bonding and two inorganic glass-formers.

  13. Glass transition temperature of a cationic polymethacrylate dependent on the plasticizer content - Simulation vs. experiment

    NASA Astrophysics Data System (ADS)

    Wagner, Karl G.; Maus, Martin; Kornherr, Andreas; Zifferer, Gerhard

    2005-04-01

    Atomistic molecular dynamics simulations ( NPT ensemble) are performed to compute the specific volume as a function of temperature of cationic polymethacrylate (Eudragit ® RS) with varying plasticizer (triethylcitrate) content ranging from pure polymer to a plasticizer weight proportion of 7.70%. The simulated glass transition temperature of these polymer-plasticizer blends is determined as the temperature marking the kink in the slope of specific volume vs. temperature plots. A linear dependence of the glass transition temperature on the plasticizer content is found. The computational findings are supported by differential scanning calorimetry experiments showing the same trend thus validating the applied computational method.

  14. Glass Transitions and Elastic Properties of Lithium Borate Glasses over a Wide Composition Range Studied by Micro-Brillouin Scattering

    NASA Astrophysics Data System (ADS)

    Fukawa, Yasuteru; Matsuda, Yu; Ike, Yuji; Kodama, Masao; Kojima, Seiji

    2008-05-01

    The elastic properties of lithium borate glasses, denoted by the composition formula xLi2O·(100 - x)B2O3 where x is the molar concentration in mol %, have been investigated over a wide composition range 6 ≤x ≤52 mol % by micro-Brillouin scattering. From the observed values of the longitudinal and transverse sound velocities, the elastic constants such as longitudinal modulus, shear modulus, Young's modulus, and Poisson's ratio have been determined. The elastic constants have shown a strong composition dependence due to the variation of intermediate structural units. The temperature dependences of the longitudinal sound velocity and absorption coefficient of 44Li2O·56B2O3 clearly show the anomalies at the glass transition and crystallization temperatures.

  15. Effects of configurational changes on electrical resistivity during glass-liquid transition of two bulk metal-alloy glasses

    SciTech Connect

    Aji, D. P. B.; Johari, G. P.

    2014-12-14

    Consequences of increase in structural fluctuations on heating Pd{sub 40}Ni{sub 10}Cu{sub 30}P{sub 20} and Zr{sub 46.75}Ti{sub 8.25}Cu{sub 7.5}Ni{sub 10}Be{sub 27.5} through their glass to liquid transition range were investigated by measuring the electrical resistivity, ρ, an electron scattering property. The temperature coefficient of resistivity (TCR = (1/ρ) dρ/dT) of the liquid and glassy states is negative. The plots of their ρ against T in the T{sub g} (glass to liquid transition) range show a gradual change in the slope similar to the change observed generally for the plots of the density, elastic modulus, and refractive index. As fluctuations in the melt structure involve fewer configurations on cooling, ρ increases. In the energy landscape description, the melt's structure explores fewer minima with decrease in T, vibrational frequencies increase, and electron scattering and ρ increase. Plots of (−dρ/dT) against T resemble the plot of the specific heat of other glasses and show a sub-T{sub g} feature and a rapid rise at T near T{sub g}. Analysis shows that the magnitude of negative TCR is dominated by change in the phonon characteristics, and configurational fluctuations make it more negative. The TCR of the liquid and glassy states seems qualitatively consistent with the variation in the structure factor in Ziman's model for pure liquid metals as extended by Nagel to metal alloys and used to explain the negative TCR of a two-component metal glass.

  16. Evidence of phase transition in Nd3+ doped phosphate glass determined by thermal lens spectrometry.

    PubMed

    Andrade, Acácio A; Lourenço, Sidney A; Pilla, Viviane; Silva, Anielle C Almeida; Dantas, Noelio O

    2014-01-28

    Thermal lens spectroscopy (TLS), differential scanning calorimetry (DSC) and Fourier transform infrared (FTIR) techniques were applied to the thermo-optical property analysis of a new phosphate glass matrix PANK with nominal composition 40P2O5·20Al2O3·35Na2O·5K2O (mol%), doped with different Nd(3+) compositions. This glass system, synthesized by the fusion protocol, presents high transparency from UV to the near infrared, excellent thermo-optical properties at room temperature and high fluorescence quantum efficiency. Thermal lens phase shift parameters, thermal diffusivity and the DSC signal present pronounced changes at about 61 °C for the PANK glass system. This anomalous behavior was associated with a phase transition in the nanostructured glass materials. The FTIR signal confirms the presence of isolated PO4 tetrahedron groups connected to different cations in PANK glass. As a main result, our experimental data suggest that these tetrahedron groups present a structural phase transition, paraelectric-ferroelectric phase transition, similar to that in potassium dihydrogen phosphate, KH2PO4, nanocrystals and which TLS technique can be used as a sensitive method to investigate changes in the structural level of nanostructured materials. PMID:24310914

  17. Thermal analysis of frozen solutions: multiple glass transitions in amorphous systems.

    PubMed

    Sacha, Gregory A; Nail, Steven L

    2009-09-01

    Frozen aqueous solutions of sucrose exhibit two "glass transition-like" thermal events below the melting endotherm of ice when examined by DSC, but the physical basis of these events has been a source of some disagreement. In this study, a series of sugars, including sucrose, lactose, trehalose, maltose, fructose, galactose, fucose, mannose, and glucose were studied by modulated DSC and freeze-dry microscopy in order to better understand whether sucrose is unique in any way with respect to this behavior, as well as to explore the physical basis, and the pharmaceutical significance of these multiple transitions. Double transitions were found to be a common feature of all sugars examined. The results are consistent with both thermal events being glass transitions in that (1) both events have second-order characteristics that appear in the reversing signals, (2) annealing experiments reveal that enthalpy recovery is associated with each transition, and (3) Lissajous plots indicate that no detectable latent heat of melting is associated with either transition. The data in this study are consistent with the idea that the lower temperature transition arises from a metastable glassy mixture containing more water than that in the maximally freeze-concentrated solute. Freeze-dry microscopy observations show that for all of the sugars examined, it is the higher temperature transition that is associated with structural collapse during freeze-drying. There is no apparent pharmaceutical significance associated with the lower-temperature transition. PMID:19384925

  18. Growing dynamical facilitation on approaching the random pinning colloidal glass transition.

    PubMed

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

    2014-01-01

    Despite decades of research, it remains to be established whether the transformation of a liquid into a glass is fundamentally thermodynamic or dynamic in origin. Although observations of growing length scales are consistent with thermodynamic perspectives, the purely dynamic approach of the Dynamical Facilitation (DF) theory lacks experimental support. Further, for vitrification induced by randomly freezing a subset of particles in the liquid phase, simulations support the existence of an underlying thermodynamic phase transition, whereas the DF theory remains unexplored. Here, using video microscopy and holographic optical tweezers, we show that DF in a colloidal glass-forming liquid grows with density as well as the fraction of pinned particles. In addition, we observe that heterogeneous dynamics in the form of string-like cooperative motion emerges naturally within the framework of facilitation. Our findings suggest that a deeper understanding of the glass transition necessitates an amalgamation of existing theoretical approaches. PMID:25119444

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

    NASA Astrophysics Data System (ADS)

    Jakobsen, Bo; Sanz, Alejandro; Niss, Kristine; Hecksher, Tina; Pedersen, Ib H.; Rasmussen, Torben; Christensen, Tage; Olsen, Niels Boye; Dyre, Jeppe C.

    2016-05-01

    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 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.

  20. Growing dynamical facilitation on approaching the random pinning colloidal glass transition

    NASA Astrophysics Data System (ADS)

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

    2014-08-01

    Despite decades of research, it remains to be established whether the transformation of a liquid into a glass is fundamentally thermodynamic or dynamic in origin. Although observations of growing length scales are consistent with thermodynamic perspectives, the purely dynamic approach of the Dynamical Facilitation (DF) theory lacks experimental support. Further, for vitrification induced by randomly freezing a subset of particles in the liquid phase, simulations support the existence of an underlying thermodynamic phase transition, whereas the DF theory remains unexplored. Here, using video microscopy and holographic optical tweezers, we show that DF in a colloidal glass-forming liquid grows with density as well as the fraction of pinned particles. In addition, we observe that heterogeneous dynamics in the form of string-like cooperative motion emerges naturally within the framework of facilitation. Our findings suggest that a deeper understanding of the glass transition necessitates an amalgamation of existing theoretical approaches.

  1. Neutron Scattering Analysis of Water's Glass Transition and Micropore Collapse in Amorphous Solid Water

    NASA Astrophysics Data System (ADS)

    Hill, Catherine R.; Mitterdorfer, Christian; Youngs, Tristan G. A.; Bowron, Daniel T.; Fraser, Helen J.; Loerting, Thomas

    2016-05-01

    The question of the nature of water's glass transition has continued to be disputed over many years. Here we use slow heating scans (0.4 K min-1 ) of compact amorphous solid water deposited at 77 K and an analysis of the accompanying changes in the small-angle neutron scattering signal, to study mesoscale changes in the ice network topology. From the data we infer the onset of rotational diffusion at 115 K, a sudden switchover from nondiffusive motion and enthalpy relaxation of the network at <121 K to diffusive motion across sample grains and sudden pore collapse at >121 K , in excellent agreement with the glass transition onset deduced from heat capacity and dielectric measurements. This indicates that water's glass transition is linked with long-range transport of water molecules on the time scale of minutes and, thus, clarifies its nature. Furthermore, the slow heating rates combined with the high crystallization resistance of the amorphous sample allow us to identify the glass transition end point at 136 K, which is well separated from the crystallization onset at 144 K—in contrast to all earlier experiments in the field.

  2. Molecular Motion in Polymers: Mechanical Behavior of Polymers Near the Glass-Rubber Transition Temperature.

    ERIC Educational Resources Information Center

    Sperling, L. H.

    1982-01-01

    The temperature at which the onset of coordinated segmental motion begins is called the glass-rubber transition temperature (Tg). Natural rubber at room temperature is a good example of a material above its Tg. Describes an experiment examining the response of a typical polymer to temperature variations above and below Tg. (Author/JN)

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

    PubMed

    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. PMID:27193003

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

    EPA Science Inventory

    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...

  5. Liquid-glass transition as the freezing of characteristic acoustic frequencies

    SciTech Connect

    Sanditov, D. S.

    2010-11-15

    Half-quantum interpretation is proposed for the liquid-glass transition as the freezing of characteristic acoustic frequencies (degrees of freedom) that are related to the molecular mobility of delocalized excited kinetic units, namely, linear quantum oscillators. There exists a correlation between the energy quantum of an elementary excitation (atom delocalization energy) and the glass transition temperature, which is proportional to the characteristic Einstein temperature. By analogy with the Einstein theory of the heat capacity of solids, the temperature range of the concentration of excited atoms in an amorphous medium is divided into the following two regions: a high-temperature region with a linear temperature dependence of this concentration and a low-temperature region, where the concentration of excited atoms decreases exponentially to the limiting minimum value (about 3%). At this value, the viscosity increases to a critical value (about 10{sup 12} Pa s), which corresponds to the glass transition temperature, i.e., the temperature of freezing the mobility of excited kinetic units. The temperature dependence of the free activation energy of viscous flow in the glass transition range is specified by the temperature dependence of the relative number of excited atoms.

  6. Neutron Scattering Analysis of Water's Glass Transition and Micropore Collapse in Amorphous Solid Water.

    PubMed

    Hill, Catherine R; Mitterdorfer, Christian; Youngs, Tristan G A; Bowron, Daniel T; Fraser, Helen J; Loerting, Thomas

    2016-05-27

    The question of the nature of water's glass transition has continued to be disputed over many years. Here we use slow heating scans (0.4  K min^{-1}) of compact amorphous solid water deposited at 77 K and an analysis of the accompanying changes in the small-angle neutron scattering signal, to study mesoscale changes in the ice network topology. From the data we infer the onset of rotational diffusion at 115 K, a sudden switchover from nondiffusive motion and enthalpy relaxation of the network at <121  K to diffusive motion across sample grains and sudden pore collapse at >121  K, in excellent agreement with the glass transition onset deduced from heat capacity and dielectric measurements. This indicates that water's glass transition is linked with long-range transport of water molecules on the time scale of minutes and, thus, clarifies its nature. Furthermore, the slow heating rates combined with the high crystallization resistance of the amorphous sample allow us to identify the glass transition end point at 136 K, which is well separated from the crystallization onset at 144 K-in contrast to all earlier experiments in the field. PMID:27284664

  7. Impact-Induced Glass Transition in Elastomeric Coatings

    NASA Astrophysics Data System (ADS)

    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.

  8. Transport properties of glass-forming liquids suggest that dynamic crossover temperature is as important as the glass transition temperature

    PubMed Central

    Mallamace, Francesco; Branca, Caterina; Corsaro, Carmelo; Leone, Nancy; Spooren, Jeroen; Chen, Sow-Hsin; Stanley, H. Eugene

    2010-01-01

    It is becoming common practice to partition glass-forming liquids into two classes based on the dependence of the shear viscosity η on temperature T. In an Arrhenius plot, ln η vs 1/T, a strong liquid shows linear behavior whereas a fragile liquid exhibits an upward curvature [super-Arrhenius (SA) behavior], a situation customarily described by using the Vogel–Fulcher–Tammann law. Here we analyze existing data of the transport coefficients of 84 glass-forming liquids. We show the data are consistent, on decreasing temperature, with the onset of a well-defined dynamical crossover η×, where η× has the same value, η× ≈ 103 Poise, for all 84 liquids. The crossover temperature, T×, located well above the calorimetric glass transition temperature Tg, marks significant variations in the system thermodynamics, evidenced by the change of the SA-like T dependence above T× to Arrhenius behavior below T×. We also show that below T× the familiar Stokes–Einstein relation D/T ∼ η-1 breaks down and is replaced by a fractional form D/T ∼ η-ζ, with ζ ≈ 0.85. PMID:21148100

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

    PubMed Central

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

    2015-01-01

    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 12 h 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. PMID:26341321

  10. Effect of mixed transition metal ions on DC conductivity in lithium bismuth borate glasses

    SciTech Connect

    Khasa, S.; Yadav, Arti Dahiya, M. S.; Seema,; Ashima; Agarwal, A.

    2015-06-24

    The DC conductivities of glasses having composition x(2NiO·V{sub 2}O{sub 5})·(30-x)Li{sub 2}O·20Bi{sub 2}O{sub 3}·50B{sub 2}O{sub 3} (with x=0, 2, 5, 7 and 10, i.e. NVLBB glasses) and glass samples having composition 7NiO·23 Li{sub 2}O·20Bi{sub 2}O{sub 3}·50B{sub 2}O{sub 3} and 7V{sub 2}O{sub 5}·23Li{sub 2}O·20Bi{sub 2}O{sub 3}·50B{sub 2}O{sub 3} (NLBB and VLBB respectively) are investigated as a function of temperature. Conductivity for glasses containing higher percentage of lithium ions is predominantly ionic and in glasses containing higher percentage of transition metal (TM) ions is predominantly electronic. The observed increase in conductivity with x and peak-like behavior at x=7 in NVLBB glasses due to competitive transport of small polaron contributing to a significant structural change in NVLBB glasses. Variation of molar volume and density was also observed with x. In NVLBB glasses, as x increases density increases except a slight decrease at x=7. Also density increases in NLBB whereas in case of VLBB it decreases in comparison to NVLBB1 glass composition. Mott’s small polaron hopping (SPH) model has been applied to analyze the high temperature conductivity data and activation energy.

  11. Spectroscopic and ultrasonic investigations on structural characterization of borate glass specimen doped with transition metal ions.

    PubMed

    Sathish, K; Thirumaran, S

    2015-08-01

    The present work describes the glass samples of composition (x% V₂O₅-(80-x)% B₂O₃-20% Na₂CO₃) VBS glass system and (x%MnO₂-(80-x)% B₂O₃-20% Na₂CO₃) in MBS glass system with mol% ranging from x=3, 6, 9, 12, 15 and 18 in steps of 3 mol% are prepared by melt quenching technique. For these prepared glass systems, sound velocity (longitudinal and shear velocities) and density have been measured. The sound velocity (longitudinal and shear) was measured by using pulse-echo technique at 5 MHz. The XRD study was carried to out to ascertain the amorphous nature of the glass specimen. Using these measured values, the elastic moduli, Poisson's ratio, Debye temperature, acoustic impedance and thermal expansion coefficient of the two glass systems were evaluated. The elastic and mechanical properties of the prepared glass systems are analyzed from ultrasonic study and the structural characterization from spectroscopic study. The effects due to the doping of transition metal ions with borate have been discussed. In the V₂O₅ doped glass system,(VBS glass system) the sound velocity, density and elastic moduli, steeply increases after 12 mol% comparatively with MnO₂ doped glass system (VBS glass system). The present study critically observes the doping of V₂O₅ with borate enhances the strengthening of network linkage and hardening of the glassy network structure than MnO₂. The IR spectral analysis reveals depolymerization of the borate network and conversion of BO₃ or BO4 units with the formation of non-bridging oxygen. The FTIR spectral studies confirm the presence of various functional groups of the sample. FTIR spectrum of sample exhibits broad absorption bands indicating the wide distribution of borate structural units. The effect of Na₂CO₃, V₂O₅ and MnO₂ contents on the structures of borate glass is evaluated from the FTIR spectra. The topological aspects of the prepared glass samples are exhaustively reported from SEM micrographs

  12. Spectroscopic and ultrasonic investigations on structural characterization of borate glass specimen doped with transition metal ions

    NASA Astrophysics Data System (ADS)

    Sathish, K.; Thirumaran, S.

    2015-08-01

    The present work describes the glass samples of composition (x% V2O5-(80-x)% B2O3-20% Na2CO3) VBS glass system and (x% MnO2-(80-x)% B2O3-20% Na2CO3) in MBS glass system with mol% ranging from x = 3, 6, 9, 12, 15 and 18 in steps of 3 mol% are prepared by melt quenching technique. For these prepared glass systems, sound velocity (longitudinal and shear velocities) and density have been measured. The sound velocity (longitudinal and shear) was measured by using pulse-echo technique at 5 MHz. The XRD study was carried to out to ascertain the amorphous nature of the glass specimen. Using these measured values, the elastic moduli, Poisson's ratio, Debye temperature, acoustic impedance and thermal expansion coefficient of the two glass systems were evaluated. The elastic and mechanical properties of the prepared glass systems are analyzed from ultrasonic study and the structural characterization from spectroscopic study. The effects due to the doping of transition metal ions with borate have been discussed. In the V2O5 doped glass system, (VBS glass system) the sound velocity, density and elastic moduli, steeply increases after 12 mol% comparatively with MnO2 doped glass system (VBS glass system). The present study critically observes the doping of V2O5 with borate enhances the strengthening of network linkage and hardening of the glassy network structure than MnO2. The IR spectral analysis reveals depolymerization of the borate network and conversion of BO3 or BO4 units with the formation of non-bridging oxygen. The FTIR spectral studies confirm the presence of various functional groups of the sample. FTIR spectrum of sample exhibits broad absorption bands indicating the wide distribution of borate structural units. The effect of Na2CO3, V2O5 and MnO2 contents on the structures of borate glass is evaluated from the FTIR spectra. The topological aspects of the prepared glass samples are exhaustively reported from SEM micrographs.

  13. Optical transitions of Dy/sup 3 +/ ions in fluorozirconate glass

    SciTech Connect

    Adam, J.L.; Docq, A.D.; Lucas, J.

    1988-08-01

    Optical absorption and emission spectra are presented for Dy/sup 3 +/ ions in fluorozirconate (ZBLA) glass. The measured oscillator strengths and radiative rates for several transitions are compared with calculated values. Radiative transition rates for the excited states are determined by using the Judd-Ofelt theory (B.R. Judd, Phys. Rev. 127, 750 (1962); G.S. Ofelt, J. Chem. Phys. 37, 511 (1962)). Thermal evolution of the radiative rate is observed for the /sup 4/F/sub 9/2/ level and is well accounted for by Start level thermalization. Energy transfer effects are responsible for the nonradiative transitions.

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

    PubMed

    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. PMID:26351671

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

    PubMed Central

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

    2015-01-01

    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. PMID:26351671

  16. Flight-measured laminar boundary-layer transition phenomena including stability theory analysis

    NASA Technical Reports Server (NTRS)

    Obara, C. J.; Holmes, B. J.

    1985-01-01

    Flight experiments were conducted on a single-engine turboprop aircraft fitted with a 92-in-chord, 3-ft-span natural laminar flow glove at glove section lift coefficients from 0.15 to 1.10. The boundary-layer transition measurement methods used included sublimating chemicals and surface hot-film sensors. Transition occurred downstream of the minimum pressure point. Hot-film sensors provided a well-defined indication of laminar, laminar-separation, transitional, and turbulent boundary layers. Theoretical calculations of the boundary-layer parameters provided close agreement between the predicted laminar-separation point and the measured transition location. Tollmien-Schlichting (T-S) wave growth n-factors between 15 and 17 were calculated at the predicted point of laminar separation. These results suggest that for many practical airplane cruise conditions, laminar separation (as opposed to T-S instability) is the major cause of transition in predominantly two-dimensional flows.

  17. Glass transition, kinetics of crystallization and anomalous phase transformations in tellurite melts

    NASA Astrophysics Data System (ADS)

    Chakraborty, Soumee; Venkata Krishnan, R.; Sivasubramanian, V.; Kalavathi, S.

    2014-12-01

    A lead-tellurite (0.3PbO:0.7TeO2) eutectic glass was investigated through a combination of thermal, structural and vibrational spectroscopic studies to examine the kinetics of crystallization and phase transformations during the heating of the glass and the cooling of the liquid. A linear relation was found to correlate the glass transition and crystallization temperatures, from which the ideal glass transition was determined. Among the several kinetic models that were analyzed, the primary crystallization was found to agree most to the Johnson-Mehl-Avrami model, suggesting the microstructural evolution as a two-dimensional crystallization and growth. The complexity of the transformation process was evidenced from the dependence of activation energy (E) on the crystallized fraction (α) using model-free isoconversional methods. The decreasing trend of E(α) was found to be characteristic of a reversible process followed by an irreversible one. Furthermore, nucleation was found to maximize at a temperature much lower than the experimentally observed crystallization onset. The structural evolution of the devitrified phases depicted the coexistence of phases (PbTeO3 and α-TeO2) during the two-stage crystallization. Anomalous crystallization into the Pb2Te3O8 phase was observed when the devitrified melt was cooled. Such an anomaly is explained using amorphous phase separation, which is inherent to the tellurite glass system owing to the presence of unique asymmetric structural units in the corresponding melts.

  18. Observation of spin glass transition in spinel LiCoMnO4

    NASA Astrophysics Data System (ADS)

    Chen, Hong; Yang, Xu; Zhang, Pei-Song; Liang, Lei; Hong, Yuan-Ze; Wei, Ying-Jin; Chen, Gang; Du, Fei; Wang, Chun-Zhong

    2015-12-01

    Spinel LiCoMnO4 is prepared by solid-state reaction and its magnetic properties are comprehensively studied by direct current (DC) and alternating current (AC) susceptibilities, isothermal remanent magnetizations, and magnetic hysteresis. Fitting to the Curie-Weiss law by using high-temperature zero-field-cooled susceptibility confirms a low-spin state of Co3+ with S = 0. Both the fitting parameters first increase and then tend to be saturated at high magnetic fields through using isothermal remanent magnetizations, which suggests a spin glass transition at low temperature. AC susceptibility study also supports this conclusion since the frequency dependence of peak position and intensity follows the tendency of a spin glass transition. The origin of the spin-glass transition in LiCoMnO4 might be attributed to a spatial segregation between non-magnetic Co3+ regions and spin glass ordered regions of Mn4+ ions. Project supported by the National Key Basic Research Program of China (Grant No. 2015CB251103), the Development Program of Science and Technology of Jilin Province, China (Grant No. 20140101093JC), and the Program of Science and Technology of Jilin City, China (Grant No. 201434006).

  19. Atomic mechanism of the heating-induced phase transitions of the simple monatomic glasses

    NASA Astrophysics Data System (ADS)

    Hoang, Vo Van

    2011-10-01

    Atomic mechanism of the heating-induced phase transitions of the monatomic Lennard-Jones (LJ) glass has been studied via molecular dynamics (MD) simulations. Monatomic LJ glass was heated up at two different heating rates, crystallization occurs at the lowest one and further heating leads to the melting of LJ crystal. Thermodynamics of the phase transitions and corresponding evolution of structural properties upon heating have been analyzed in details. Atomic mechanism of a crystallization of the glassy state was monitored via spatio-temporal arrangements of the atoms involved in the 1421 bond-pair of the fcc crystalline structure. The 1421 bond-pair was detected via the Honeycutt-Andersen analysis [J.D. Honeycutt, H.C. Andersen, J. Phys. Chem. 91 (1987) 4950]. We found that crystallization of the monatomic LJ glass occurs via homogeneous local rearrangements of atoms in the glassy matrix and we found an important role of the liquid-like atoms (existed in the glassy state) in crystallization of the system. In addition, spatio-temporal arrangements of the liquid-like atoms in the system upon further heating were shown in order to clarify the atomic mechanism of a melting of the obtained LJ crystal. Liquid-like atoms were defined by the Lindemann melting criterion. Our results provide previously un-reported data and give deeper understanding of the heating-induced phase transitions in the less stable metallic glasses, which have been observed in practice.

  20. Spacelab experiment definition study on phase transition and critical phenomena in fluids: Interim report on experimental justification

    NASA Technical Reports Server (NTRS)

    Moldover, M. R.; Hocken, M. R.; Gammon, R. W.; Sengers, J. V.

    1976-01-01

    Pure fluids and fluid mixtures near critical points are identified and are related to the progress of several disciplines. Consideration is given to thermodynamic properties, transport properties, and the complex nonlinear phenomena which occur when fluids undergo phase transitions in the critical region. The distinction is made between practical limits which may be extended by advances in technology and intrinsic ones which arise from the modification of fluid properties by the earth's gravitational field. The kinds of experiments near critical points which could best exploit the low gravity environment of an orbiting laboratory are identified. These include studies of the index of refraction, constant volume specific heat, and phase separation.

  1. Deuteron NMR (Nuclear Magnetic Resonance) in relation to the glass transition in polymers

    NASA Technical Reports Server (NTRS)

    Roessler, E.; Sillescu, H.; Spiess, H. W.; Wallwitz, R.

    1983-01-01

    H-2NMR is introduced as a tool for investigating slow molecular motion in the glass transition region of amorphous polymers. In particular, we compare H-2 spin alignment echo spectra of chain deuterated polystyrene with model calculations for restricted rotational Brownian motion. Molecular motion in the polyztyrene-toluene system has been investigated by analyzing H-2NMR of partially deuterated polystyrene and toluene, respectively. The diluent mobility in the mixed glass has been decomposed into solid and liquid components where the respective average correlation times differ by more than 5 decades.

  2. Nonlinear phenomena and multiphonon transitions in the exciton region of a spectrum

    NASA Astrophysics Data System (ADS)

    Lisitsa, M. P.; Taratuta, R. A.; Yaremko, A. M.

    1990-08-01

    Using the Keldysh diagram method, the nonlinear susceptibility for a Frenkel exciton with account for the multiquantum transitions is obtained. Propagation of the strong resonance electromagnetic wave through the crystal and the optical bistability phenomenon are considered.

  3. Estimation of the fragility index of indomethacin by DSC using the heating and cooling rate dependency of the glass transition.

    PubMed

    Ramos, Joaquim J Moura; Taveira-Marques, Raquel; Diogo, Hermínio P

    2004-06-01

    In this study we have investigated the features of the glass transition relaxation of indomethacin using Differential Scanning Calorimetry (DSC). The purpose of this work is to provide an estimation of the activation energy at the glass transition temperature, as well as of the fragility index, of amorphous indomethacin from DSC data. To do so, the glass transition temperature region of amorphous indomethacin was characterized in both cooling and heating regimes. The activation energy for structural relaxation (directly related to glass fragility) was estimated from the heating and cooling rate dependence of the location of the DSC profile of the glass transition. The obtained results were similar in the heating and in the cooling modes. The results on the fragility index of indomethacin obtained in the present study, m = 60 in the cooling mode and m = 56 in the heating mode, are compared with other values previously published in the literature. PMID:15124208

  4. Effects of dynamic heterogeneity and density scaling of molecular dynamics on the relationship among thermodynamic coefficients at the glass transition

    SciTech Connect

    Koperwas, K. Grzybowski, A.; Grzybowska, K.; Wojnarowska, Z.; Paluch, M.

    2015-07-14

    In this paper, we define and experimentally verify thermodynamic characteristics of the liquid-glass transition, taking into account a kinetic origin of the process. Using the density scaling law and the four-point measure of the dynamic heterogeneity of molecular dynamics of glass forming liquids, we investigate contributions of enthalpy, temperature, and density fluctuations to spatially heterogeneous molecular dynamics at the liquid-glass transition, finding an equation for the pressure coefficient of the glass transition temperature, dTg/dp. This equation combined with our previous formula for dTg/dp, derived solely from the density scaling criterion, implies a relationship among thermodynamic coefficients at Tg. Since this relationship and both the equations for dTg/dp are very well validated using experimental data at Tg, they are promising alternatives to the classical Prigogine-Defay ratio and both the Ehrenfest equations in case of the liquid-glass transition.

  5. Boundary layer transition: A review of theory, experiment and related phenomena

    NASA Technical Reports Server (NTRS)

    Kistler, E. L.

    1971-01-01

    The overall problem of boundary layer flow transition is reviewed. Evidence indicates a need for new, basic physical hypotheses in classical fluid mechanics math models based on the Navier-Stokes equations. The Navier-Stokes equations are challenged as inadequate for the investigation of fluid transition, since they are based on several assumptions which should be expected to alter significantly the stability characteristics of the resulting math model. Strong prima facie evidence is presented to this effect.

  6. The superspin glass transition in zinc ferrite nanoparticles

    NASA Astrophysics Data System (ADS)

    Kaman, O.; Kořínková, T.; Jirák, Z.; Maryško, M.; Veverka, M.

    2015-05-01

    Nanoparticles of the ZnxFe3-xO4 (x = 0.3-0.4) spinel phase having 5 and 15 nm size were synthesized by thermal decomposition of the respective acetylacetonates in a high boiling-point solvent employing surfactants. The collective behaviour of the nanoparticles was probed by dc and ac magnetic measurements of tightly compressed pellets of the particles and silica coated products which were prepared by reverse microemulsion technique. The assembly of bare 5 nm particles remains in the superparamagnetic state with Curie-Weiss characteristics down to 35 K when a rather sharp freezing of superspins is detected. The larger particles show a similar but more diffusive transition at 250 K. The cores encapsulated into the diamagnetic silica do not exhibit glassy freezing.

  7. Mott glass to superfluid transition for random bosons in two dimensions

    NASA Astrophysics Data System (ADS)

    Iyer, S.; Pekker, D.; Refael, G.

    2012-03-01

    We study the zero-temperature superfluid-insulator transition for a two-dimensional model of interacting, lattice bosons in the presence of quenched disorder and particle-hole symmetry. We follow the approach of a recent series of papers by Altman, Kafri, Polkovnikov, and Refael, in which the strong disorder renormalization group is used to study disordered bosons in one dimension. Adapting this method to two dimensions, we study several different species of disorder and uncover universal features of the superfluid-insulator transition. In particular, we locate an unstable finite disorder fixed point that governs the transition between the superfluid and a gapless, glassy insulator. We present numerical evidence that this glassy phase is the incompressible Mott glass and that the transition from this phase to the superfluid is driven by a percolation-type process. Finally, we provide estimates of the critical exponents governing this transition.

  8. A Mott Glass to Superfluid Transition for Random Bosons in Two Dimensions

    NASA Astrophysics Data System (ADS)

    Pekker, David; Iyer, Shankar; Refael, Gil

    2012-02-01

    We study the zero temperature superfluid-insulator transition for a two-dimensional model of interacting, lattice bosons in the presence of quenched disorder and particle-hole symmetry. We follow the approach of a recent series of papers by Altman, Kafri, Polkovnikov, and Refael, in which the strong disorder renormalization group is used to study disordered bosons in one dimension. Adapting this method to two dimensions, we study several different species of disorder and uncover universal features of the superfluid-insulator transition. In particular, we locate an unstable finite disorder fixed point that governs the transition between the superfluid and a gapless, glassy insulator. We present numerical evidence that this glassy phase is the incompressible Mott glass and that the transition from this phase to the superfluid is driven by percolation-type process. Finally, we provide estimates of the critical exponents governing this transition.

  9. Thermodynamically constrained averaging theory approach for modeling flow and transport phenomena in porous medium systems: 9. Transition region models

    NASA Astrophysics Data System (ADS)

    Jackson, A. S.; Rybak, I.; Helmig, R.; Gray, W. G.; Miller, C. T.

    2012-06-01

    This work is the ninth in a series of papers on the thermodynamically constrained averaging theory (TCAT) approach for modeling flow and transport phenomena in multiscale porous medium systems. A fundamental approach is developed to model the transition region between a two-fluid-phase porous medium system and a single-fluid-phase system, including species transport. A general model formulation is developed along with an entropy inequality to guide the specification of closure relations. The general model formulation and entropy inequality are then used to specify a closed system. The transition region model developed in this work is a generalization and extension of coupling conditions commonly used in sharp interface models. The theoretical framework has multiple areas of potential applicability including terrestrial-atmospheric contact zones, surface water-sediment interface zones, and industrial drying processes.

  10. Influence of molecular-weight polydispersity on the glass transition of polymers.

    PubMed

    Li, Shu-Jia; Xie, Shi-Jie; Li, Yan-Chun; Qian, Hu-Jun; Lu, Zhong-Yuan

    2016-01-01

    It is well known that the polymer glass transition temperature T_{g} is dependent on molecular weight, but the role of molecular-weight polydispersity on T_{g} is unclear. Using molecular-dynamics simulations, we clarify that for polymers with the same number-average molecular weight, the molecular-weight distribution profile (either in Schulz-Zimm form or in bimodal form) has very little influence on the glass transition temperature T_{g}, the average segment dynamics (monomer motion, bond orientation relaxation, and torsion transition), and the relaxation-time spectrum, which are related to the local nature of the glass transition. By analyzing monomer motions in different chains, we find that the motion distribution of monomers is altered by molecular-weight polydispersity. Molecular-weight polydispersity dramatically enhances the dynamic heterogeneity of monomer diffusive motions after breaking out of the "cage," but it has a weak influence on the dynamic heterogeneity of the short time scales and the transient spatial correlation between temporarily localized monomers. The stringlike cooperative motion is also not influenced by molecular-weight polydispersity, supporting the idea that stringlike collective motion is not strongly correlated with chain connectivity. PMID:26871128