Science.gov

Sample records for glass transition region

  1. 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.

  2. 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.

  3. 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.

  4. Reversing and nonreversing heat capacity of poly(lactic acid) in the glass transition region by TMDSC

    SciTech Connect

    Pyda, Marek {nmn}; Wunderlich, Bernhard {nmn}

    2005-11-01

    A study of the glass transition of an amorphous and a semicrystalline poly(lactic acid) (PLA) is performed with adiabatic calorimetry, differential scanning calorimetry (DSC), and temperature-modulated DSC (TMDSC). The reversing, total, and nonreversing apparent heat capacities of samples with different contents of L- and D-lactic acid and with various thermal histories were evaluated. Different modes of TMDSC analyses of amorphous and semicrystalline PLA were compared to the total heat capacity from standard DSC. The enthalpy relaxation and the cold crystallization in the glass transition region are largely irreversible. The melting is largely irreversible, but a 100% reversing fraction is observed at low temperatures from 375 to 420 K, which becomes small inside the major melting peak at about 440 K. From the TMDSC of amorphous PLA, the combined information on endothermic and exothermic enthalpy relaxation and glass transition were deconvoluted into the reversing and nonreversing components. The glass transition temperature from the reversing heat capacity and the enthalpy relaxation peaks from the nonreversing component shift to higher temperature for increasingly annealed PLA. The relaxation times for aging decrease on cooling until the glass transition is reached and then increase. This behavior is linked to cooperativity. All quantitative thermal analyses are based on the heat capacity of the solid and liquid, evaluated earlier with the advanced thermal analysis system (ATHAS).

  5. A review of the slow relaxation processes in the glass-rubber transition region of amorphous polymers

    NASA Astrophysics Data System (ADS)

    Zhang, Rui; He, Xianru; Huang, Guangsu

    2015-09-01

    This article is a review that introduces several articles about slow relaxation processes, also known as slower segmental dynamics. According to the literature, the coupling effect and free volume holes are two important elements for slower micro-dynamics. In addition, the slower processes of many-body systems (blend and diluted systems) are summarised. A good numerical method for detecting multiple modes in the glass-rubber transition region is introduced.

  6. A phenomenological model of dynamical arrest of electron transfer in solvents in the glass-transition region

    SciTech Connect

    Matyushov, Dmitry V.

    2005-02-22

    A phenomenological model of electron transfer reactions in solvents undergoing glass transition is discussed. The reaction constant cuts off slow polarization modes from the spectrum of nuclear thermal motions active on the observation time scale. The arrest of nuclear solvation in turn affects the reaction activation barrier making it dependent on the rate. The resultant rate constant is sought from a self-consistent equation. The model describes well the sharp change in the solvent Stokes shift of optical lines in the glass-transition region. It is also applied to describe the temperature dependence of primary charge separation and reduction of primary pair in photosynthetic reaction centers. The model shows that a weak dependence of the primary charge separation rate on temperature can be explained by dynamical arrest of nuclear solvation on the picosecond time scale of electron transfer. For reduction of primary pair by cytochrome, the model yields a sharp turnover of the reaction kinetics at the transition temperature when nuclear solvation freezes in.

  7. 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.

  8. 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.

  9. 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.

  10. 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.

  11. 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.

  12. Modification of the mechanical behavior in the glass transition region of poly(lactic acid) (PLA) through catalyzed reactive extrusion with poly(carbonate) (PC)

    NASA Astrophysics Data System (ADS)

    Phuong, Vu Thanh; Coltelli, Maria-Beatrice; Anguillesi, Irene; Cinelli, Patrizia; Lazzeri, Andrea

    2014-05-01

    In order to improve the thermal stability of PLA based materials the strategy of blending it with poly(carbonate) of bisphenol A (PC), having a higher glass transition temperature, was followed and PLA/PC blends with different compositions, obtained also in the presence of an interchange reaction catalyst, Tetrabutylammonium tetraphenylborate (TBATPB) and triacetin were prepared by melt extrusion. The dynamical mechanical characterization showed an interesting change of the storage modulus behavior in the PLA glass transition region, evident exclusively in the catalyzed blends. In particular, a new peak in the Tanδ trend at a temperature in between the one of PLA and the one of PC was observed only in the blends obtained in the presence of triacetin and TBATPB. The height and maximum temperature of the peak was different after the annealing of samples at 80°C. The data, showing an interesting improvement of thermal stability above the PLA glass transition, were explained keeping into account the formation of PLA-PC copolymer during the reactive extrusion. Furthermore, the glass transition temperature of the copolymer as a function of composition was studied and the obtained trend was discussed by comparing with literature models developed for copolymers.

  13. 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.

  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.

    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

  16. 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.

  17. 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.

  18. 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

  19. 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.

  20. 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.

  1. 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.

  2. 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.

  3. 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

  4. 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.

  5. 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

  6. 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

  7. 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.

  8. 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

  9. 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.

  10. 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

  11. 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).

  12. Transition Region Flows

    NASA Astrophysics Data System (ADS)

    Brekke, P.; Murdin, P.

    2000-11-01

    Ultraviolet emission lines emitted from the SOLAR TRANSITION REGION are often shifted from their expected rest wavelengths. Shifts of spectral lines are due to the so-called DOPPLER EFFECT, where the source of emission is moving either away from or towards the observer, causing a change in the apparent wavelength. The shifted emission lines are most often interpreted as a flow of plasma along ...

  13. 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.

  14. 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.

  15. 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.

  16. 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.

  17. 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,

  18. 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.

  19. 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.

  20. 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

  1. 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

  2. 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.

  3. 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.

  4. 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.

  5. 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

  6. 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.

  7. 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

  8. 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.

  9. 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.

  10. 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.

  11. 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

  12. 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.

  13. Magnetic TRAnsition Region Probe (MTRAP)

    NASA Technical Reports Server (NTRS)

    Moore, R. L.; Davis, John; Hathaway, David; Six, N. Frank (Technical Monitor)

    2002-01-01

    MTRAP (Magnetic Transition Region Probe) will reveal the fine-scale physical processes in the Sun's magnetic transition region, the complex layer from the upper photosphere to the upper chromosphere/lower transition region. In the magnetic transition region plasma forces and magnetic forces are of comparable strength, which results in complex interplay of the two, which interplay governs the coupling of the convectively-driven deeper layers to the magnetically-driven upper transition region and inner corona. The fine-scale magnetic structure, processes, and events in the magnetic transition region are key to the genesis of the Sun's entire hot, dynamic outer atmosphere and to the initiation of large eruptive events. MTRAP will be a single spacecraft in Sun-synchronous Earth orbit. Because MTRAP will probe and measure the 3-D structure and dynamics of the magnetic field and plasma in the chromosphere and transition region with unprecedented resolution, the required telescope size and telemetry rates dictate that MTRAP be in Earth orbit, not in deep space. The observations will feature visible and infrared maps of vector magnetic and velocity fields in the magnetic transition region and photosphere. These will have large field of view (greater than 100,000 km), high resolution (greater than 100 km), and high sensitivity (greater than 30 G in transverse field). These observations of the lower atmosphere will be complemented by UV maps of the structure, velocity, and magnetic field (including the full vector field if technically feasible) higher up, in the upper chromosphere and lower transition region. MTRAP will also have an EUV imaging spectrograph observing coronal structure and dynamics in the same field of view with comparable resolution. Specific phenomena to be analyzed include spicules, bright points, jets, the base of plumes, and the triggering of eruptive flares and coronal mass ejections. Additional information is included in the original extended abstract.

  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. 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

  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. 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.

  19. 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 .

  20. 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

  1. 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)

  2. 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

  3. 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.

  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

    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.

  8. 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

  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. 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)].

  14. 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

  15. 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

  16. The transition regions of Capella

    NASA Technical Reports Server (NTRS)

    Linsky, Jeffrey L.; Wood, Brian E.; Judge, Philip; Brown, Alexander; Andrulis, Catherine; Ayers, Thomas R.

    1995-01-01

    We have used the Goddard High Resolution Spectrometer (GHRS) to observe the spectoscopic binary system Capella (G8 III + G1 III). Exposures with the G140L, G140M, G160M, G200M, and echelle gratings provide emission line profiles with unprecedented signal-to-noise and spectral resolving power (lambda/Delta-lambda) up to 92,000. Multi-Gaussin fits to the line profiles show that the hotter star contributes 60%-70% of the total flux in the chromospheric O I and Mg II resonance lines, but about 90% of the flux in the Si III, Si IV, and C IV lines formed in the transition region at T less than or = 10(exp 5) K. We find clear evidence that the emission lines from the hotter star are systemtically redshifted relative to the photosphere with Doppler shifts of 5 +/- 1 km/s for the +9 +/- 3 km/s in the chromospheric Mg II and O I lines, respectively, increasing to +24 +/- 5 km/s for the transition region Si IV 1393.8A line. The multi-Gaussian fits to permitted transition region lines of SI III, Si IV, C IV, and N V indicate the presence of three components: moderately broad lines formed in the transition region of the hotter star (component H), narrow lines formed in the transition region of the cooler star (component C), and very broad lines that we think are formed in microflares on the hotter star (component B). The He II 1640.4 A feature has an broad profile, which indicates that it is formed by collisional excitation primarily from the hotter star, and a weak narrow component that we interpret as due to radiative recombination on the cooler star. We observed spin-forbidden emission lines of C III), O III), Si III), O IV), O V), and S IV) that are sensitive to electron density. Fainter members of the O IV) multiplet and all of the S IV) lines have never before been seen in any star than the Sun. We determine electron densities in the transition regions of the Capella stars using lines ratios of O IV) lines and emission measure analysis. The emission measures are self

  17. 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

  18. 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

  19. 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.

  20. Localized Excitations and the Morphology of Cooperatively Rearranging Regions in a Colloidal Glass-Forming Liquid

    NASA Astrophysics Data System (ADS)

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

    2016-02-01

    We develop a scheme based on a real space microscopic analysis of particle dynamics to ascertain the relevance of dynamical facilitation as a mechanism of structural relaxation in glass-forming liquids. By analyzing the spatial organization of localized excitations within clusters of mobile particles in a colloidal glass former and examining their partitioning into shell-like and corelike regions, we establish the existence of a crossover from a facilitation-dominated regime at low area fractions to a collective activated hopping-dominated one close to the glass transition. This crossover occurs in the vicinity of the area fraction at which the peak of the mobility transfer function exhibits a maximum and the morphology of cooperatively rearranging regions changes from stringlike to a compact form. Collectively, our findings suggest that dynamical facilitation is dominated by collective hopping close to the glass transition, thereby constituting a crucial step towards identifying the correct theoretical scenario for glass formation.

  1. 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

  2. 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.

  3. Vortex glass transition in a YBa 2Cu 3O 7- δ film with patterned pinning geometry

    NASA Astrophysics Data System (ADS)

    Kyoso, T.; Nojima, T.; Okayasu, S.; Kobayashi, N.

    2004-10-01

    We report on multiterminal transport measurement in YBa 2Cu 3O y films, where a vortex flow channel is artificially introduced in a strong pinning environment with columnar defects. The samples were prepared by partially masked heavy-ion irradiation. Two kinds of phase transitions with different transition temperatures, TVG and TBG, which correspond to the vortex glass transition and the Bose glass transition, are observed for the unirradiated region and the irradiated one, respectively. At high field, the situation of TVG< TBG, where the flux flow in unirradiated channel is confined between Bose glass solids of the irradiated region, is realized. The vortex velocity distribution is almost homogeneous inside the channel. Around the boundary, however, we find that the vortices flowing in the unirradiated channel drag the vortices of the Bose glass solid in the irradiated region.

  4. 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.

  5. 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.

  6. 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.

  7. 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

  8. 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

  9. 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.

  10. 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.

  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. 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.

  13. 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.

  14. Connection between the energy landscape and glass transition in a two-dimensional Lennard-Jones mixture

    NASA Astrophysics Data System (ADS)

    Somer, Frank

    2005-03-01

    Results of recent molecular dynamics simulations of a two-dimensional glass forming system are presented. The system's inherent structures are investigated over a wide range of temperature and cooling rate and compared to previous results for three-dimensional liquids and glasses. A method for analyzing the regions of the energy landscape sampled under various conditions is introduced and used to characterize the glass transition. Connections with inherent-structures theory, mode-coupling theory, and spatially inhomogeneous dynamics are discussed.

  15. 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.

  16. 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

  17. The peculiar behavior of the glass transition temperature of amorphous drug-polymer films coated on inert sugar spheres.

    PubMed

    Dereymaker, Aswin; Van Den Mooter, Guy

    2015-05-01

    Fluid bed coating has been proposed in the past as an alternative technology for manufacturing of drug-polymer amorphous solid dispersions, or so-called glass solutions. It has the advantage of being a one-step process, and thus omitting separate drying steps, addition of excipients, or manipulation of the dosage form. In search of an adequate sample preparation method for modulated differential scanning calorimetry analysis of beads coated with glass solutions, glass transition broadening and decrease of the glass transition temperature (Tg ) were observed with increasing particle size of crushed coated beads and crushed isolated films of indomethacin (INDO) and polyvinylpyrrolidone (PVP). Substituting INDO with naproxen gave comparable results. When ketoconazole was probed or the solvent in INDO-PVP films was switched to dichloromethane (DCM) or a methanol-DCM mixture, two distinct Tg regions were observed. Small particle sizes had a glass transition in the high Tg region, and large particle sizes had a glass transition in the low Tg region. This particle size-dependent glass transition was ascribed to different residual solvent amounts in the bulk and at the surface of the particles. A correlation was observed between the deviation of the Tg from that calculated from the Gordon-Taylor equation and the amount of residual solvent at the Tg of particles with different sizes. PMID:25702912

  18. 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.

  19. 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.

  20. 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.

  1. 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.

  2. Intensity Distribution of the Solar Transition Region

    NASA Technical Reports Server (NTRS)

    Fisher, George H.

    1999-01-01

    The objective of this research project was to use high resolution spectroscopic observations from the SUMER instrument on SOHO to study the structure of the solar transition region. Our focus in this grant was to study the structure of the transition region in a small active region, and compare it to similar observations we made of the quiet Sun. We also used SXT and EIT data to constrain the coronal and transition region emission measure distribution.

  3. 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

  4. 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.

  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. 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.

  7. 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.

  8. 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).

  9. 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.

  10. 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.

  11. 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

  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 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.

  14. Thermo-physical and structural studies of sodium zinc borovanadate glasses in the region of high concentration of modifier oxides

    SciTech Connect

    Chethana, B.K.; Reddy, C. Narayana; Rao, K.J.

    2012-07-15

    Highlights: ► Highly modified sodium zinc borovanadate glasses. ► Structural model for borovanadate glasses. ► Network forming tendency of ZnO in borovanadate glasses. ► Fragility can be limited to NBO concentration in borovanadate glasses. -- Abstract: This paper reports investigation of Na{sub 2}O and ZnO modified borovanadate glasses in the highly modified regime of compositions. These glasses have been prepared by microwave route. Ultraviolet (UV) and visible, infrared (IR), Magic Angle Spinning Nuclear Magnetic Resonance (MAS NMR) and Electron Paramagnetic Resonance (EPR) spectroscopies have been used to characterize the speciation in the glasses. Together with the variation of properties such as molar volume and glass transition temperatures, spectroscopic data indicate that at high levels of modification, ZnO tends to behave like network former. It is proposed that the observed variation of all the properties can be reasonably well understood with a structural model. The model considers that the modification and speciation in glasses are strongly determined by the hierarchy of group electronegativities. Further, it is proposed that the width of the transitions of glasses obtained under same condition reflects the fragility of the glasses. An empirical expression has been suggested to quantify fragility on the basis of width of the transition regions.

  15. 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

  16. 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

  17. 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.

  18. Revisiting the glass transition and dynamics of supercooled benzene by calorimetric studies

    NASA Astrophysics Data System (ADS)

    Tu, Wenkang; Chen, Zeming; Li, Xiangqian; Gao, Yanqin; Liu, Riping; Wang, Li-Min

    2015-10-01

    The glass transition and dynamics of benzene are studied in binary mixtures of benzene with five glass forming liquids, which can be divided into three groups: (a) o-terphenyl and m-xylene, (b) N-butyl methacrylate, and (c) N,N-dimethylpropionamide and N,N-diethylformamide to represent the weak, moderate, and strong interactions with benzene. The enthalpies of mixing, ΔHmix, for the benzene mixtures are measured to show positive or negative signs, with which the validity of the extrapolations of the glass transition temperature Tg to the benzene-rich regions is examined. The extrapolations for the Tg data in the mixtures are found to converge around the point of 142 K, producing Tg of pure benzene. The fragility m of benzene is also evaluated by extrapolating the results of the mixtures, and a fragility m ˜ 80 is yielded. The obtained Tg and m values for benzene allow for the construction of the activation plot in the deeply supercooled region. The poor glass formability of benzene is found to result from the high melting point, which in turn leads to low viscosity in the supercooled liquid.

  19. 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.

  20. Stable Freestanding Thin Films of Copolymer Melts Far from the Glass Transition

    PubMed Central

    2015-01-01

    Thin polymer films have attracted attention because of both their broad range of applications and of the fundamental questions they raise regarding the dynamic response of confined polymers. These films are unstable if the temperature is above their glass transition temperature Tg. Here, we describe freestanding thin films of centimetric dimensions made of a comb copolymer melt far from its glass transition that are stable for more than a day. These long lifetimes allowed us to characterize the drainage dynamics and the thickness profile of the films. Stratified regions appear as the film drains. We have evidence that the stability, thinning dynamics, and thickness profile of the films result from structural forces in the melt. Understanding the key mechanisms behind our observations may lead to new developments in polymeric thin films, foams, and emulsions without the use of stabilizing agents. PMID:26527410

  1. Release mechanism of omega-3 fatty acid in κ-carrageenan/polydextrose undergoing glass transition.

    PubMed

    Paramita, Vilia Darma; Bannikova, Anna; Kasapis, Stefan

    2015-08-01

    A high-solid matrix of κ-carrageenan with polydextrose was developed to entrap α-linolenic acid, which is an omega-3 bioactive compound. Physicochemical analysis of this system utilised modulated DSC, dynamic oscillation in shear, ESEM, FTIR and WAX diffraction. The carbohydrate matrix was conditioned through an extensive temperature range to induce changes in molecular morphology and identify the network glass transition temperature. Thermally induced variation in phase morphology was employed to rationalise transportation patterns of the bioactive compound within the high-solid preparation. Thus, experimental observations using UV-vis spectroscopy modelled diffusion kinetics to document the mobility arresting effect of the vitrifying matrix on the micro-constituent. Within the glass transition region, results argue that free volume theory is the molecular process governing structural relaxation. Further, Less Fickian diffusion follows well the rate of molecular transport of α-linolenic acid as a function of time and temperature of observation in the condensed matrix. PMID:25933532

  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. 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.

  6. 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

  7. 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

  8. 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.

  9. 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.

  10. 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

  11. Cooperative rearranging region size and free volume in As-Se glasses.

    PubMed

    Saiter, A; Saiter, J-M; Golovchak, R; Shpotyuk, M; Shpotyuk, O

    2009-02-18

    Glasses of the As-Se system have been used as model objects of the covalent disordered inorganic polymers to investigate the correlation between the cooperative rearranging region (CRR) size determined at the glass transition temperature and the free volume fraction in the glassy state. The CRR size has been determined using temperature modulated differential scanning calorimetry data according to Donth's approach, while the free volume fraction in the investigated materials has been estimated using positron annihilation lifetime spectroscopy data. The obtained results testify that the appearance of open-volume defects greater than 80 Å(3) leads to a significant decrease in the CRR size. PMID:21817320

  12. 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

  13. 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

  14. 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.

  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. 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.

  17. 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

  18. 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

  19. 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

  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. Transition Region and Coronal Explorer

    NASA Technical Reports Server (NTRS)

    Wolfson, C. Jacob

    2001-01-01

    This contract is for the development and flight of an experiment to study the solar atmosphere with excellent spatial and temporal resolution; and reduction and analysis of the resultant data. After being launched into a near perfect orbit on 2 April 1998, the spacecraft and instrument remain in good condition and the resultant data are spectacular. Over 6.6 million images have now been taken. Observing highlights this month included several coordinations with CDS, studies of the quiet Sun with SUMER and NMI, coordinations with observers at the SPO Dunn Tower Telescope, and a variety of active region observations. Some of the latter were relatively unique in that they emphasized using the hottest (284A) channel of TRACE. We were informed of the results of the Senior Review Committee's evaluation of all Space Science on-orbit missions and the corresponding fiscal year budgets for TRACE. The budget for FY-02 is modestly less than is being spent in FY-01 and for the years beyond that it is much, much lower.

  2. 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.

  3. Plasticity in the Supercooled Liquid Region of Bulk Metallic Glasses

    SciTech Connect

    Nieh, T G; Wadsworth, J; Liu, C T; Ice, G E

    2000-10-30

    Intensive efforts have been carried out over the past decade to develop means to slow down the phase transformation kinetics during the forming of metallic glasses. As a result of these efforts, some metallic glasses can now be fabricated in bulk forms (BMG) from the liquid state at cooling rates on the order of 1-10 K/s, which is close to that of conventional casting. This enables the production of bulk amorphous alloys with a thickness of {approx}10 mm. While advances in amorphous metallic alloy development have been impressive, they have been made largely through experience [1]. Three main conclusions drawn from this study are: (1) Bulk metallic glasses generally have excellent mechanical formability in the supercooled liquid region. (2) Bulk metallic glasses may not be necessarily behave like a Newtonian fluid (i.e. m=1). The non-Newtonian behavior is associated with glass instability during deformation. (3) Multi-component Bulk metallic glasses can be used as the precursor of a nanocrystalline solid. However, the nanocrystalline solid is not necessarily superplastic. The non-superplastic behavior is caused by the difficult strain accommodation at grain triple junctions.

  4. 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.

  5. 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

  6. 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.

  7. 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

  8. 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.

  9. 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

  10. 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.

  11. 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).

  12. 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

  13. Glass transitions and physical aging of cassava starch - corn oil blends.

    PubMed

    Pérez, Adriana; Sandoval, Aleida J; Cova, Aura; Müller, Alejandro J

    2014-05-25

    Glass transition temperatures and physical aging of amorphous cassava starch and their blends with corn oil were assessed by differential scanning calorimetry (DSC). Two enthalpic relaxation endotherms, well separated in temperature values, were exhibited by neat amorphous cassava starch with 10.6% moisture content, evidencing two amorphous regions within the starch with different degrees of mobility. The phase segregation of these two amorphous regions was favored by added corn oil at low moisture contents during storage. The presence of amylose-lipid complexes in this matrix, may also affect the molecular dynamics of these two amorphous regions at low moisture contents. Increasing moisture content, leads to a homogeneous amorphous phase, with an aging process characterized by a single enthalpic relaxation peak. In all cases, after deleting the thermal history of the samples only one glass transition temperature was detected (during DSC second heating runs) indicating that a single homogeneous amorphous phase was attained after erasing the effects of physical aging. Trends of the enthalpic relaxation parameters were also different at the two moisture contents considered in this work. PMID:24708977

  14. 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

  15. 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.

  16. 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.

  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. 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.

  19. 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

  20. 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

  1. Confinement effects on glass transition temperature, transition breadth, and expansivity: Comparison of ellipsometry and fluorescence measurements on polystyrene films

    NASA Astrophysics Data System (ADS)

    Kim, S.; Hewlett, S. A.; Roth, C. B.; Torkelson, J. M.

    2009-09-01

    Using ellipsometry, we characterized the nanoconfinement effect on the glass transition temperature (T gof supported polystyrene (PS) films employing two methods: the intersection of fits to the temperature (Tdependences of rubbery- and glassy-state thicknesses, and the transition mid-point between rubbery- and glassy-state expansivities. The results demonstrate a strong effect of thickness: ensuremath Tg(bulk)-Tg(23{ nm})= 10 circ C. The T -range needed for accurate measurement increases significantly with decreasing thickness, an effect that arises from the broadening of the transition with confinement and a region below T g where expansivity slowly decreases with decreasing T . As determined from expansivities, the T g breadth triples in going from bulk films to a 21-nm-thick film; this broadening of the transition may be a more dramatic effect of confinement than the T g reduction itself. In contrast, there is little effect of confinement on the rubbery- and glassy-state expansivities. Compared with ellipsometry, T g ’s from fluorescence agree well in bulk films but yield lower values in nanoconfined films: T g(bulk) - T g(23 nm) = 15° C via fluorescence. This small difference in the T g confinement effect reflects differences in how fluorescence and ellipsometry report “average T g ” with confinement. With decreasing nanoscale thickness, fluorescence may slightly overweight the contribution of the free-surface layer while ellipsometry may evenly weight or underweight its contribution. in here

  2. 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

  3. 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.

  4. 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

  5. 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.

  6. Investigation of glass transition and dielectric behavior of nanoporous PEI (polyetherimide)

    NASA Astrophysics Data System (ADS)

    Liu, Tong

    Nanoporous polymers are of great interest for their potential applications as low dielectric constant materials in the microelectronics industry. In general, nanoporous polymers can be viewed as nanocomposite materials, which consist of three parts: polymer matrix, nanopores and the interface region surrounding the nanopores. Evidence has been shown that the interface region has unique properties different from the polymer matrix, which would cause property changes in the polymer nanocomposites. However, the understanding of the interface region and its influence on properties are still limited. Therefore, the main objectives of this work were to create a controlled nanoporous polymer structure and to investigate the interface effects on glass transition temperature and dielectric constant in the nanoporous polymer system. Nanoporous polyetherimide (PEI) was developed based on a blend of PEI and polycaprolactone-diol (PCLD). Because PEI and PCLD are immiscible, dispersed PCLD phase domains were formed in the PEI matrix. Nanoporous PEI was created by immersing the phase-separated samples in acetone, which dissolved the PCLD phase only. The pore size in spin-coated samples was found to be in the nanometer scale due to the fast phase separation process. In this case, the phase separation was far from thermal equilibrium, and kinetic factors played an important role in the process. The pore structure was characterized by microscopy methods. The pore size was found to depend on the processing time and the initial PCLD phase content (PCLD is the minor phase) due to the kinetics of phase coarsening. The glass transition temperature and dielectric constant of the nanoporous PEI system were investigated with various means. The relationship between the properties and the pore structure was studied by controlling the pore volume fraction through varying the initial minor phase content in the blend. It was found that the glass transition temperature of nanoporous PEI would

  7. 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

  8. 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.

  9. Structural changes in a-Se near the glass transition by thermal relaxation kinetics

    NASA Astrophysics Data System (ADS)

    Stephens, Richard B.

    1984-11-01

    A multiple-relaxation-rate approach is used to model the enthalpic relaxation behavior of amorphous selenium (a-Se) near its glass-transition temperature (Tg). The model parameters are completely determined by matching the behavior predicted by the model to that of the real material as shown in viscosity and heat-capacity measurements. The family of structure-dependent relaxation curves, Rm(T), derived from this model, provides a new insight on the structural dynamics of a-Se. Two distinct regimes are observed, with a transition near the normally observed Tg. For T>Tg, the relaxation curves are of the form RHm(T)=Amexp[a+b(T-T0)], where the range of Am is relatively small, and T0<~Tg. For Tglass transition of Cohen and Grest. Previous investigators had not seen this effect so clearly; it was not noticeable in network glasses, and was only of minor importance in polymers. Its importance in a-Se is a consequence of its mutable chain structure. In addition, the observation that the relaxation time measured by the viscosity is faster than the thermal relaxation rates implies that the viscosity is not determined by the slippage of entangled chains, as one might imagine by analogy to the sulfur system, but rather by shear in low-density regions; i.e., selenium should be considered to be more like wet sand than like seaweed.

  10. Glass transition dynamics and cooperativity length of poly(ethylene 2,5-furandicarboxylate) compared to poly(ethylene terephthalate).

    PubMed

    Codou, Amandine; Moncel, Matthieu; van Berkel, Jesper Gabriël; Guigo, Nathanaël; Sbirrazzuoli, Nicolas

    2016-06-22

    The glass transition of poly(ethylene 2,5-furandicarboxylate) (PEF), an emergent bio-based polyester, was investigated in comparison to one of its chemical analogues: poly(ethylene terephthalate) (PET). These investigations were conducted at different crystallinities by means of stochastic modulated differential scanning calorimetry (stochastic TMDSC) and dynamic mechanical analysis (DMA). Amorphous PEF presents a higher ΔCp at the glass transition and a broader relaxation spectrum attributed to a higher free volume. The higher Tg of PEF is then purely related to segmental mobility and specific interactions in PEF. The length of cooperative rearranging regions (CRR) was similar for both materials. Additionally, the variations of the effective activation energy E of PEF and PET at glass transitions were determined by isoconversional kinetic analysis. The rate of decrease in E was similar for the two amorphous polyesters. Upon crystallization, the glass transition of PEF is broadened but its temperature range is not increased as with PET. The creation of the rigid amorphous fraction (RAF) with crystallinity is lower in PEF than in PET. The difference in free volume also explains the lower coupling between the crystalline phase and the amorphous phase in PEF. PMID:27067510

  11. 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

  12. 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

  13. 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.

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

    NASA Technical Reports Server (NTRS)

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

    1996-01-01

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

  15. The transition region and coronal explorer (TRACE)

    NASA Technical Reports Server (NTRS)

    Title, Alan; Bruner, M.; Jurcevich, B.; Lemen, J.; Strong, K.; Tarbell, Ted; Wolfson, C. Jacob; Golub, L.; Bookbinder, J.; Fisher, R.

    1995-01-01

    The transition region and coronal explorer (TRACE) NASA small explorer mission and instrument are presented. The TRACE scientific investigation explores the relationships between fine-scale magnetic fields and the associated solar plasma structures. The instrument collects images of solar plasmas at temperatures from 10(exp 4) to 10(exp 7) K with one arcsec spatial resolution. The design specifications of the trace instrument are presented.

  16. Transition region of the earth's upper mantle

    NASA Technical Reports Server (NTRS)

    Anderson, D. L.; Bass, J. D.

    1986-01-01

    The chemistry of the earth's mantle is discussed using data from cosmochemistry, geochemistry, petrology, seismology, and mineral physics. The chondritic earth, the upper mantle and the 400-km discontinuity, the transition region, lower mantle mineralogy, and surface wave tomography are examined. Three main issues are addressed: (1) whether the mantle is homogeneous in composition or chemically stratified, (2) whether the major element chemistry of the mantle is more similar to upper mantle peridotites or to chondrites, and (3) the nature of the composition of the source region of basalts erupted at midocean ridges.

  17. 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.

  18. 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.

  19. 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.

  20. 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.

  1. 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

  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. 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.

  4. 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.

  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. The upper mantle transition region - Eclogite

    NASA Technical Reports Server (NTRS)

    Anderson, D. L.

    1979-01-01

    The upper mantle transition region is usually considered to be peridotite which undergoes a series of phase changes involving spinel and post-spinel assemblages. There are difficulties associated with attempts to explain the 220, 400 and 670 km discontinuities in terms of phase changes in a peridotitic mantle. Moreover, in a differentiated earth there should be large quantities of eclogite in the upper mantle. Eclogite is denser than Al2O3-poor mantle to depths of 670 km, but it stays in the garnet stability field to pressures in excess of those required to transform depleted mantle to denser phases such as ilmenite and perovskite. Eclogite, therefore, remains above 670 km. The seismic properties of the transition region are more consistent with eclogite than peridotite. Most of the mantle's inventory of incompatible trace elements may be in this layer, which is a potential source region for some basalt magmas. The radioactivity in this layer is the main source of mantle heat flow, 0.7 microcalorie/sq cm-sec, and drives upper mantle convection.

  8. 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.

  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. KT boundary impact glasses from the Gulf of Mexico region

    NASA Technical Reports Server (NTRS)

    Claeys, Philippe; Alvarez, Walter; Smit, Jan; Hildebrand, A. R.; Montanari, Alessandro

    1993-01-01

    Cretaceous-Tertiary boundary (KTB) tektite glasses occur at several sites around the Gulf of Mexico. Contrary to rumor among KTB workers, glass fragments have been found by several researchers in the base of the spherule bed at Arroyo el Mimbral in NE Mexico. The presence of green, red, and transparent glass fragments at Mimbral only, demonstrates that the Mimbral glass is not a laboratory contamination by Beloc glass. The chemistry and ages of the glass are consistent with an origin from the Chixculub impact crater in Yucatan. No evidence supports a volcanic origin for the KTB glasses. A discussion of tektite glass from the KT boundary is presented.

  12. 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.

  13. 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

  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. 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.

  16. 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.

  17. 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

  18. 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

  19. Fundamental considerations in the effect of molecular weight on the glass transition of the gelatin/cosolute system.

    PubMed

    Jiang, Bin; Kasapis, Stefan; Kontogiorgos, Vassilis

    2012-05-01

    Four molecular fractions of gelatin produced by alkaline hydrolysis of collagen were investigated in the presence of cosolute to record the mechanical properties of the glass transition in high-solid preparations. Dynamic oscillatory and stress relaxation moduli in shear were recorded from 40°C to temperatures as low as -60°C. The small-deformation behavior of these linear polymers was separated by the method of reduced variables into a basic function of time alone and a basic function of temperature alone. The former allowed the reduction of isothermal runs into a master curve covering 17 orders of magnitude in the time domain. The latter follows the passage from the rubbery plateau through the glass transition region to the glassy state seen in the variation of shift factor, a(T) , as a function of temperature. The mechanical glass transition temperature (T(g) ) is pinpointed at the operational threshold of the free volume theory and the predictions of the reaction rate theory. Additional insights into molecular dynamics are obtained via the coupling model of cooperativity, which introduces the concept of coupling constant or interaction strength of local segmental motions that govern structural relaxation at the vicinity of T(g) . The molecular weight of the four gelatin fractions appears to have a profound effect on the transition temperature or coupling constant of vitrified matrices, as does the protein chemistry in relation to that of amorphous synthetic polymers or gelling polysaccharides. PMID:22189701

  20. 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).

  1. 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

  2. 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

  3. 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.

  4. 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

  5. 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

  6. A novel difference between strong liquids and fragile liquids in their dynamics near the glass transition

    NASA Astrophysics Data System (ADS)

    Tokuyama, Michio; Enda, Shohei; Kawamura, Junichi

    2016-01-01

    The systematic method to explore how the dynamics of strong liquids (S) is different from that of fragile liquids (F) near the glass transition is proposed from a unified point of view discussed recently by Tokuyama. The extensive molecular-dynamics simulations are performed on different glass-forming materials. The simulation results for the mean- nth displacement Mn(t) are then analyzed from the unified point of view, where n is an even number. Thus, it is first shown that in each type of liquids there exists a master curve Hn(α) as Mn(t) =RnHn(α) (vth t / R ; D / Rvth) onto which any simulation results collapse at the same value of D / Rvth, where R is a characteristic length such as an interatomic distance, D a long-time self-diffusion coefficient, vth a thermal velocity, and α = F and S. The master curves Hn(F) and Hn(S) are then shown not to coincide with each other in the so-called cage region even at the same value of D / Rvth. Thus, it is emphasized that the dynamics of strong liquids is quite different from that of fragile liquids.

  7. 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).

  8. MTRAP: The Magnetic Transition Region Probe

    NASA Technical Reports Server (NTRS)

    Davis, J. M.; West, E. A.; Moore, R. L.; Gary, G. A.; Kobayashi, K.; Oberright, J. F.; Evans, D. C.; Wood, H. J.; Saba, J. L. R.; Alexander, D.

    2005-01-01

    The Magnetic Transition Region Probe is a space telescope designed to measure the magnetic field at several heights and temperatures in the solar atmosphere, providing observations spanning the chromospheric region where the field is expected to become force free. The primary goal is to provide an early warning system (hours to days) for solar energetic particle events that pose a serious hazard to astronauts in deep space and to understand the source regions of these particles. The required magnetic field data consist of simultaneous circular and linear polarization measurements in several spectral lines over the wavelength range from 150 to 855 nm. Because the observations are photon limited an optical telescope with a large (>18sq m) collecting area is required. To keep the heat dissipation problem manageable we have chosen to implement MTRAP with six separate Gregorian telescopes, each with approx. 3 sq m collecting area, that are brought to a common focus. The large field of view (5 x 5 arcmin(sup 2)) and angular resolution (0.025 arcsec pixels) require large detector arrays and, because of the requirements on signal to noise (10(exp 3)), pixels with large full well depths to reduce the readout time and improve the temporal resolution. The optical and engineering considerations that have gone into the development of a concept that meets MTRAP's requirements are described.

  9. LAMPF transition-region mechanical fabrication

    SciTech Connect

    Bush, E.D. Jr.; Gallegos, J.D.F.; Harrison, R.; Hart, V.E.; Hunter, W.T.; Rislove, S.E.; Sims, J.R.; Van Dyke, W.J.

    1984-07-01

    The primary purpose of the new Transition Region (TR-II) is to optimize the phase matching of the H/sup +/ and H/sup -/ beams during simultaneous transport. TR-II incorporates several design improvements that include larger aperture, a straight beam track, greater beam-path length adjustments, and utility lines integrated with the support system. The close pack density of magnets and beam-line hardware required innovative solutions to magnet design and mounting, vacuum manifolding, and utility routing. Critical magnet placement was accomplished using a new three-dimensional alignment system that does real-time vector calculations on a computer with input from two digital theodolites. All assembly and a large fraction of the mechanical fabrication were done by LAMPF personnel. The TR-II has been operational since September 1983 and routinely transports production beams up to 900-..mu..A current with no major problems.

  10. An Explanation of the Solar Transition Region

    NASA Astrophysics Data System (ADS)

    Judge, Philip

    2008-08-01

    Prompted by high-resolution observations, I propose an explanation for the 40+ year old problem of structure and energy balance in the solar transition region. The ingredients are simply cross-field diffusion of neutral atoms from cool threads extending into the corona, and the subsequent excitation, radiation, and ionization of these atoms via electron impact. The processes occur whenever chromospheric plasma is adjacent to coronal plasma, and are efficient even when ion gyrofrequencies exceed collision frequencies. Cool threads—fibrils and spicules perhaps—grow slowly in thickness as a neutral, ionizing front expands across the magnetic field into coronal plasma. Radiative intensities estimated for H Lyα are within an order of magnitude of those observed, with no ad hoc parameters; only thermal parameters and geometric considerations are needed. I speculate that the subsequent dynamics of the diffused material might also explain observed properties of trace elements.

  11. 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.

  12. 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.

  13. Effect of 3d-transition metal doping on the shielding behavior of barium borate glasses: a spectroscopic study.

    PubMed

    ElBatal, H A; Abdelghany, A M; Ghoneim, N A; ElBatal, F H

    2014-12-10

    UV-visible and FT infrared spectra were measured for prepared samples before and after gamma irradiation. Base undoped barium borate glass of the basic composition (BaO 40%-B2O3 60mol.%) reveals strong charge transfer UV absorption bands which are related to unavoidable trace iron impurities (Fe(3+)) within the chemical raw materials. 3d transition metal (TM)-doped glasses exhibit extra characteristic absorption bands due to each TM in its specific valence or coordinate state. The optical spectra show that TM ions favor generally the presence in the high valence or tetrahedral coordination state in barium borate host glass. Infrared absorption bands of all prepared glasses reveal the appearance of both triangular BO3 units and tetrahedral BO4 units within their characteristic vibrational modes and the TM-ions cause minor effects because of the low doping level introduced (0.2%). Gamma irradiation of the undoped barium borate glass increases the intensity of the UV absorption together with the generation of an induced broad visible band at about 580nm. These changes are correlated with suggested photochemical reactions of trace iron impurities together with the generation of positive hole center (BHC or OHC) within the visible region through generated electrons and positive holes during the irradiation process. PMID:24983922

  14. Glass transition of partially crystallized gelatin-water mixtures studied by broadband dielectric spectroscopy

    NASA Astrophysics Data System (ADS)

    Sasaki, Kaito; Kita, Rio; Shinyashiki, Naoki; Yagihara, Shin

    2014-03-01

    The glass transition of partially crystallized gelatin-water mixtures was investigated for gelatin concentrations of 40 and 20 wt. % by broadband dielectric spectroscopy (BDS) in wide frequency (10 mHz-50 GHz) and temperature (113-298 K) ranges. Three dielectric relaxation processes were clearly observed. The origin of each relaxation process was the same as that observed for partially crystallized bovine serum albumin (BSA)-water mixtures [N. Shinyashiki et al., J. Phys. Chem. B 113, 14448 (2009)]. The relaxation process at the highest frequency is originated from uncrystallized water (UCW) in the hydration shell of gelatin. Its relaxation time is almost the same as that of water in uncrystallized system; water in various binary aqueous mixtures and confined water in nanoscale region. The relaxation process at the intermediate frequency is originated from ice, and its relaxation time and strength were similar to those for the relaxation of pure ice, particularly above 240 K. The glass transition temperature Tg, is defined by BDS measurement as the temperature at which dielectric relaxation time τ, is 100-1000 s. The relaxation process at the lowest frequency, Tg is approximately 200 K, is originated from the cooperative motion of water and gelatin. This relaxation is strong and has a similar relaxation strength to that of hydrated BSA. At Tg for the relaxation process involving the cooperative motion of gelatin and water, the temperature dependence of the relaxation process of UCW crosses over from Vogel-Fulcher behavior to Arrhenius behavior with decreasing temperature. A characteristic property of the gelatin-water mixture is a change in the temperature dependence of the relaxation time of the relaxation processes of hydrated gelatin at approximately 260 K.

  15. 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+).

  16. 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

  17. 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

  18. 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

  19. 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.

  20. 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.

  1. Kinetic-freezing and unfreezing of local-region fluctuations in a glass structure observed by heat capacity hysteresis

    SciTech Connect

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

    2015-06-07

    Fluctuations confined to local regions in the structure of a glass are observed as the Johari-Goldstein (JG) relaxation. Properties of these regions and their atomic configuration are currently studied by relaxation techniques, by electron microscopy, and by high-energy X-ray scattering and extended x-ray absorption fine structure methods. One expects that these fluctuations (i) would kinetically freeze on cooling a glass, and the temperature coefficient of its enthalpy, dH/dT, would consequently show a gradual decrease with decrease in T, (ii) would kinetically unfreeze on heating the glass toward the glass-liquid transition temperature, T{sub g}, and dH/dT would gradually increase, and (iii) there would be a thermal hysteresis indicating the time and temperature dependence of the enthalpy. Since no such features have been found, thermodynamic consequences of these fluctuations are debated. After searching for these features in glasses of different types, we found it in one of the most stable metal alloy glasses of composition Pd{sub 40}Ni{sub 10}Cu{sub 30}P{sub 20}. On cooling from its T{sub g}, dH/dT decreased along a broad sigmoid-shape path as local-region fluctuations kinetically froze. On heating thereafter, dH/dT increased along a similar path as these fluctuations unfroze, and there is hysteresis in the cooling and heating paths, similar to that observed in the T{sub g}-endotherm range. After eliminating other interpretations, we conclude that local-region fluctuations seen as the JG relaxation in the non-equilibrium state of a glass contribute to its entropy, and we suggest conditions under which such fluctuations may be observed.

  2. 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.

  3. 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.

  4. 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

  5. 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

  6. The glass transition in cured epoxy thermosets: A comparative molecular dynamics study in coarse-grained and atomistic resolution

    NASA Astrophysics Data System (ADS)

    Langeloth, Michael; Sugii, Taisuke; Böhm, Michael C.; Müller-Plathe, Florian

    2015-12-01

    We investigate the volumetric glass transition temperature Tg in epoxy thermosets by means of molecular dynamics simulations. The epoxy thermosets consist of the resin bisphenol A diglycidyl ether and the hardener diethylenetriamine. A structure based coarse-grained (CG) force field has been derived using iterative Boltzmann inversion in order to facilitate simulations of larger length scales. We observe that Tg increases clearly with the degree of cross-linking for all-atomistic (AA) and CG simulations. The transition Tg in CG simulations of uncured mixtures is much lower than in AA-simulations due to the soft nature of the CG potentials, but increases all the more with the formation of rigid cross-links. Additional simulations of the CG mixtures in contact with a surface show the existence of an interphase region of about 3 nm thickness in which the network properties deviate significantly from the bulk. In accordance to experimental studies, we observe that Tg is reduced in this interphase region and gradually increases to its bulk value with distance from the surface. The present study shows that the glass transition is a local phenomenon that depends on the network structure in the immediate environment.

  7. The glass transition in cured epoxy thermosets: A comparative molecular dynamics study in coarse-grained and atomistic resolution

    SciTech Connect

    Langeloth, Michael; Böhm, Michael C.; Müller-Plathe, Florian; Sugii, Taisuke

    2015-12-28

    We investigate the volumetric glass transition temperature T{sub g} in epoxy thermosets by means of molecular dynamics simulations. The epoxy thermosets consist of the resin bisphenol A diglycidyl ether and the hardener diethylenetriamine. A structure based coarse-grained (CG) force field has been derived using iterative Boltzmann inversion in order to facilitate simulations of larger length scales. We observe that T{sub g} increases clearly with the degree of cross-linking for all-atomistic (AA) and CG simulations. The transition T{sub g} in CG simulations of uncured mixtures is much lower than in AA-simulations due to the soft nature of the CG potentials, but increases all the more with the formation of rigid cross-links. Additional simulations of the CG mixtures in contact with a surface show the existence of an interphase region of about 3 nm thickness in which the network properties deviate significantly from the bulk. In accordance to experimental studies, we observe that T{sub g} is reduced in this interphase region and gradually increases to its bulk value with distance from the surface. The present study shows that the glass transition is a local phenomenon that depends on the network structure in the immediate environment.

  8. Critical exponents of the superfluid-Bose-glass transition in three dimensions.

    PubMed

    Yao, Zhiyuan; da Costa, Karine P C; Kiselev, Mikhail; Prokof'ev, Nikolay

    2014-06-01

    Recent experimental and numerical studies of the critical-temperature exponent ϕ for the superfluid-Bose-glass universality in three-dimensional systems report strong violations of the key quantum critical relation, ϕ=νz, where z and ν are the dynamic and correlation-length exponents, respectively; these studies question the conventional scaling laws for this quantum critical point. Using Monte Carlo simulations of the disordered Bose-Hubbard model, we demonstrate that previous work on the superfluid-to-normal-fluid transition-temperature dependence on the chemical potential (or the magnetic field, in spin systems), T_{c}∝(μ-μ_{c})^{ϕ}, was misinterpreting transient behavior on approach to the fluctuation region with the genuine critical law. When the model parameters are modified to have a broad quantum critical region, simulations of both quantum and classical models reveal that the ϕ=νz law [with ϕ=2.7(2), z=3, and ν=0.88(5)] holds true, resolving the ϕ-exponent "crisis." PMID:24949775

  9. 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.

  10. 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.

  11. 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

  12. Thermodynamics and ideal glass transition on the surface of a monatomic system modeled as quasi "2-dimensional" recursive lattices

    NASA Astrophysics Data System (ADS)

    Huang, Ran

    Two quasi 2-dimensional recursive lattices formed by planar elements have been designed to investigate the surface thermodynamics of monatomic Ising glass system with the aim to study the metastability of supercooled liquids and the ideal glass transition. Both lattices are constructed as hybrids of a Husimi lattice representing the bulk and lower dimensional recursive trees representing the surface. The coordination number, i.e. the number of neighbor sites surrounding one site, is designed to be 3 on the surface and 4 inside the bulk to mimic the 2D regular square lattice case. The recursive properties of recursive lattices were adopted to obtain exact thermodynamic calculations without approximation. The model has a strong anti-ferromagnetic interaction to give rise to an ordered phase identified as a crystal, and a metastable solution is also found to represent the amorphous phase. Interactions between particles farther away than the nearest neighbor distance are taken into consideration. The calculations were done with C/C++ programs. A recursive calculation technique was employed to approach an exact description of the system with the ratio of partial partition functions (PPF) on each site of the lattice. Thermal properties including free energy, energy density and entropy of the ideal crystal and supercooled liquid state of the model on the surface are calculated by the PPF. By analyzing the free energies and entropies of the crystal and supercooled liquid state, we are able to identify the melting transition and the second order ideal glass transition on the surface. The effects of different energy terms that produce competitions between crystallization and glass transition are studied. The results show that due to the coordination number change, the transition temperature on the surface decreases significantly compared to the transition temperature of the bulk system obtained in our previous research. Our theoretical calculation agrees with experiments and

  13. 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

  14. 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...

  15. 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.

  16. 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)

  17. 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

  18. 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

  19. The glass transition of polymers with different side-chain stiffness confined in free-standing thin films

    NASA Astrophysics Data System (ADS)

    Xie, Shi-Jie; Qian, Hu-Jun; Lu, Zhong-Yuan

    2015-02-01

    The effect of confinement on the glass transition temperature Tg of polymeric glass formers with different side chain stiffness is investigated by coarse-grained molecular dynamics simulations. We find that polymer with stiffer side groups exhibits much more pronounced Tg variation in confinement compared to that with relatively flexible side groups, in good agreement with experiments. Our string analysis demonstrates that the polymer species dependence of dynamics can be described by an Adam-Gibbs like relation between the size of cooperatively rearranging regions and relaxation time. However, the primary effect of changing side-group stiffness is to alter the activation barrier for rearrangement, rather than string size. We clarify that free-surface perturbation is the primary factor in determining the magnitude of Tg variation for polymers in confinement: It is more significant for polymers having higher Tg and results in much more pronounced reduction of surface Tg and then the overall Tg of the polymers.

  20. 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.

  1. 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

  2. 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

  3. 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.

  4. 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

  5. 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.

  6. 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.

  7. 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

  8. 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

  9. Photo-thermo-refractive glass with sensitivity extended to near infrared region

    NASA Astrophysics Data System (ADS)

    Kompan, F.; Venus, G.; Glebova, L.; Mingareev, H.; Glebov, L.

    2016-02-01

    Photo-thermo-refractive (PTR) glass is a multicomponent silicate glass doped with Ce3+ and Ag+ which is extensively used for holographic recording of volume Bragg gratings (VBGs). Possibility of recording of advanced, complex holograms in the PTR glass is of current interest as it offers great opportunities in imaging and laser systems control. However, the glass does not have capabilities for recording of complex holograms with using light from the visible / IR spectral region due to its UV photosensitivity. Extension of the PTR-glass sensitivity range into the visible / IR spectral region was carried out by doping the original glass with trivalent terbium ions. Photosensitivity mechanism was implemented by means of excited state absorption using a UV photon and a visible photon for excitation of the Tb3+ 5d14f7 band. For the first time refractive index modulation on the order of 2x10-4 was obtained in PTR glass after exposure to the visible / IR light. Resulting magnitude of induced refractive index allows for high efficiency complex hologram fabrication in Tb3+ doped PTR glass for use which in the visible / IR region. Holographic capabilities of Tb3+ doped PTR glass were demonstrated by recording a complex hologram in the glass using green and blue light.

  10. 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.

  11. Optical and infrared absorption spectra of 3d transition metal ions-doped sodium borophosphate glasses and effect of gamma irradiation

    NASA Astrophysics Data System (ADS)

    Abdelghany, A. M.; ElBatal, F. H.; Azooz, M. A.; Ouis, M. A.; ElBatal, H. A.

    2012-12-01

    Undoped and transition metals (3d TM) doped sodium borophosphate glasses were prepared. UV-visible absorption spectra were measured in the region 200-900 nm before and after gamma irradiation. Experimental optical data indicate that the undoped sodium borophosphate glass reveals before irradiation strong and broad UV absorption and no visible bands could be identified. Such UV absorption is related to the presence of unavoidable trace iron impurities within the raw materials used for preparation of this base borophosphate glass. The TMs-doped glasses show absorption bands within the UV and/or visible regions which are characteristic to each respective TM ion in addition to the UV absorption observed from the host base glass. Infrared absorption spectra of the undoped and TMs-doped glasses reveal complex FTIR consisting of extended characteristic vibrational bands which are specific for phosphate groups as a main constituent but with the sharing of some vibrations due to the borate groups. This criterion was investigated and approved using DAT (deconvolution analysis technique). The effects of different TMs ions on the FTIR spectra are very limited due to the low doping level (0.2%) introduced in the glass composition. Gamma irradiation causes minor effect on the FTIR spectra specifically the decrease of intensities of some bands. Such behavior is related to the change of bond angles and/or bond lengths of some structural building units upon gamma irradiation.

  12. 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.

  13. The Evolution of Transition Region Loops Using IRIS and AIA

    NASA Technical Reports Server (NTRS)

    Winebarger, Amy R.; DePontieu, Bart

    2014-01-01

    Over the past 50 years, the model for the structure of the solar transition region has evolved from a simple transition layer between the cooler chromosphere to the hotter corona to a complex and diverse region that is dominated by complete loops that never reach coronal temperatures. The IRIS slitjaw images show many complete transition region loops. Several of the "coronal" channels in the SDO AIA instrument include contributions from weak transition region lines. In this work, we combine slitjaw images from IRIS with these channels to determine the evolution of the loops. We develop a simple model for the temperature and density evolution of the loops that can explain the simultaneous observations. Finally, we estimate the percentage of AIA emission that originates in the transition region.

  14. 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.

  15. Analysis of the thermally stimulated discharge current around glass-rubber transition temperature in polyethylene terephthalate

    NASA Astrophysics Data System (ADS)

    Neagu, Eugen R.; Marat-Mendes, Jose N.; Das-Gupta, Dilip K.; Neagu, Rodica M.; Igreja, Rui

    1997-09-01

    The nature of the thermally stimulated discharge current (TSDC) for polyethylene terephthalate samples in the temperature range from room temperature to above glass-rubber transition temperature of the amorphous phase is analyzed. The well conditioning of the sample is strictly necessary in order to have a good reproducibility and accuracy of results. A main peak was observed whose maximum temperature moves towards a lower value with the decreasing of the amount of charge that flows through the sample during polarization. The peak position changes as well, if the sample is polarized in air or in oxygen and the nature of change is more important in the case of oxygen. The shape of the peak is complex and at least four shoulders have been identified around 85, 90, 105, and 125 °C using the cleaning technique. The activation energy tends to increase with repetition of the TSDC runs, in the glass-rubber transition temperature range, in the case when the cleaning technique is used for the peaks separation. For the conditioned samples, there is a good agreement between the experimental results and the analytical expression of the current, particularly in the region where it reaches a maximum, and so relevant values for the characteristic parameters of the peak are determined. The time interval of the short circuiting of the sample, at room temperature, before the TSDC measurement, strongly influences the initial rise of the current and consequently the parameters of the peak. A possible redistribution of the internal field arising from the injected charge, the heterocharge, and the existing charge in the sample as received, has been put forward to account for the experimental evidences. The conclusion is that the current is mainly determined by the space-charge released from the traps that are likely continuously distributed in energy. For the stated polarization conditions, the charge is released from the shallow traps with an activation energy in the range 0.23-0.32 e

  16. 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.

  17. 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.

  18. 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.

  19. Molecular Reorientation Dynamics Govern the Glass Transitions of the Amorphous Ices.

    PubMed

    Shephard, J J; Salzmann, C G

    2016-06-16

    The glass transitions of low-density amorphous ice (LDA) and high-density amorphous ice (HDA) are the topic of controversial discussions. Understanding their exact nature may be the key to explaining the anomalies of liquid water but has also got implications in the general context of polyamorphism, the occurrence of multiple amorphous forms of the same material. We first show that the glass transition of hydrogen-disordered ice VI is associated with the kinetic unfreezing of molecular reorientation dynamics by measuring the calorimetric responses of the corresponding H2O, H2(18)O, and D2O materials in combination with X-ray diffraction. Well-relaxed LDA and HDA show identical isotopic-response patterns in calorimetry as ice VI, and we conclude that the glass transitions of the amorphous ices are also governed by molecular reorientation processes. This "reorientation scenario" seems to resolve the previously conflicting viewpoints and is consistent with the fragile-to-strong transition from water to the amorphous ices. PMID:27243277

  20. Probing the Bose glass-superfluid transition using quantum quenches of disorder

    NASA Astrophysics Data System (ADS)

    Meldgin, Carolyn; Ray, Ushnish; Russ, Philip; Chen, David; Ceperley, David M.; Demarco, Brian

    2016-07-01

    The disordered Bose-Hubbard model--a paradigm for strongly correlated and disordered bosonic systems--is central to our understanding of quantum phase transitions. Despite extensive theoretical work on the disordered Bose-Hubbard model, little is known about the impact of temperature, the dynamical behaviour of quantum phases, and how equilibrium is affected during quantum phase transitions. These issues are critically important to applications such as quantum annealing and electronics based on quantum phase transitions. Here, we use a quantum quench of disorder in an ultracold lattice gas to dynamically probe the superfluid-Bose glass quantum phase transition at non-zero temperature ( Fig. 1). By measuring excitations generated during the quench, we provide evidence for superfluid puddles in the Bose glass phase and produce a superfluid-Bose glass phase diagram consistent with completely constrained, finite temperature, and equilibrium quantum Monte Carlo simulations. The residual energy from the quench, which is an efficacy measure for optimization through quantum annealing, is unchanged for quench times spanning nearly a hundred tunnelling times.

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

    NASA Astrophysics Data System (ADS)

    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 Tg is dependent on molecular weight, but the role of molecular-weight polydispersity on Tg 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 Tg, 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.

  2. 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

  3. On the Importance of Transition Regions for Automatic Speaker Recognition

    NASA Astrophysics Data System (ADS)

    Lee, Bong-Jin; Jung, Chi-Sang; Choi, Jeung-Yoon; Kang, Hong-Goo

    This letter describes the importance of transition regions, e.g. at phoneme boundaries, for automatic speaker recognition compared with using steady-state regions. Experimental results of automatic speaker identification tasks confirm that transition regions include the most speaker distinctive features. A possible reason for obtaining such results is described in view of articulation, in particular, the degree of freedom of articulators. These results are expected to provide useful information in designing an efficient automatic speaker recognition system.

  4. Elastic properties of Pd40Cu30Ni10P20 bulk glass in supercooled liquid region

    NASA Astrophysics Data System (ADS)

    Nishiyama, N.; Inoue, A.; Jiang, J. Z.

    2001-04-01

    In situ ultrasonic measurements for the Pd40Cu30Ni10P20 bulk glass in three states: Glassy solid, supercooled liquid, and crystalline, have been performed. It is found that velocities of both longitudinal and transverse waves and elastic moduli (shear modulus, bulk modulus, Young's modulus, and Lamé parameter), together with Debye temperature, gradually decrease with increasing temperature through the glass transition temperature as the Poisson's ratio increases. The behavior of the velocity of transverse wave vs. temperature in the supercooled liquid region could be explained by viscosity flow, rather than the two different crystallization processes in the region, suggested in the literature. No decomposition was detected at a temperature only 5 K below the crystallization temperature.

  5. Effect of free surface roughness on the apparent glass transition temperature in thin polymer films measured by ellipsometry.

    PubMed

    Efremov, Mikhail Yu

    2014-12-01

    Ellipsometry is one of the standard methods for observation of glass transition in thin polymer films. This work proposes that sensitivity of the method to surface morphology can complicate manifestation of the transition in a few nm thick samples. Two possible mechanisms of free surface roughening in the vicinity of glass transition are discussed: roughening due to lateral heterogeneity and roughening associated with thermal capillary waves. Both mechanisms imply an onset of surface roughness in the glass transition temperature range, which affects the experimental data in a way that shifts apparent glass transition temperature. Effective medium approximation models are used to introduce surface roughness into optical calculations. The results of the optical modeling for a 5 nm thick polystyrene film on silicon are presented. PMID:25554303

  6. Survey and research on up-conversion emission character and energy transition of Yb3+/Er3+/Tm3+ co-doped phosphate glass and glass ceramic

    NASA Astrophysics Data System (ADS)

    Yu, Yin; Song, Feng; Ming, Chengguo; Liu, Jiadong; Li, Wei; Liu, Yanling; Zhao, Hongyan

    2012-11-01

    By conventional high-temperature melting method, Yb3+/Er3+/Tm3+ co-doped phosphate glass was synthesized. After annealing the precursor glass, the phosphate glass ceramic (GC) was obtained. By measuring the X-ray diffraction (XRD) spectrum, it is proved that the LiYbP4O12 and Li6P6O18 nano-crystals have existed in the phosphate GC. The up-conversion (UC) emission intensity of the GC is obvious stronger compared to that of the glass. The reason is that the shorter distance between rare earth ions in the glass ceramic increases the energy transitions from the sensitized ions (Yb3+) to the luminous ions (Er3+ and Tm3+). By studying the dependence of UC emissions on the pump power, the 523 and 546 nm green emissions of Er3+ ions in the glass are two-photon processes. But in the glass ceramic, they are two/three-photon processes. The phenomenon implies that a three-photon process has participated in the population of the two green emissions. Using Dexter theory, we discuss the energy transitions of Er3+ and Tm3+. The results indicate the energy transition of Tm3+ to Er3+ is very strong in the GC, which changes the population mechanism of UC emissions of Er3+.

  7. Difference in variation of glass transition activation energy between 1,2-propanediamine and 1,2-propanediol

    NASA Astrophysics Data System (ADS)

    Terashima, Yukio

    2016-05-01

    Variations of the effective activation energy (Eα) throughout the glass transition were determined for 1,2-propanediamine (12PDA) and 1,2-propanediol (12PDO) by applying an isoconversional method to differential scanning calorimetry (DSC) data. Eα was found to markedly decrease throughout the glass transition of 12PDA, whereas such drastic change in Eα was not observed for 12PDO. Although the two simple liquids are similar in molecular structure and size, their trends in Eα and fragility m throughout the glass transition can be quite different. The significant disparity in the kinetic parameters can be caused by differences in hydrogen-bonding structure between 12PDA and 12PDO.

  8. Overlap and activity glass transitions in plaquette spin models with hierarchical dynamics.

    PubMed

    Turner, Robert M; Jack, Robert L; Garrahan, Juan P

    2015-08-01

    We consider thermodynamic and dynamic phase transitions in plaquette spin models of glasses. The thermodynamic transitions involve coupled (annealed) replicas of the model. We map these coupled-replica systems to a single replica in a magnetic field, which allows us to analyze the resulting phase transitions in detail. For the triangular plaquette model (TPM), we find for the coupled-replica system a phase transition between high- and low-overlap phases, occurring at a coupling ɛ*(T), which vanishes in the low-temperature limit. Using computational path sampling techniques, we show that a single TPM also displays "space-time" transitions between active and inactive dynamical phases. These first-order dynamical transitions occur at a critical counting field sc(T)≳0 that appears to vanish at zero temperature in a manner reminiscent of the thermodynamic overlap transition. In order to extend the ideas to three dimensions, we introduce the square pyramid model, which also displays both overlap and activity transitions. We discuss a possible common origin of these various phase transitions, based on long-lived (metastable) glassy states. PMID:26382352

  9. Overlap and activity glass transitions in plaquette spin models with hierarchical dynamics

    NASA Astrophysics Data System (ADS)

    Turner, Robert M.; Jack, Robert L.; Garrahan, Juan P.

    2015-08-01

    We consider thermodynamic and dynamic phase transitions in plaquette spin models of glasses. The thermodynamic transitions involve coupled (annealed) replicas of the model. We map these coupled-replica systems to a single replica in a magnetic field, which allows us to analyze the resulting phase transitions in detail. For the triangular plaquette model (TPM), we find for the coupled-replica system a phase transition between high- and low-overlap phases, occurring at a coupling ɛ*(T ) , which vanishes in the low-temperature limit. Using computational path sampling techniques, we show that a single TPM also displays "space-time" transitions between active and inactive dynamical phases. These first-order dynamical transitions occur at a critical counting field sc(T ) ≳0 that appears to vanish at zero temperature in a manner reminiscent of the thermodynamic overlap transition. In order to extend the ideas to three dimensions, we introduce the square pyramid model, which also displays both overlap and activity transitions. We discuss a possible common origin of these various phase transitions, based on long-lived (metastable) glassy states.

  10. Apollo 14 Impact Glasses and Clementine Data: Implications for Regional Geology

    NASA Technical Reports Server (NTRS)

    Zellner, N. E. B.; Spudis, P. D.; Delano, J. W.; Whittet, D. C. B.

    2002-01-01

    Clementine color image data and analyses of 778 lunar impact glasses have been used together to suggest that the highlands of the Fra Mauro region consist of a KREEP-rich regolith overlying a feldspathic terrain. Low-KREEP impact glasses may possess a memory of impacts prior to 3.9 Ga ago. Additional information is contained in the original extended abstract.

  11. Anomalous glass transition behavior of SBR-Al2O3 nanocomposites at small filler concentrations

    NASA Astrophysics Data System (ADS)

    Sushko, Rymma; Filimon, Marlena; Dannert, Rick; Elens, Patrick; Sanctuary, Roland; Baller, Jörg

    2014-10-01

    Elastomers filled with hard nanoparticles are of great technical importance for the rubber industry. In general, fillers improve mechanical properties of polymer materials, e.g. elastic moduli, tensile strength etc. The smaller the size of the particles, the larger is the interface where interactions between polymer molecules and fillers can generate new properties. Using temperature-modulated differential scanning calorimetry and dynamic mechanical analysis, we investigated the properties of pure styrene-butadiene rubber (SBR) and SBR/alumina nanoparticles. Beside a reinforcement effect seen in the complex elastic moduli, small amounts of nanoparticles of about 2 wt% interestingly lead to an acceleration of the relaxation modes responsible for the thermal glass transition. This leads to a minimum in the glass transition temperature as a function of nanoparticle content in the vicinity of this critical concentration. The frequency dependent elastic moduli are used to discuss the possible reduction of the entanglement of rubber molecules as one cause for this unexpected behavior.

  12. The effect of glass transition in fullerite C60 on Ar impurity diffusion

    NASA Astrophysics Data System (ADS)

    Dolbin, A. V.; Esel'son, V. B.; Gavrilko, V. G.; Manzhelii, V. G.; Vinnikov, N. A.; Basnukaeva, R. M.

    2013-04-01

    The kinetics of sorption and subsequent desorption of argon gas by powdered fullerite C60 has been investigated in the temperature interval 58-290 K. The temperature dependence of the Ar diffusion coefficients in fullerite has been obtained using measured characteristic times of sorption. The diffusion coefficients for Ar decrease monotonically with decreasing temperature in the entire temperature range, which corresponds to the thermally activated diffusion of Ar atoms in fullerite. The glass transition in fullerite induces an order-of magnitude decrease in the activation energy of Ar diffusion in fullerite. This appears to be due to new paths that appeared as a result of the glass transition, in which the barriers separating the interstitial voids in the C60 lattice are significantly lower.

  13. Mechanics at the glass-to-gel transition of thermoresponsive microgel suspensions.

    PubMed

    Appel, Jeroen; Fölker, Bart; Sprakel, Joris

    2016-02-23

    We study the rheology of systems of thermoresponsive microgels which can transition between a repulsive glass and an attractive gel state. We find marked differences between these two colloidal solids, within the same experimental system, due to the different origins for their dynamic arrest. While the rigidity of the repulsive systems depends solely on particle volume fraction, we find that the change in linear elasticity upon introducing attractive bonds in the system scales linearly with the adhesive bond strength which can be tuned with the temperature in our experiments. And while the glasses yield reversibly and with a rate-dependent energy dissipation, bond-reorganisation in the gels is suppressed so that their rupture is irreversible and accompanied by a high, but rate-independent, dissipation. These results highlight how colloids with responsive interactions can be employed to shed new light onto solid-solid transitions. PMID:26843322

  14. Demonstration of glass transition temperature shift in thin supported polystyrene films by internal reference method

    NASA Astrophysics Data System (ADS)

    Efremov, Mikhail Yu.; Thode, Christopher; Nealey, Paul F.

    2013-02-01

    An internal reference method is used for the first time to clearly demonstrate the glass transition temperature (Tg) depression effect in 5 nm thick polystyrene films spin-cast on silicon wafers. Initially flat films exhibit depressed Tg at approximately 85 °C. Temperature-induced dewetting on hexamethyldisilazane-treated silicon substrates leads to formation of discontinuous films with average effective thickness of 15-30 nm. Dewetted films demonstrate Tg close to the bulk value (≈ 100 °C) and are used as internal references. Data both for continuous and discontinuous films are obtained in the same experimental run for the same sample, which allows direct comparison between datasets. Phase-modulated ellipsometry in vacuum is used to monitor glass transition. Both traditional linear temperature scan method and a novel temperature modulated technique have been employed in the measurements.

  15. Disorder-Assisted Melting and the Glass Transition in Amorphous Solids

    NASA Astrophysics Data System (ADS)

    Zaccone, Alessio; Terentjev, Eugene M.

    2013-04-01

    The mechanical response of solids depends on temperature, because the way atoms and molecules respond collectively to deformation is affected at various levels by thermal motion. This is a fundamental problem of solid state science and plays a crucial role in materials science. In glasses, the vanishing of shear rigidity upon increasing temperature is the reverse process of the glass transition. It remains poorly understood due to the disorder leading to nontrivial (nonaffine) components in the atomic displacements. Our theory explains the basic mechanism of the melting transition of amorphous (disordered) solids in terms of the lattice energy lost to this nonaffine motion, compared to which thermal vibrations turn out to play only a negligible role. The theory is in good agreement with classic data on melting of amorphous polymers (for which no alternative theory can be found in the literature) and offers new opportunities in materials science.

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

    SciTech Connect

    Komatsu, Marina; Mizuno, Maya; Fukunaga, Kaori; Saito, Shingo; Ohki, Yoshimichi

    2015-04-07

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

  17. Modified shape memory cyanate polymers with a wide range of high glass transition temperatures

    NASA Astrophysics Data System (ADS)

    Xie, Fang; Huang, Longnan; Liu, Yanju; Leng, Jinsong

    2012-04-01

    Shape memory cyanate polymers (SMCPs) are a new kind of smart materials, which have huge development potential and a promising future. A series of shape memory cyanate polymers were prepared by cyanate ester and varying content of a linear modifier. The thermal properties of the SMCPs were investigated by Differential Scanning Calorimetry (DSC), Thermal Gravimetric Analysis (TGA) and Dynamic Mechanical Analysis (DMA). The SMCPs we prepared have high glass transition temperature and show good heat resistance. The glass transition temperature Tg can be adjusted from 156.9°C to 259.6°C with the modifier. The initial temperature of thermal decomposition comes up to 300°C, which is enough high for the application in aerospace fields. The shape memory polymer we prepared shows a good shape memory effect, as the shape recovery time is less than 65s and the shape recovery rate reaches 95%.

  18. Fine structure of the solar transition region - Observations and interpretation

    NASA Technical Reports Server (NTRS)

    Cook, J. W.; Brueckner, G. E.

    1991-01-01

    An evaluation is conducted of recent high spatial resolution observations of the solar transition region and temperature minimum, in the form of UV spectra and spectroheliographs from both sounding rockets and the Spacelab 2 flights of the High Resolution Telescope and Spectrograph (HRTS). Attention is given to the solar atmosphere structure implications of the HRST's observational results. The inclusion of fine structure in conjectures concerning the transition region affects the plausibility of 1D average models of the solar atmosphere, as well as the determination of temperature gradients, possible nonradiative-heating mechanisms, and the comparison of transition region structures with corresponding observations of the photosphere and corona.

  19. Dynamic and thermodynamic characteristics associated with the glass transition of amorphous trehalose-water mixtures

    PubMed Central

    Weng, Lindong; Elliott, Gloria D.

    2014-01-01

    The glass transition temperature Tg of biopreservative formulations is important for predicting the longterm storage of biological specimens. As a complementary tool to thermal analysis techniques, which are the mainstay for determining Tg, molecular dynamics simulations have been successfully applied to predict the Tg of several protectants and their mixtures with water. These molecular analyses, however, rarely focused on the glass transition behavior of aqueous trehalose solutions, a subject that has attracted wide scientific attention via experimental approaches. Important behavior, such as hydrogen-bonding dynamics and self-aggregation has yet to be explored in detail, particularly below, or in the vicinity of, Tg. Using molecular dynamics simulations of several dynamic and thermodynamic properties, this study reproduced the supplemented phase diagram of trehalose-water mixtures (i.e., Tg as a function of the solution composition) based on experimental data. The structure and dynamics of the hydrogen-bonding network in the trehalose-water systems were also analyzed. The hydrogen-bonding lifetime was determined to be an order of magnitude higher in the glassy state than in the liquid state, while the constitution of the hydrogen-bonding network exhibited no noticeable change through the glass transition. It was also found that trehalose molecules preferred to form small, scattered clusters above Tg, but self-aggregation was substantially increased below Tg. The average cluster size in the glassy state was observed to be dependent on the trehalose concentration. Our findings provided insights into the glass transition characteristics of aqueous trehalose solutions as they relate to biopreservation. PMID:24803351

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

    PubMed Central

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

    2014-01-01

    We study the equilibrium liquid structure and dynamics of dilute and concentrated bovine eye lens α-crystallin solutions, using small-angle X-ray scattering, static and dynamic light scattering, viscometry, molecular dynamics simulations, and mode-coupling theory. We find that a polydisperse Percus–Yevick hard-sphere liquid-structure model accurately reproduces both static light scattering data and small-angle X-ray scattering liquid structure data from α-crystallin solutions over an extended range of protein concentrations up to 290 mg/mL or 49% vol fraction and up to ca. 330 mg/mL for static light scattering. The measured dynamic light scattering and viscosity properties are also consistent with those of hard-sphere colloids and show power laws characteristic of an approach toward a glass transition at α-crystallin volume fractions near 58%. Dynamic light scattering at a volume fraction beyond the glass transition indicates formation of an arrested state. We further perform event-driven molecular dynamics simulations of polydisperse hard-sphere systems and use mode-coupling theory to compare the measured dynamic power laws with those of hard-sphere models. The static and dynamic data, simulations, and analysis show that aqueous eye lens α-crystallin solutions exhibit a glass transition at high concentrations that is similar to those found in hard-sphere colloidal systems. The α-crystallin glass transition could have implications for the molecular basis of presbyopia and the kinetics of molecular change during cataractogenesis. PMID:25385638

  1. Optical absorption of gamma-irradiated lithium-borate glasses doped with different transition metal oxides

    NASA Astrophysics Data System (ADS)

    Marzouk, S. Y.; Elalaily, N. A.; Ezz-Eldin, F. M.; Abd-Allah, W. M.

    2006-06-01

    We have investigated the effect of gamma irradiation on the optical properties of Li 2O-B 2O 3 containing two concentrations (0.2 or 0.5 g) of each one of the following transition metals, V, Mn, Fe or Ni oxide glass samples. We studied the impacts of gamma irradiation in terms of the mechanism by which radiation-induced defects are generated. A resolution of the observed absorption spectra showed several bands which were induced by photo-reduction or photo-oxidation assumed to take place by photo-chemical reaction according to the type of transition metal oxide (TMO). Small deviations of these induced bands characteristic of the glass constituents were observed and explained in terms of the physical properties, in relation to different oxidation states of TMO in the glass matrix. The series Mn 2+, Fe 2+ and Ni 2+ ions shows a trend of increased photo-oxidation with increasing electronegativity or decreasing mass of the ions. The prepared samples were studied in terms of their dosimetric characteristics: calibration curves from 1.0524 to 42.096 kGy and fading at (25 and 50 °C). Thermal bleaching of irradiated glass was found to permit the reduction of the larger part of TMO ions in Li 2O-B 2O 3. Also, the results showed that the degeneration of the induced bands was faster at 50 than at 25 °C. The optical energy gap Eg was found to decrease with the increase of the radiation dose, and it is suggested that the mechanism of optical transition is forbidden by indirect transition.

  2. Dynamic and thermodynamic characteristics associated with the glass transition of amorphous trehalose-water mixtures.

    PubMed

    Weng, Lindong; Elliott, Gloria D

    2014-06-21

    The glass transition temperature Tg of biopreservative formulations is important for predicting the long-term storage of biological specimens. As a complementary tool to thermal analysis techniques, which are the mainstay for determining Tg, molecular dynamics simulations have been successfully applied to predict the Tg of several protectants and their mixtures with water. These molecular analyses, however, rarely focused on the glass transition behavior of aqueous trehalose solutions, a subject that has attracted wide scientific attention via experimental approaches. Important behavior, such as hydrogen-bonding dynamics and self-aggregation has yet to be explored in detail, particularly below, or in the vicinity of, Tg. Using molecular dynamics simulations of several dynamic and thermodynamic properties, this study reproduced the supplemented phase diagram of trehalose-water mixtures (i.e., Tg as a function of the solution composition) based on experimental data. The structure and dynamics of the hydrogen-bonding network in the trehalose-water systems were also analyzed. The hydrogen-bonding lifetime was determined to be an order of magnitude higher in the glassy state than in the liquid state, while the constitution of the hydrogen-bonding network exhibited no noticeable change through the glass transition. It was also found that trehalose molecules preferred to form small, scattered clusters above Tg, but self-aggregation was substantially increased below Tg. The average cluster size in the glassy state was observed to be dependent on the trehalose concentration. Our findings provided insights into the glass transition characteristics of aqueous trehalose solutions as they relate to biopreservation. PMID:24803351

  3. Nonuniqueness of H23 and H2 field-temperature transition lines in spin-glasses

    NASA Astrophysics Data System (ADS)

    Wenger, L. E.; Mydosh, J. A.

    1984-04-01

    Including the magnetic field dependence on the superparamagnetic relaxation time τ, "transition" lines in the H-T plane are obtained for constant τ. These lines follow the relation TH-T0~Hν where ν~23 except for H-->0 which shows a crossover to ν=2. Thus a power law similar to that derived from mean-field models of spin-glasses is obtained, based strictly on a superparamagnetic relaxation-time approach. This questions the conclusion that experimental observations of H-T lines are solely the result of a mean-field phase transition.

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

    NASA Astrophysics Data System (ADS)

    Li, Yiming; Zhao, Lijuan; Fu, Yuting; Shi, Yahui; Zhang, Xiaoyu; Yu, Hua

    2016-02-01

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

  5. Transition to Glass: Pilot Training for High-Technology Transport Aircraft

    NASA Technical Reports Server (NTRS)

    Wiener, Earl L.; Chute, Rebecca D.; Moses, John H.

    1999-01-01

    This report examines the activities of a major commercial air carrier between 1993 and late 1996 as it acquired an advanced fleet of high-technology aircraft (Boeing 757). Previously, the airline's fleet consisted of traditional (non-glass) aircraft, and this report examines the transition from a traditional fleet to a glass one. A total of 150 pilots who were entering the B-757 transition training volunteered for the study, which consisted of three query phases: (1) first day of transition training, (2) 3 to 4 months after transition training, and (3) 12 to 14 months after initial operating experience. Of these initial 150 pilots, 99 completed all three phases of the study, with each phase consisting of probes on attitudes and experiences associated with their training and eventual transition to flying the line. In addition to the three questionnaires, 20 in-depth interviews were conducted. Although the primary focus of this study was on the flight training program, additional factors such as technical support, documentation, and training aids were investigated as well. The findings generally indicate that the pilot volunteers were highly motivated and very enthusiastic about their training program. In addition, the group had low levels of apprehension toward automation and expressed a high degree of satisfaction toward their training. However, there were some concerns expressed regarding the deficiencies in some of the training aids and lack of a free-play flight management system training device.

  6. Glass transition in polymers: Comparison of results from DSC, TMA, and TOA measurements

    SciTech Connect

    Wiedemann, H.G.; Widmann, G.; Bayer, G.

    1994-09-01

    The determination of the glass transition temperature, T{sub g}, of polymers by differential scanning calorimetry (DSC) and thermomechanical analysis (TMA) is sometimes problematic and rather subjective. This was shown previously in the ICTA certificate (distributed by NBS as GM-754) for the certified reference material polystyrene (PS). The not very good reproducibility of the measured value of the onset is due to a variety of instrumental and experimental parameters. This is true also for the determination of the glass transition by TMA measurements. The main reasons are temperature gradients caused by the relatively high sample mass required for DSC and by the limited heat transfer in TMA, respectively. Their own experiments which were carried out with polystyrene and with [poly(ethyleneterephthalate)] (PET) proved that a combination of DSC with TOA (thermo-optical analysis or hot stage microscopy under polarized light) can solve some of these problems. TOA is a nonsubjective method since the changes in birefringence and light transmittance during the glass transition which are visible under the microscope are measured with a photocell. TOA allows T{sub g} measurements of small samples (fraction of milligrams).

  7. Influence of crossing angles of columnar defects on vortex glass transition in YBCO thin films

    NASA Astrophysics Data System (ADS)

    Sueyoshi, T.; Sogo, T.; Yonekura, K.; Fujiyoshi, T.; Mitsugi, F.; Ikegami, T.; Ishikawa, N.; Awaji, S.; Watanabe, K.

    2011-11-01

    To investigate the influence of the crossing angles of columnar defects (CDs) on the in-field properties of the critical current density Jc and the scaling parameter m derived from the isothermal current-voltage characteristics near the glass-liquid transition at B|| c-axis, YBCO thin films were irradiated using the 200 MeV Xe ions at two angles ± θ i relative to the c-axis. For the thin films, the obvious effect of the crossing angle of CDs occurred on the vortex glass-liquid transition more than the Jc properties. On the glass-liquid transition line, two inflection points induced by the c-axis correlated pinning were confirmed even for the samples of θ i = ±45°. In the magnetic field dependence of m, the peak or kink appeared near B/ B ϕ = 1/3 for the smaller crossing angles, whereas that was slightly visible for the samples of θ i = ±45°. In addition, the values of m for the small crossing angle were larger than those for the parallel CD configuration, while those for the larger crossing angle became smaller. These results suggested that the morphologies of correlated pinning centers strongly affect the dynamics of flux lines even in the disordered system such as thin films.

  8. 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.

  9. Unveiling the Dependence of Glass Transitions on Mixing Thermodynamics in Miscible Systems

    NASA Astrophysics Data System (ADS)

    Tu, Wenkang; Wang, Yunxi; Li, Xin; Zhang, Peng; Tian, Yongjun; Jin, Shaohua; Wang, Li-Min

    2015-02-01

    The dependence of the glass transition in mixtures on mixing thermodynamics is examined by focusing on enthalpy of mixing, ΔHmix with the change in sign (positive vs. negative) and magnitude (small vs. large). The effects of positive and negative ΔHmix are demonstrated based on two isomeric systems of o- vs. m- methoxymethylbenzene (MMB) and o- vs. m- dibromobenzene (DBB) with comparably small absolute ΔHmix. Two opposite composition dependences of the glass transition temperature, Tg, are observed with the MMB mixtures showing a distinct negative deviation from the ideal mixing rule and the DBB mixtures having a marginally positive deviation. The system of 1, 2- propanediamine (12PDA) vs. propylene glycol (PG) with large and negative ΔHmix is compared with the systems of small ΔHmix, and a considerably positive Tg shift is seen. Models involving the properties of pure components such as Tg, glass transition heat capacity increment, ΔCp, and density, ρ, do not interpret the observed Tg shifts in the systems. In contrast, a linear correlation is revealed between ΔHmix and maximum Tg shifts.

  10. What is the Actual Low-Temperature Glass Transition for Fish Flesh ?

    NASA Astrophysics Data System (ADS)

    Viriyarattanasak, Chotika; Kawai, Kiyoshi; Watanabe, Manabu; Suzuki, Toru

    We measured glass transition temperatures in the maximally freeze-concentrated phase (Tg') of tuna and cod tissue by differential scanning calorimetry (DSC) using an annealing technique. In our experiment, the Tg' (approximately -71°C) of tuna and cod tissue did not exhibit any significant change after isothermal holding for several weeks at a temperature higher than the Tg. Another Tg' appeared above -45°C when annealing was performed at a temperature higher than -60°C for one week. We also collected Tg' data for fish flesh from many published studies and discussed them in the light of our data. The Tg' values for fish flesh in most published reports are higher than -40°C, although there have been several reports that give values of around -70°C. The high glass transition temperature (i.e., -45°C) measured in our study agrees with most of the data in the literature. Furthermore, the results suggest that the glass transition behavior at the higher temperature may be correlated to the vitrification of protein itself.

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

    PubMed

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

    2016-04-01

    The mechanical response of glasses remains challenging to understand. Recent results indicate that the oscillatory rheology of soft glasses is accompanied by a sharp non-equilibrium transition in the microscopic dynamics. Here, we use simultaneous x-ray scattering and rheology to investigate the reversibility and hysteresis of the sharp symmetry change from anisotropic solid to isotropic liquid dynamics observed in the oscillatory shear of colloidal glasses (D. Denisov, M.T. Dang, B. Struth, A. Zaccone, P. Schall, Sci. Rep. 5 14359 (2015)). We use strain sweeps with increasing and decreasing strain amplitude to show that, in analogy with equilibrium transitions, this sharp symmetry change is reversible and exhibits systematic frequency-dependent hysteresis. Using the non-affine response formalism of amorphous solids, we show that these hysteresis effects arise from frequency-dependent non-affine structural cage rearrangements at large strain. These results consolidate the first-order-like nature of the oscillatory shear transition and quantify related hysteresis effects both via measurements and theoretical modelling. PMID:27106107

  12. Unveiling the Dependence of Glass Transitions on Mixing Thermodynamics in Miscible Systems

    PubMed Central

    Tu, Wenkang; Wang, Yunxi; Li, Xin; Zhang, Peng; Tian, Yongjun; Jin, Shaohua; Wang, Li-Min

    2015-01-01

    The dependence of the glass transition in mixtures on mixing thermodynamics is examined by focusing on enthalpy of mixing, ΔHmix with the change in sign (positive vs. negative) and magnitude (small vs. large). The effects of positive and negative ΔHmix are demonstrated based on two isomeric systems of o- vs. m- methoxymethylbenzene (MMB) and o- vs. m- dibromobenzene (DBB) with comparably small absolute ΔHmix. Two opposite composition dependences of the glass transition temperature, Tg, are observed with the MMB mixtures showing a distinct negative deviation from the ideal mixing rule and the DBB mixtures having a marginally positive deviation. The system of 1, 2- propanediamine (12PDA) vs. propylene glycol (PG) with large and negative ΔHmix is compared with the systems of small ΔHmix, and a considerably positive Tg shift is seen. Models involving the properties of pure components such as Tg, glass transition heat capacity increment, ΔCp, and density, ρ, do not interpret the observed Tg shifts in the systems. In contrast, a linear correlation is revealed between ΔHmix and maximum Tg shifts. PMID:25686751

  13. Low-density to high-density transition in Ce75Al23Si2 metallic glass.

    PubMed

    Zeng, Q S; Fang, Y Z; Lou, H B; Gong, Y; Wang, X D; Yang, K; Li, A G; Yan, S; Lathe, C; Wu, F M; Yu, X H; Jiang, J Z

    2010-09-22

    Using in situ high-pressure x-ray diffraction (XRD), we observed a pressure-induced polyamorphic transition from the low-density amorphous (LDA) state to the high-density amorphous (HDA) state in Ce(75)Al(23)Si(2) metallic glass at about 2 GPa and 300 K. The thermal stabilities of both LDA and HDA metallic glasses were further investigated using in situ high-temperature and high-pressure XRD, which revealed different pressure dependences of the onset crystallization temperature (T(x)) between them with a turning point at about 2 GPa. Compared with Ce(75)Al(25) metallic glass, minor Si doping shifts the onset polyamorphic transition pressure from 1.5 to 2 GPa and obviously stabilizes both LDA and HDA metallic glasses with higher T(x) and changes their slopes dT(x)/dP. The results obtained in this work reveal another polyamorphous metallic glass system by minor alloying (e.g. Si), which could modify the transition pressure and also properties of LDA and HDA metallic glasses. The minor alloying effect reported here is valuable for the development of more polyamorphous metallic glasses, even multicomponent bulk metallic glasses with modified properties, which will trigger more investigations in this field and improve our understanding of polyamorphism and metallic glasses. PMID:21403196

  14. Regional differences in erythrocyte transit in normal lungs.

    PubMed

    Hogg, J C; Martin, B A; Lee, S; McLean, T

    1985-10-01

    We measured regional blood volume and flow in the lungs of nine mongrel dogs. The time taken for the erythrocytes to transit through individual lung regions was calculated from the relationship t = V/Q, where V is blood volume and Q is flow. The data show that the total pulmonary blood volume was 82 +/- 6 ml and that the average time spent in the pulmonary vascular bed was 2.86 +/- 0.31 s. The frequency distribution of the transit times ranged from 0.41 to 6 s in the experiment with the shortest mean transit (1.62 s) and from 0.9 to greater than 20 s in the experiment with the longest mean transit time (4.6 s). The regional data show that the longer transit times were in the upper lung and that expansion of the blood volume as flow increased down the lung prevented an excessive shortening of the transit time. We conclude that increasing regional blood flow is associated with an expansion of regional blood volumes so that the transit times remain relatively constant. PMID:4055606

  15. Glass transition in ferroic glass K x (ND4)1-x D2PO4: a complete x-ray diffraction line shape analysis

    NASA Astrophysics Data System (ADS)

    Ranjan Choudhury, Rajul; Chitra, R.; Jayakrishnan, V. B.

    2016-03-01

    Quenching of dynamic disorder in glassy systems is termed as the glass transition. Ferroic glasses belong to the class of paracrystalline materials having crystallographic order in-between that of a perfect crystal and amorphous material, a classic example of ferroic glass is the solid solution of ferroelectric deuterated potassium dihydrogen phosphate and antiferroelectric deuterated ammonium dihydrogen phosphate. Lowering temperature of this ferroic glass can lead to a glass transition to a quenched disordered state. The subtle atomic rearrangement that takes place at such a glass transition can be revealed by careful examination of the temperature induced changes occurring in the x-ray powder diffraction (XRD) patterns of these materials. Hence we report here results of a complete diffraction line shape analysis of the XRD patterns recorded at different temperatures from deuterated mixed crystals DK x A1-x DP with mixing concentration x ranging as 0 < x < 1. Changes observed in diffraction peak shapes have been explained on the basis of structural rearrangements induced by changing O-D-O hydrogen bond dynamics in these paracrystals.

  16. Optical transitions of Tm3+ in oxyfluoride glasses and compositional and thermal effect on upconversion luminescence of Tm3+/Yb3+-codoped oxyfluoride glasses.

    PubMed

    Feng, Li; Wu, Yinsu; Liu, Zhuo; Guo, Tao

    2014-01-24

    Optical properties of Tm(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 Tm(3+)/Yb(3+)-codoped SiO2-BaF2-ZnF2 glasses under 980 nm excitation. The effects of composition, concentration of the doping ions, temperature, and excitation pump power on the upconversion emissions were also systematically studied. PMID:24051289

  17. Thermodynamic evidence for the Bose glass transition in twinnedYBa2Cu3O7-δcrystals

    DOE PAGESBeta

    Pérez-Morelo, D. J.; Osquiguil, E.; Kolton, A. B.; Nieva, G.; Jung, I. W.; López, D.; Pastoriza, H.

    2015-07-21

    We used a micromechanical torsional oscillator to measure the magnetic response of a twinned YBaBa2Cu3O7-δ single crystal disk near the Bose glass transition. We observe an anomaly in the temperature dependence of the magnetization consistent with the appearance of a magnetic shielding perpendicular to the correlated pinning of the twin boundaries. This effect is related to the thermodynamic transition from the vortex liquid phase to a Bose glass state.

  18. Threshold transitions in a regional urban system

    EPA Science Inventory

    In this paper we analyze the evolution of city size distributions over time in a regional urban system. This urban complex system is in constant flux with changing groups and city migration across existing and newly created groups. Using group formation as an emergent property, t...

  19. Pressure-Induced Glass Transition Probed via the Mobility of Coumarin 1 Fluorescent Molecule.

    PubMed

    Bonetti, Marco

    2016-05-12

    The route to form a glass is generally achieved upon cooling where the slowing down might be interpreted as the trapping of molecules in potential wells. On the other hand, isothermal compression induces a glassy state by modifying the molecular packing ending in jamming. Here, we focus on how isothermal compression perturbs the mobility of a probe molecule in three different host liquids up to the pressure-induced glass transition. By use of the fluorescence recovery technique, the diffusion of the fluorescent molecule Coumarin 1 (C1) is measured in poly(propylene glycol) (PPG-1000M and -2700M), in the fragile van der Waals propylene carbonate (PC), and in hydrogen-bonded methanol and ethanol. High pressures up to 6 GPa are obtained with a diamond anvil cell. In PC at a pressure ∼1.3 GPa close to the glass-transition pressure, the diffusion coefficient of C1 follows an Arrhenius behavior with an ∼5 orders of magnitude increase of the diffusive time. No decoupling from the Stokes-Einstein equation is noticed. A similar exponential behavior is measured in ethanol and methanol but extended to different pressure ranges up to 2.5 and 6.2 GPa, respectively. In PPG-1000M a decoupling from the Stokes-Einstein relation is observed between 0.3 and 0.8 GPa that could be related to a modification of the interaction between polymer segments and the probe molecule. These results might indicate that interaction between probe and dynamic heterogeneities become less important under applied pressure, unlike in the temperature-induced glass transition. PMID:27110923

  20. Implications of storage and handling conditions on glass transition and potential devitrification of oocytes and embryos.

    PubMed

    Sansinena, M; Santos, M V; Taminelli, G; Zaritky, N

    2014-08-01

    Devitrification, the process of crystallization of a formerly crystal-free, amorphous glass state, can lead to damage during the warming of cells. The objective of this study was to determine the glass transition temperature of a cryopreservation solution typically used in the vitrification, storage, and warming of mammalian oocytes and embryos using differential scanning calorimetry. A numerical model of the heat transfer process to analyze warming and devitrification thresholds for a common vitrification carrier (open-pulled straw) was conducted. The implications on specimen handling and storage inside the dewar in contact with nitrogen vapor phase at different temperatures were determined. The time required for initiation of devitrification of a vitrified sample was determined by mathematical modeling and compared with measured temperatures in the vapor phase of liquid nitrogen cryogenic dewars. Results indicated the glass transition ranged from -126 °C to -121 °C, and devitrification was initiated at -109 °C. Interestingly, samples entered rubbery state at -121 °C and therefore could potentially initiate devitrification above this value, with the consequent damaging effects to cell survival. Devitrification times were calculated considering an initial temperature of material immersed in liquid nitrogen (-196 °C), and two temperatures of liquid nitrogen vapors within the dewar (-50 °C and -70 °C) to which the sample could be exposed for a period of time, either during storage or upon its removal. The mathematical model indicated samples could reach glass transition temperatures and undergo devitrification in 30 seconds. Results of the present study indicate storage of vitrified oocytes and embryos in the liquid nitrogen vapor phase (as opposed to completely immersed in liquid nitrogen) poses the potential risk of devitrification. Because of the reduced time-handling period before samples reach critical rubbery and devitrification values, caution should be

  1. Strain glass transition in a multifunctional β-type Ti alloy

    PubMed Central

    Wang, Yu; Gao, Jinghui; Wu, Haijun; Yang, Sen; Ding, Xiangdong; Wang, Dong; Ren, Xiaobing; Wang, Yunzhi; Song, Xiaoping; Gao, Jianrong

    2014-01-01

    Recently, a class of multifunctional Ti alloys called GUM metals attracts tremendous attentions for their superior mechanical behaviors (high strength, high ductility and superelasticity) and novel physical properties (Invar effect, Elinvar effect and low modulus). The Invar and Elinvar effects are known to originate from structural or magnetic transitions, but none of these transitions were found in the GUM metals. This challenges our fundamental understanding of their physical properties. In this study, we show that the typical GUM metal Ti-23Nb-0.7Ta-2Zr-1.2O (at%) alloy undergoes a strain glass transition, where martensitic nano-domains are frozen gradually over a broad temperature range by random point defects. These nano-domains develop strong texture after cold rolling, which causes the lattice elongation in the rolling direction associated with the transition upon cooling and leads to its Invar effect. Moreover, its Elinvar effect and low modulus can also be explained by the nano-domain structure of strain glass. PMID:24500779

  2. The influence of gamma radiation on the molecular weight and glass transition of PLLA and HAp/PLLA nanocomposite

    NASA Astrophysics Data System (ADS)

    Milicevic, D.; Trifunovic, S.; Dojcilovic, J.; Ignjatovic, N.; Suljovrujic, E.

    2010-09-01

    The influence of gamma radiation on the molecular weight and glass transition behaviour of poly- L-lactide (PLLA) and hydroxyapatite/poly- L-lactide (HAp/PLLA) nanocomposite has been studied. Since PLLA exposed to high-energy radiation in the presence of air is prone to chain scission reactions and large degradation, changes in molecular weight were obtained by gel permeation chromatography (GPC). Alterations in the glass transition behaviour were investigated by differential scanning calorimetry (DSC). The apparent activation energy (Δ H∗) for glass transition was determined on the basis of the heating rate dependence of the glass transition temperature ( T g). Our findings support the fact that chain scission is the main reason for the decrease of T g and Δ H∗ with the absorbed dose. Furthermore, more intensive chain scission degradation of PLLA was observed in HAp/PLLA and can only be ascribed to the presence of HAp nanoparticles. Consequently, initial differences in the glass transition temperature and/or apparent activation energy of PLLA and HAp/PLLA became more pronounced with absorbed dose. This study reveals that radiation-induced changes in molecular weight and glass transition temperature occur in a predictable and fairly accurate manner. Therefore, gamma radiation can be used not only for sterilization but also for tailoring desirable end-use properties of these biomaterials.

  3. Effect of the glass transition of coating adhesive on temperature performance of fiber optic gyroscope and its optimization

    NASA Astrophysics Data System (ADS)

    Wang, Yueze; Wang, Tieshui; Ma, Lin; Yu, Hao; Liu, Bohan

    2015-10-01

    The fiber optic gyroscope (FOG)based on Sagnac effect has became to one of the most important sensors in developing due to light in quality, high accuracy, compact in dimension and long life and has played a very important role in both military and civil use. It is the most difficult problem that the FOG has an obvious bias drift caused by temperature change and temperature grade, so its application is limited to a great extent. Fiber coil is one of the most critical components in FOG. Here, the characteristic of temperature error of the fiber optical coil was analyzed. At first, by studying the glass transition of coating adhesive in the fiber coil, the element model of the fiber coil with the glass transition of coating adhesive in FOG was built. Then the discrete mathematics model of SHUPE error with the glass transition of coating adhesive in FOG was built. Finally, based on the temperature models mentioned above, the effects caused by the glass transition of coating adhesive on temperature performance of fiber optic gyroscope were analyzed. Theoretical analysis and experimental results show that effect caused by the glass transition of coating adhesive had seriously affected the temperature performance of FOG. By optimizing the glass transition temperature of coating adhesive, the SHUPE error of fiber coils can be reduced. At the same time, the amplitude uniformity of the SHUPE error can be improved greatly to reduce the difficulty in temperature compensation.

  4. Thermal denaturation of myoglobin in water--disaccharide matrixes: relation with the glass transition of the system.

    PubMed

    Bellavia, Giuseppe; Cottone, Grazia; Giuffrida, Sergio; Cupane, Antonio; Cordone, Lorenzo

    2009-08-20

    Proteins embedded in glassy saccharide systems are protected against adverse environmental conditions [Crowe et al. Annu. Rev. Physiol. 1998, 60, 73-103]. To further characterize this process, we studied the relationship between the glass transition temperature of the protein-containing saccharide system (T(g)) and the temperature of thermal denaturation of the embedded protein (T(den)). To this end, we studied by differential scanning calorimetry the thermal denaturation of ferric myoglobin in water/disaccharide mixtures containing nonreducing (trehalose, sucrose) or reducing (maltose, lactose) disaccharides. All the samples studied are, at room temperature, liquid systems whose viscosity varies from very low to very large values, depending on the water content. At a high water/saccharide mole ratio, homogeneous glass formation does not occur; regions of glass form, whose T(g) does not vary by varying the saccharide content, and the disaccharide barely affects the myoglobin denaturation temperature. At a suitably low water/saccharide mole ratio, by lowering the temperature, the systems undergo transition to the glassy state whose T(g) is determined by the water content; the Gordon-Taylor relationship between T(g) and the water/disaccharide mole ratio is obeyed; and T(den) increases by decreasing the hydration regardless of the disaccharide, such effect being entropy-driven. The presence of the protein was found to lower the T(g). Furthermore, for nonreducing disaccharides, plots of T(den) vs T(g) give linear correlations, whereas for reducing disaccharides, data exhibit an erratic behavior below a critical water/disaccharide ratio. We ascribe this behavior to the likelihood that in the latter samples, proteins have undergone Maillard reaction before thermal denaturation. PMID:19719261

  5. Response of water to electric fields at temperatures below the glass transition: A molecular dynamics analysis

    SciTech Connect

    Hu, Xiaohu; Elghobashi-Meinhardt, Nadia; Gembris, Daniel; Smith, Jeremy C

    2011-01-01

    The electric field dependence of the structure and dynamics of water at 77 K, i.e., below the glass transition temperature (136 K), is investigated using molecular dynamics simulations. Transitions are found at two critical field strengths, denoted E1 and E2. The transition around E1 3.5 V/nm is characterized by the onset of significant structural disorder, a rapid increase in the orientational polarization, and a maximum in the dynamical fluctuations. At E2 40 V/nm, the system crystallizes in discrete steps into a body-centered-cubic unit cell that minimizes the potential energy by simultaneous superpolarization of the water molecular dipoles and maximization of the intermolecular hydrogen bonds. The stepwise and discontinuous increase of the orientational polarization with the increasing electric field indicates that the dipole relaxation in the electric field is highly cooperative.

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

    PubMed

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

    2016-09-21

    We re-examine the physical origin of the polymer glass transition from the point of view of marginal rigidity, which is achieved at a certain average number of mechanically active intermolecular contacts per monomer. In the case of polymer chains in a melt/poor solvent, each monomer has two neighbors bound by covalent bonds and also a number of central-force contacts modelled by the Lennard-Jones (LJ) potential. We find that when the average number of contacts per monomer (covalent and non-covalent) exceeds the critical value z* ≈ 4, the system becomes solid and the dynamics arrested - a state that we declare the glass. Coarse-grained Brownian dynamics simulations show that at sufficient strength of LJ attraction (which effectively represents the depth of quenching, or the quality of solvent) the polymer globule indeed crosses the threshold of z*, and becomes a glass with a finite zero-frequency shear modulus, G∝ (z-z*). We verify this by showing the distinction between the 'liquid' polymer droplet at z < z*, which changes shape and adopts the spherical conformation in equilibrium, and the glassy 'solid' droplet at z > z*, which retains its shape frozen at the moment of z* crossover. These results provide a robust microscopic criterion to tell the liquid apart from the glass for the linear polymers. PMID:27517325

  7. Rigidity transitions in glasses driven by changes in network dimensionality and structural groupings

    NASA Astrophysics Data System (ADS)

    Vignarooban, K.; Boolchand, P.; Micoulaut, M.; Malki, M.; Bresser, W. J.

    2014-12-01

    Calorimetric, Raman and electrical conductivity properties of alkali borates {(100-x)}\\text{B}_2\\text{O}_3\\text-x\\text{M}_2\\text{O} (\\text{M}=\\text{Li} , Na) are studied as a function of composition (x) and these show the presence of stiffness transitions and an intermediate phase which are driven by a combination of network dimensionality change and usual topological constraint changes. This picture is confirmed by a detailed Raman analysis showing that specific modes of molecular structural groupings dominate the network structure in the intermediate phase. Their evolution shows a one-to-one correspondance with the observed non-reversing heat flow at the glass transition, and are correlated with thresholds in ionic conductivity that allows identifying a flexible phase at high alkali content, whereas the mildly stressed-rigid \\text{B}_2\\text{O}3 -rich glasses are driven by the conversion of planar 2D boroxol ring structures into the 3D structural groupings. These findings deeply modify the usual picture of these archetypal glasses, and reveal the very first example of the onset of rigidity tuned by network dimensional conversion.

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

    PubMed

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

    2014-03-01

    The microscopic nonlinear Langevin equation theory is applied to study the localization and activated hopping of two-dimensional hard disks in the deeply supercooled and glass states. Quantitative comparisons of dynamic characteristic length scales, barrier, and their dependence on the reduced packing fraction are presented between hard-disk and hard-sphere suspensions. The dynamic barrier of hard disks emerges at higher absolute and reduced packing fractions and correspondingly, the crossover size of the dynamic cage which correlates to the Lindemann length for melting is smaller. The localization lengths of both hard disks and spheres decrease exponentially with packing fraction. Larger localization length of hard disks than that of hard spheres is found at the same reduced packing fraction. The relaxation time of hard disks rises dramatically above the reduced packing fraction of 0.88, which leads to lower reduced packing fraction at the kinetic glass transition than that of hard spheres. The present work provides a foundation for the subsequent study of the glass transition of binary or polydisperse mixtures of hard disks, normally adopted in experiments and simulations to avoid crystallization, and further, the rheology and mechanical response of the two-dimensional glassy colloidal systems. PMID:24606367

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

    PubMed

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

    2016-06-01

    High-performance magnetic materials have immense industrial and scientific importance in wide-ranging electronic, electromechanical, and medical device technologies. Metallic glasses with a fully amorphous structure are particularly suited for advanced soft-magnetic applications. However, fundamental scientific understanding is lacking for the spin-exchange interaction between metal and metalloid atoms, which typically constitute a metallic glass. Using an integrated experimental and molecular dynamics approach, we demonstrate the mechanism of electron interaction between transition metals and metalloids. Spin-exchange interactions were investigated for a Fe-Co metallic glass system of composition [(Co1-x Fe x )0.75B0.2Si0.05]96Cr4. The saturation magnetization increased with higher Fe concentration, but the trend significantly deviated from simple rule of mixtures. Ab initio molecular dynamics simulation was used to identify the ferromagnetic/anti-ferromagnetic interaction between the transition metals and metalloids. The overlapping band-structure and density of states represent 'Stoner type' magnetization for the amorphous alloys in contrast to 'Heisenberg type' in crystalline iron. The enhancement of magnetization by increasing iron was attributed to the interaction between Fe 3d and B 2p bands, which was further validated by valence-band study. PMID:27143686

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

    NASA Astrophysics Data System (ADS)

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

    2016-06-01

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

  11. A thin float glass MRPC for the outer region of CBM-TOF wall

    NASA Astrophysics Data System (ADS)

    Weiping, Zhu; Yi, Wang; Shengqin, Feng; Jingbo, Wang; Xinjie, Huang; Li, Shi; Babkin, V.; Golovatyuk, V.; Rumiantсev, M.; Eppley, G.; Nussbaum, T.

    2014-01-01

    A Multi-gap Resistive Plate Chamber (MRPC) made out of thin float glass is proposed for the outer region of the time of flight (TOF) system for the Compressed Baryonic Matter experiment at FAIR. Usually MRPCs are assembled with ordinary glass plates of 0.5 mm or more thickness, but their rate capability is less than the CBM requirement (1.5 kHz/cm2). There are two ways to improve the rate capability. The first way is to reduce the bulk resistivity of the glass plates. The second is to reduce the thickness of the glass plates. Tsinghua University has made significant progress in the development of low resistive glass and high rate MRPCs. In this paper we report on three MRPCs produced with float glass plates of 0.7 mm, 0.5 mm and 0.35 mm thickness. Tests with cosmic rays and X-rays were performed at Tsinghua University. The results show that thin float glass MRPCs work well and have the rate capability necessary to meet the demands of the CBM-TOF outer region. Further studies were performed using a continuous 1 GeV deuterium beam at the Nuclotron accelerator at the Joint Institute for Nuclear Research (JINR). Time resolution of about 70 ps and efficiency higher than 90% were obtained for flux densities up to 3 kHz/cm2, exceeding the requirement for the CBM-TOF outer region.

  12. Are rare, long waiting times between rearrangement events responsible for the slowdown of the dynamics at the glass transition?

    NASA Astrophysics Data System (ADS)

    Ahn, Ji Won; Falahee, Bryn; Del Piccolo, Chiara; Vogel, Michael; Bingemann, Dieter

    2013-03-01

    The dramatic slowdown of the structural relaxation at the glass transition is one of the most puzzling features of glass dynamics. Single molecule orientational correlation times show this strong Vogel-Fulcher-Tammann temperature dependence typical for glasses. Through statistical analysis of single molecule trajectories, we can identify individual glass rearrangement events in the vicinity of a probe molecule in the glass former poly(vinyl acetate) from 8 K below to 6 K above the glass transition temperature. We find that changes in the distribution of waiting times between individual glass rearrangement events are much less dramatic with temperature, the main difference being a small, but decisive number of increasingly long waiting times at lower temperatures. We notice similar individual, local relaxation events in molecular dynamics trajectories for a variety of glassy systems further from the glass transition, leading to waiting time distributions with similar features as those observed in the single molecule experiments. We show that these rare long waiting times are responsible for the dramatic increase in correlation time upon cooling.

  13. Testing of transition-region models: Test cases and data

    NASA Technical Reports Server (NTRS)

    Singer, Bart A.; Dinavahi, Surya; Iyer, Venkit

    1991-01-01

    Mean flow quantities in the laminar turbulent transition region and in the fully turbulent region are predicted with different models incorporated into a 3-D boundary layer code. The predicted quantities are compared with experimental data for a large number of different flows and the suitability of the models for each flow is evaluated.

  14. Glass transition of two-dimensional 80-20 Kob-Andersen model at constant pressure.

    PubMed

    Li, D; Xu, H; Wittmer, J P

    2016-02-01

    We reconsider numerically the two-dimensional version of the Kob-Andersen model (KA2d) with a fraction of 80% of large spheres. A constant moderate pressure is imposed while the temperature T is systematically quenched from the liquid limit through the glass transition at [Formula: see text] down to very low temperatures. Monodisperse Lennard-Jones (mdLJ) bead systems, forming a crystal phase at low temperatures, are used to highlight several features of the KA2d model. As can be seen, e.g. from the elastic shear modulus G(T), determined using the stress-fluctuation formalism, our KA2d model is a good glass-former. A continuous cusp-singularity, [Formula: see text] with [Formula: see text], is observed in qualitative agreement with other recent numerical and theoretical work, however in striking conflict with the additive jump discontinuity predicted by mode-coupling theory. PMID:26740502

  15. The microscopic basis of the glass transition in polymers from neutron scattering studies.

    PubMed

    Frick, B; Richter, D

    1995-03-31

    Recent neutron scattering experiments on the microscopic dynamics of polymers below and above the glass transition temperature T(g) are reviewed. The results presented cover different dynamic processes appearing in glasses: local motions, vibrations, and different relaxation processes such as alpha- and beta-relaxation. For the alpha-relaxation, which occurs above T(g), it is possible to extend the time-temperature superposition principle, which is valid for polymers on a macroscopic scale, to the microscopic time scale. However, this principle is not applicable for temperatures approaching T(g). Below T(g), an inelastic excitation at a frequency of some hundred gigahertz (on the order of several wave numbers), the "boson peak," survives from a quasi-elastic overdamped scattering law at high temperatures. The connection between this boson peak and the fast dynamic process appearing near T(g) is discussed. PMID:17770103

  16. Aging at the spin-glass/ferromagnet transition: Monte Carlo simulations using graphics processing units

    NASA Astrophysics Data System (ADS)

    Manssen, Markus; Hartmann, Alexander K.

    2015-05-01

    We study the nonequilibrium aging behavior of the ±J Edwards-Anderson model in three dimensions for samples of size up to N =1283 and for up to 108 Monte Carlo sweeps. In particular we are interested in the change of the aging when crossing from the spin-glass phase to the ferromagnetic phase. The necessary long simulation times are reached by employing a CUDA-based GPU implementation, which allows for single-spin flip times as small as 8 ps. We measure typical spin-glass correlation functions in space and time to determine the growing length scale and extract the constituting exponents. We observe a clear signature of the disorder-driven equilibrium transition in the nonequilibrium behavior.

  17. Observation of the transition state for pressure-induced BO₃→ BO₄ conversion in glass.

    PubMed

    Edwards, Trenton; Endo, Takatsugu; Walton, Jeffrey H; Sen, Sabyasachi

    2014-08-29

    A fundamental mechanistic understanding of the pressure- and/or temperature-induced facile transformation of the coordination environment of boron is important for changing the physical properties of glass. We have used in situ high-pressure (up to 2 gigapascals) boron-11 solid-state nuclear magnetic resonance spectroscopy in combination with ab initio calculations to investigate the nature of the transition state for the pressure-induced BO3→ BO4 conversion in a borosilicate glass at ambient temperature. The results indicate an anisotropic elastic deformation of the BO3 planar triangle, under isotropic stress, into a trigonal pyramid that likely serves as a precursor for the subsequent formation of a BO4 tetrahedron. PMID:25170146

  18. Relaxation map of a 100% green thermoplastic film. Glass transition and fragility

    NASA Astrophysics Data System (ADS)

    Saiter, J. M.; Dobircau, L.; Saiah, R.; Sreekumar, P. A.; Galandon, A.; Gattin, R.; Leblanc, N.; Adhikari, R.

    2010-02-01

    A 100% green thermoplastic obtained by extrusion of a mixture of wheat flour and plasticizers has been realized. The existence of two vitreous phases in this 100% green thermoplastic film has been pointed out by means of calorimetric measurements ( T g=-56 °C and T g=10 °C) and confirmed by electron microscopy. The molecular dynamics have been investigated by means of DMA measurements for temperature domains in the vicinity of the glass transition of each phase. We show that each phase exhibits a molecular dynamic characteristic of a fragile glass liquid former. The size of the cooperative domain engaged in the relaxation processes have also been estimated and we show that this new green thermoplastic exhibits relaxation mechanisms as expected for a conventional thermoplastic, as for instance a PMMA.

  19. Combustion characteristics in the transition region of liquid fuel sprays

    NASA Technical Reports Server (NTRS)

    Cernansky, N. P.; Namer, I.; Tidona, R. J.

    1984-01-01

    A number of important effects were observed in the droplet size transition region in spray combustion systems. In this region, where the mechanism of flame propagation is transformed from diffusive to premixed dominated combustion, the following effects have been observed: (1) maxima in burning velocity; (2) extension of flammability limits; (3) minima in ignition energy; and (4) minima in NO(x) formation. Unfortunately, because of differences in experimental facilities and limitations in the ranges of experimental data, a unified description of these transition region effects is not available at this time. Consequently, a fundamental experimental investigation was initiated to study the effect of droplet size, size distribution, and operating parameters on these transition region phenomena in a single well controlled spray combustion facility.

  20. The Impact of Opioid Treatment on Regional Gastrointestinal Transit

    PubMed Central

    Poulsen, Jakob L; Nilsson, Matias; Brock, Christina; Sandberg, Thomas H; Krogh, Klaus; Drewes, Asbjørn M

    2016-01-01

    Background/Aims To employ an experimental model of opioid-induced bowel dysfunction in healthy human volunteers, and evaluate the impact of opioid treatment compared to placebo on gastrointestinal (GI) symptoms and motility assessed by questionnaires and regional GI transit times using the 3-dimensional (3D)-Transit system. Methods Twenty-five healthy males were randomly assigned to oxycodone or placebo for 5 days in a double blind, crossover design. Adverse GI effects were measured with the bowel function index, gastrointestinal symptom rating scale, patient assessment of constipation symptom questionnaire, and Bristol stool form scale. Regional GI transit times were determined using the 3D-Transit system, and segmental transit times in the colon were determined using a custom Matlab® graphical user interface. Results GI symptom scores increased significantly across all applied GI questionnaires during opioid treatment. Oxycodone increased median total GI transit time from 22.2 to 43.9 hours (P < 0.001), segmental transit times in the cecum and ascending colon from 5.7 to 9.9 hours (P = 0.012), rectosigmoid colon transit from 2.7 to 9.0 hours (P = 0.044), and colorectal transit time from 18.6 to 38.6 hours (P = 0.001). No associations between questionnaire scores and segmental transit times were detected. Conclusions Self-assessed GI adverse effects and increased GI transit times in different segments were induced during oxycodone treatment. This detailed information about segmental changes in motility has great potential for future interventional head-to-head trials of different laxative regimes for prevention and treatment of constipation. PMID:26811503

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

    SciTech Connect

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

    1998-12-31

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

  2. Spin-glass phase transitions and minimum energy of the random feedback vertex set problem.

    PubMed

    Qin, Shao-Meng; Zeng, Ying; Zhou, Hai-Jun

    2016-08-01

    A feedback vertex set (FVS) of an undirected graph contains vertices from every cycle of this graph. Constructing a FVS of sufficiently small cardinality is very difficult in the worst cases, but for random graphs this problem can be efficiently solved by converting it into an appropriate spin-glass model [H.-J. Zhou, Eur. Phys. J. B 86, 455 (2013)EPJBFY1434-602810.1140/epjb/e2013-40690-1]. In the present work we study the spin-glass phase transitions and the minimum energy density of the random FVS problem by the first-step replica-symmetry-breaking (1RSB) mean-field theory. For both regular random graphs and Erdös-Rényi graphs, we determine the inverse temperature β_{l} at which the replica-symmetric mean-field theory loses its local stability, the inverse temperature β_{d} of the dynamical (clustering) phase transition, and the inverse temperature β_{s} of the static (condensation) phase transition. These critical inverse temperatures all change with the mean vertex degree in a nonmonotonic way, and β_{d} is distinct from β_{s} for regular random graphs of vertex degrees K>60, while β_{d} are identical to β_{s} for Erdös-Rényi graphs at least up to mean vertex degree c=512. We then derive the zero-temperature limit of the 1RSB theory and use it to compute the minimum FVS cardinality. PMID:27627285

  3. Gelation and glass transition of particles with short-range attraction induced by adsorbing microgel

    NASA Astrophysics Data System (ADS)

    Yuan, Guangcui; Luo, Junhua; Han, Charles C.

    2015-03-01

    Mixed suspensions of large hard polystyrene microsphere and small poly(N-isopropylacrylamide) microgel is used as model systems to investigate the static and viscoelastic properties of suspensions which go through liquid to gel and to glass transitions. The microgels cause short-range attraction between microspheres through bridging and depletion mechanism whose strength can be tuned by the microgel concentration. Baxter's sticky hard-sphere model is used to extract the effective inter-microsphere interaction introduced by bridging or depletion of microgels despite the fact that the physical mechanisms of bridging attraction and depletion attraction are different at a molecular level. A new state diagram of gelation and even of glass transition was constructed by taking the bridges as a short-ranged attractive interaction With the help of the well-defined bridging bonds, some controversies regarding to the interference between two origins for ergodic to\\ non-ergodic transition in condensed system, i.e. cage effect and bond effect, were clarified. This work is supported by the National Basic Research Program of China (973 Program, 2012CB821503).

  4. 93 Nb NMR investigation of vortex- glass transition in layered NbSe2

    NASA Astrophysics Data System (ADS)

    Wilson, Douglas; Saraswat, Garima; Shirage, Parasharam; Kuhns, Philip; Hoch, Michael J. R.; Reyes, Arneil

    We report a detailed low temperature investigation of vortex glass transition in layered superconducting compound NbSe2 using 93Nb NMR at fields below Hc2. Preliminary measurements show that spin-lattice relaxation rate 1/T1 demonstrates a classic Korringa behavior 1/T1~ T above the superconducting transition Tc , consistent with previous measurements on this compound. However, for field H perpendicular to the layers, we observed that 1/T1 exhibits an anomalous plateau between Tc (H = 0) and Tc (H) and a suppression of the superconducting enhancement expected below Tc. Instead, a power law behavior, 1/T1 ~T 1 . 2 below Tc down to 360mK was observed which suggests a strong anisotropy in the low energy excitations. However, the possibility of enhancement in 1/T1 due to vortex fluctuations which competes with electronic mechanisms cannot be excluded. The implications of these results with regards to vortex-glass transition will be discussed. This work was performed at the National High Magnetic Field Laboratory, which is supported by NSF DMR-1157490 and the State of Florida.

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

    NASA Astrophysics Data System (ADS)

    Zhang, W.; Mi, J.

    2016-03-01

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

  6. Condensation of Si-rich region inside soda-lime glass by parallel femtosecond laser irradiation.

    PubMed

    Sakakura, Masaaki; Yoshimura, Kouhei; Kurita, Torataro; Shimizu, Masahiro; Shimotsuma, Yasuhiko; Fukuda, Naoaki; Hirao, Kazuyuki; Miura, Kiyotaka

    2014-06-30

    Local melting and modulation of elemental distributions can be induced inside a glass by focusing femtosecond (fs) laser pulses at high repetition rate (>100 kHz). Using only a single beam of fs laser pulses, the shape of the molten region is ellipsoidal, so the induced elemental distributions are often circular and elongate in the laser propagation direction. In this study, we show that the elongation of the fs laser-induced elemental distributions inside a soda-lime glass could be suppressed by parallel fsing of 250 kHz and 1 kHz fs laser pulses. The thickness of a Si-rich region became about twice thinner than that of a single 250 kHz laser irradiation. Interestingly, the position of the Si-rich region depended on the relative positions between 1 kHz and 250 kHz photoexcited regions. The observation of glass melt during laser exposure showed that the vortex flow of glass melt occurred and it induced the formation of a Si-rich region. Based on the simulation of the transient temperature and viscosity distributions during laser exposure, we temporally interpreted the origin of the vortex flow of glass melt and the mechanism of the formation of the Si-rich region. PMID:24977898

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

    NASA Astrophysics Data System (ADS)

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

    2016-05-01

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

  8. Deviations of the glass transition temperature in amorphous conjugated polymer thin films

    NASA Astrophysics Data System (ADS)

    Liu, Dan; Osuna Orozco, Rodrigo; Wang, Tao

    2013-08-01

    The deviations of the glass transition temperature (Tg) in thin films of an amorphous conjugated polymer poly(9,9-dioctylfluorene-co-N-(4-butylphenyl)diphenylamine) (TFB) are reported. Monotonic and nonmonotonic Tg deviations are observed in TFB thin films supported on Si-SiOx and poly(3,4-ethylenedioxythiophene) poly(styrenesulfonate) (PEDOT:PSS), respectively. A three-layer model is developed to fit both monotonic and nonmonotonic Tg deviations in these films. A 5-nm PEDOT:PSS capping layer was not found to be effective to remove the free-surface effect in Si-SiOx supported TFB films.

  9. Dielectric study of the glass transition of PET/PEN blends

    NASA Astrophysics Data System (ADS)

    Sellarès, J.; Diego, J. A.; Cañadas, J. C.; Mudarra, M.; Belana, J.; Colomer, P.; Román, F.; Calventus, Y.

    2012-12-01

    An analysis of the glass transition of four materials with similar chemical structures is performed: PET, PEN and two PET/PEN blends (90/10 and 70/30 w/w). During the melt processing of the blends transesterification reactions yield block and random PET/PEN copolymers that act as compatibilizers. The blends obtained in this way have been characterized by 1H-NMR and differential scan calorimetry (DSC). A degree of randomness of 0.38 and 0.26 has been found for the 90/10 and 70/30 copolymers. It is shown by DSC that this copolimerization is enough to compatibilize the blends. The α relaxation, the dielectric manifestation of the glass transition, has been studied by thermally stimulated depolarization currents. The relaxation has been analysed into its elementary modes by means of a relaxation map analysis. The activation energies of the modes of the glass transition do not change significantly between the four materials: in all cases the modes with a larger contribution have around 3 eV and modes with less than 1 eV are not detected. The change in the pre-exponential factor accounts entirely for the relaxation time change from material to material, that is larger as the PEN content increases. The compensation law is fulfilled and compensation plots converge for high-frequency modes. The polarizability decreases as the PEN content increases due to the increased stiffness of the polymer backbone. An analysis of the cooperativity shows that the central modes of the distribution are the most cooperative while high-frequency modes tend to behave more as Arrhenius. The low-frequency modes are difficult to study due to the asymmetry of the distribution of relaxation times. PEN turns out to be the less cooperative material. It is demonstrated how the parameters obtained from the dielectric study are able to reproduce calorimetric data from DSC scans and are, therefore, a valid description of the glass transition.

  10. Glass transition temperature of water confined in lipid membranes as determined by anelastic spectroscopy

    NASA Astrophysics Data System (ADS)

    Castellano, C.; Generosi, J.; Congiu, A.; Cantelli, R.

    2006-12-01

    The research of gene delivery vehicles used in gene therapy is focused on nonviral vectors like lipid membranes. Such vectors, nonimmunogenic and biodegradable, are formed by complexation of DNA with a mixture of cationic lipids and a neutral colipid which improve the transfection efficiency. A main topic related to lipid membrane dynamics is their capability to spontaneously confine water. At present the value of the glass transition temperature (Tg) is largely debated and determined only by some indirect methods. Here the authors show that anelastic spectroscopy allows the confined water Tg value to be directly identified in several lipid mixtures.

  11. Frustration of photocrystallization in amorphous selenium films and film-polymer structures near the glass transition

    NASA Astrophysics Data System (ADS)

    Lindberg, G. P.; Tallman, R. E.; Abbaszadeh, S.; Karim, K. S.; Rowlands, J. A.; Reznik, A.; Weinstein, B. A.

    2013-12-01

    We investigate the stability against photo-induced crystallization (PiC) and photo-induced darkening (PiD) in a series of amorphous selenium (a-Se) films grown with and without polyimide buffer layers[1] for temperatures below and above the glass transition (Tg ˜ 313 K). The a-Se films are bulk-like (˜16.5 μm thick), and contain a low concentration of As (< 0.2%). We find that due to strain relief, a thin layer (˜1 μm) of polyimide greatly stabilizes the samples against PiC and reduces the effect of PiD.

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

    SciTech Connect

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

    1989-01-01

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

  13. Ductile to brittle transition in dynamic fracture of brittle bulk metallic glass

    SciTech Connect

    Wang, G.; Han, Y. N.; Han, B. S.; Wang, W. H.; Xu, X. H.; Ke, F. J.

    2008-05-01

    We report an unusual transition from a locally ductile to a pure brittle fracture in the dynamic fracture of brittle Mg{sub 65}Cu{sub 20}Gd{sub 10} bulk metallic glass. The fractographic evolution from a dimple structure to a periodic corrugation pattern and then to the mirror zone along the crack propagation direction during the dynamic fracture process is discussed within the framework of the meniscus instability of the fracture process zone. This work might provide an important clue in understanding of the energy dissipation mechanism for dynamic crack propagation in brittle glassy materials.

  14. Glass-transition temperature gradient in nanocomposites: evidence from nuclear magnetic resonance and differential scanning calorimetry.

    PubMed

    Papon, Aurélie; Montes, Hélène; Hanafi, Mohamed; Lequeux, François; Guy, Laurent; Saalwächter, Kay

    2012-02-10

    The slowing-down of the dynamics of a polymer chain near a surface has been observed for many years now. Here we show that the behavior of model nanocomposites can be quantitatively described with a gradient of glass-transition temperature. We describe with a single parameter-the range of this gradient-the temperature and solvent effect on the spin relaxation dynamics. Moreover, this parameter allows a quantitative description of the nanocomposite calorimetric response from the one of the bulk polymer. PMID:22401088

  15. A phenomenological molecular model for yielding and brittle-ductile transition of polymer glasses

    NASA Astrophysics Data System (ADS)

    Wang, Shi-Qing; Cheng, Shiwang; Lin, Panpan; Li, Xiaoxiao

    2014-09-01

    This work formulates, at a molecular level, a phenomenological theoretical description of the brittle-ductile transition (BDT) in tensile extension, exhibited by all polymeric glasses of high molecular weight (MW). The starting point is our perception of a polymer glass (under large deformation) as a structural hybrid, consisting of a primary structure due to the van der Waals bonding and a chain network whose junctions are made of pairs of hairpins and function like chemical crosslinks due to the intermolecular uncrossability. During extension, load-bearing strands (LBSs) emerge between the junctions in the affinely strained chain network. Above the BDT, i.e., at "warmer" temperatures where the glass is less vitreous, the influence of the chain network reaches out everywhere by activating all segments populated transversely between LBSs, starting from those adjacent to LBSs. It is the chain network that drives the primary structure to undergo yielding and plastic flow. Below the BDT, the glassy state is too vitreous to yield before the chain network suffers a structural breakdown. Thus, brittle failure becomes inevitable. For any given polymer glass of high MW, there is one temperature TBD or a very narrow range of temperature where the yielding of the glass barely takes place as the chain network also reaches the point of a structural failure. This is the point of the BDT. A theoretical analysis of the available experimental data reveals that (a) chain pullout occurs at the BDT when the chain tension builds up to reach a critical value fcp during tensile extension; (b) the limiting value of fcp, extrapolated to far below the glass transition temperature Tg, is of a universal magnitude around 0.2-0.3 nN, for all eight polymers examined in this work; (c) pressurization, which is known [K. Matsushige, S. V. Radcliffe, and E. Baer, J. Appl. Polym. Sci. 20, 1853 (1976)] to make brittle polystyrene (PS) and poly(methyl methacrylate) (PMMA) ductile at room temperature

  16. Transition-metal ions in Nd-doped glasses: spectra and effects on Nd fluorescence

    SciTech Connect

    Stokowski, S.E.; Krashkevich, D.

    1985-12-19

    We have measured transition-metal ion (Ti, V, Cr, Mn, Fe, Co, Ni, Cu) spectra and their effects on Nd fluorescence quenching in Nd-doped phosphate and silicate glasses. Our purpose was to determine the maximum allowable impurity content given particular limits on the absorption loss at 1053 nm and the Nd fluorescence quenching rate. To keep the absorption loss <0.1 m/sup -1/ the transition-metal impurity content should be kept below 0.5 ppMw. To keep the increase in the Nd fluorescence decay rate below 1%, the impurity content should be <3 ppMw. We have also found that the Nd quenching rates do not scale as predicted by the Forster-Dexter dipole-dipole energy transfer theory if we assume that the dominant variation with transition metal is the overlap integral of the Nd fluorescence spectrum and the transition-metal absorption. We suggest that phonon-assisted energy transfer to transition metals is effective in quenching Nd. We find that quenching rates increase 1.5 to 4 times as the Nd concentration increases from 0.5 to 10 x 10/sup 20/ cm/sup -3/.

  17. Glass transition in the quenched and annealed version of the frustrated lattice gas model

    NASA Astrophysics Data System (ADS)

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

    2000-12-01

    In this paper we study the three-dimensional frustrated lattice gas model in the annealed version, where the disorder is allowed to evolve in time with a suitable kinetic constraint. Although the model does not exhibit any thermodynamic transition it shows a diverging peak at some characteristic time in the dynamical nonlinear susceptibility, similar to the results on the p-spin model in mean field and the Lennard-Jones mixture recently found by Donati et al. (e-print cond-mat/9905433). Comparing these results to those obtained in the model with quenched interactions, we conclude that the critical behavior of the dynamical susceptibility is reminiscent of the thermodynamic transition present in the quenched model, and signaled by the divergence of the static nonlinear susceptibility, suggesting therefore a similar mechanism also in supercooled glass-forming liquids.

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

    NASA Astrophysics Data System (ADS)

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

    2004-02-01

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

  19. The thermal structure of the magnetized solar transition region

    NASA Technical Reports Server (NTRS)

    Mok, Y.; Van Hoven, G.

    1993-01-01

    The detailed thermal structure of the magnetized solar transition region, as measured by its differential emission measure DEM(T), is unknown. Proposals have been made that envision a significant lower-temperature contribution to the energy balance from cross-field (ion) heat flux. In this paper, we describe a self-consistent 2D MHD simulation (including the full effects of anisotropic thermal conduction) of a conceptual model due to Athay (1990). We display the detailed irregular thermal and magnetic structure of the transition region and demonstrate that the predicted DEM agrees with observations, particularly in the T less than 10 exp 5 K regime where previous theories had difficulty.

  20. Radiative Transfer and Absorbing Structures in the Transition Region

    NASA Astrophysics Data System (ADS)

    Plovanic, Jacob; Kankelborg, C. C.

    2012-05-01

    A fully satisfactory explanation for the anomalous He II 304 Å intensity in the solar transition region has yet to be offered. As an extension of previous work, we use a full radiative transfer code to build a more consistent model of the transition region that allows the He II line to form with low filling factor and low opacity. Our results are constrained by the quiet sun center-to-limb profile of He II 304 Å obtained from the MOSES sounding rocket mission and by AIA full-disk data.

  1. A study of the glass transition in the amorphous interlamellar phase of highly crystallized poly(ethylene terephthalate)

    NASA Astrophysics Data System (ADS)

    Sellarès, J.; Diego, J. A.; Belana, J.

    2010-09-01

    The glass transition of poly(ethylene terephthalate) (PET) crystallized for 4 h at temperatures between 413 and 453 K was studied. Secondary crystallization processes were monitored by differential scanning calorimetry and the glass transition of the remaining interlamellar amorphous phase was studied by thermally stimulated depolarization currents measurements. Non-isothermal window polarization is employed to resolve the relaxation in modes with a well-defined relaxation time that is subsequently adjusted to several standard models. An analysis of experimental results reveals that cooperativity can be disregarded in the modelization of data. The evolution of modes during secondary crystallization, once primary crystallization has been completed, gives more weight to lower energy modes. As a consequence, secondary crystallization tends to lower the glass transition temperature of the amorphous interlamellar phase, although remaining noticeably higher than in amorphous samples. The evolution of calorimetric scans of the glass transition is simulated from the obtained results and shows the same behaviour. Regarding the glass transition temperature of the material, it can be concluded that primary and secondary crystallization act in opposite directions even though the effect of secondary crystallization is much smaller. The interpretation of these results in terms of current views about secondary crystallization is discussed.

  2. Temperature-Modulated Ellipsometry in Vacuum: A New Tool for Probing Glass Transition in Thin Supported Polymer Films

    NASA Astrophysics Data System (ADS)

    Efremov, Mikhail; Soofi, Shauheen; Kiyanova, Anna; Cerrina, Franco; Nealey, Paul

    2009-03-01

    Observation of glass transition in thin polymer films is a good example of experimental challenges that measurements at the nanoscale may present. The standard technique in the field, ellipsometry, has been advanced by state-of-the-art approaches: measurements in vacuum and temperature modulation. Glass transition in 5 -- 200 nm thick spin-cast polystyrene (PS) and poly(methyl methacrylate) (PMMA) films on silicon has been studied at 10-6 -- 10-8 torr residual gas pressure, using both linear and modulated temperature scans [1, 2]. A well-defined glass transition in 5 nm thick PS and 10 nm thick PMMA films is observed. Factors that can alter glass transition temperature assignment will be discussed. Residual gas can affect data even at the pressures mentioned above [1]. An ionization gauge, the standard vacuum equipment, causes sample deterioration [1]. Temperature modulation effectively separates reversible glass transition from accompanying irreversible processes [2]. [1]. M. Yu. Efremov, S. S. Soofi, A. V. Kiyanova, C. J. Munoz, P. Burgardt, F. Cerrina, and P. F. Nealey, Rev. Sci. Instr., 79, 043903 (2008). [2]. M. Yu. Efremov, A. V. Kiyanova, and P. F. Nealey, Macromolecules, 41, 5978 (2008).

  3. Impact of caramelization on the glass transition temperature of several caramelized sugars. Part I: Chemical analyses.

    PubMed

    Jiang, Bin; Liu, Yeting; Bhandari, Bhesh; Zhou, Weibiao

    2008-07-01

    This study aims to investigate the relationship between caramelization of several sugars including fructose, glucose, and sucrose and their glass transition temperature (Tg). Differential scanning calorimetry (DSC) was used for creating caramelized sugar samples as well as determining their glass transition temperature, which was found to decrease first and then increase as the holding time at the highest temperature increased. The extent of caramelization was quantified by UV-vis absorbance measurement and high-performance liquid chromatography analysis. Results showed that the amount of small molecules from the degradation of sugar increased very fast at the beginning of heating, and this increase slowed down in the later stage of caramelization. On the other hand, there was a lag phase in the formation of large molecules from the degradation of sugar at the beginning of heating, followed by a fast increase in the later stage of caramelization. The obtained results clearly indicate the impact of melting condition on the T g of sugars through formation of intermediates and end products of caramelization. Generally, when the heating condition is relatively mild, small molecules are formed first by decomposition of the sugar, which leads to a decrease of the overall Tg, and as the heating time becomes longer and/or the heating condition becomes more severe, polymerization takes over and more large molecules are formed, which results in an increase of the overall Tg. Mathematical modeling of the relationship will be presented as part II of the study in a separate paper. PMID:18553889

  4. Determination of Material Properties Near the Glass Transition Temperature for an Isogrid Boom

    NASA Technical Reports Server (NTRS)

    Blandino, Joseph R.; Woods-Vedeler, Jessica A. (Technical Monitor)

    2002-01-01

    Experiments were performed and results obtained to determine the temperature dependence of the modulus of elasticity for a thermoplastic isogrid tube. The isogrid tube was subjected to axial tensile loads of 0-100 lbf and strain was measured at room and elevated temperatures of 100, 120, 140, 160, 180, 190, and 200 F. These were based on tube manufacturer specifying an incorrect glass transition temperature of 210 F. Two protocols were used. For the first protocol the tube was brought to temperature and a tensile test performed. The tube was allowed to cool between tests. For the second protocol the tube was ramped to the desired test temperature and held. A tensile test was performed and the tube temperature ramped to the next test temperature. The second protocol spanned the entire test range. The strain rate was constant at 0.008 in/min. Room temperature tests resulted in the determination of an average modulus of 2.34 x 106 Psi. The modulus decreased above 100 F. At 140 F the modulus had decreased by 7.26%. The two test protocols showed good agreement below 160 F. At this point the glass transition temperature had been exceeded. The two protocols were not repeated because the tube failed.

  5. Glass Transition Temperature of Polyetherimide: Relationship between Thin Films and Nanoporous Materials

    NASA Astrophysics Data System (ADS)

    Ozisik, Rahmi; Liu, Tong; Siegel, Richard W.

    2006-03-01

    The glass transition temperature (Tg) of nanoporous polyetherimide (PEI) was investigated using differential scanning calorimetry. Nanosized pores were created by spin coating a solution of PEI and polycaprolactone-diol (PCLD) in their common solvent dichloromethane. The nanoporous structure was created by fast phase separation during spin coating and subsequent removal of PCLD with acetone. Atomic force microscopy, scanning electron microscopy and statistical methods were used to characterize the pore structure. The glass transition temperatures of both the thin PEI films and nanoporous PEI samples were lower than that of bulk PEI. The Tg of nanoporous PEI was found to depend strongly on pore volume fraction. A Monte Carlo simulation was performed to investigate the relationship between thin films and nanoporous systems. The distribution of nearest neighbor distances (h) were obtained from the Monte Carlo simulation, which was biased to create the pore size distribution obtained from experiments. Various moments of h was calculated and used to compare the findings to thin film data.

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

    PubMed

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

    2016-05-15

    The effect of calcium chloride on the structural properties of condensed potato starch undergoing a thermally induced glass transition has been studied using dynamic mechanical analysis and modulated differential scanning calorimetry. Extensive starch gelatinisation was obtained by hot pressing at 120°C for 7 min producing materials that covered a range of moisture contents from 3.7% w/w (11% relative humidity) to 18.8% w/w (75% relative humidity). FTIR, ESEM and WAXD were also performed in order to elucidate the manner by which salt addition affects the molecular interactions and morphology of condensed starch. Experimental protocol ensured the development of amorphous matrices that exhibited thermally reversible glassy consistency. Both moisture content and addition of calcium chloride affected the mechanical strength and glass transition temperature of polymeric systems. Highly reactive calcium ions form a direct interaction with starch to alter considerably its structural properties via an anti-plasticizing effect, as compared to the polymer-water matrix. PMID:26776036

  7. Structure and dynamical intra-molecular heterogeneity of star polymer melts above glass transition temperature.

    PubMed

    Chremos, Alexandros; Glynos, Emmanouil; Green, Peter F

    2015-01-28

    Structural and dynamical properties of star melts have been investigated with molecular dynamics simulations of a bead-spring model. Star polymers are known to be heterogeneous, but a systematic simulation study of their properties in melt conditions near the glass transition temperature was lacking. To probe their properties, we have expanded from linear to star polymers the applicability of Dobkowski's chain-length dependence correlation function [Z. Dobkowski, Eur. Polym. J. 18, 563 (1982)]. The density and the isokinetic temperature, based on the canonical definition of the laboratory glass-transition, can be described well by the correlation function and a subtle behavior manifests as the architecture becomes more complex. For linear polymer chains and low functionality star polymers, we find that an increase of the arm length would result in an increase of the density and the isokinetic temperature, but high functionality star polymers have the opposite behavior. The effect between low and high functionalities is more pronounced for short arm lengths. Complementary results such as the specific volume and number of neighbors in contact provide further insights on the subtle relation between structure and dynamics. The findings would be valuable to polymer, colloidal, and nanocomposites fields for the design of materials in absence of solution with the desired properties. PMID:25638003

  8. Glass transitions in native silk fibres studied by dynamic mechanical thermal analysis.

    PubMed

    Guan, Juan; Wang, Yu; Mortimer, Beth; Holland, Chris; Shao, Zhengzhong; Porter, David; Vollrath, Fritz

    2016-07-01

    Silks are a family of semi-crystalline structural materials, spun naturally by insects, spiders and even crustaceans. Compared to the characteristic β-sheet crystalline structure in silks, the non-crystalline structure and its composition deserves more attention as it is equally critical to the filaments' high toughness and strength. Here we further unravel the structure-property relationship in silks using Dynamic Mechanical Thermal Analysis (DMTA). This technique allows us to examine the most important structural relaxation event of the disordered structure the disordered structure, the glass transition (GT), in native silk fibres of the lepidopteran Bombyx mori and Antheraea pernyi and the spider Nephila edulis. The measured glass transition temperature Tg, loss tangent tan δ and dynamic storage modulus are quantitatively modelled based on Group Interaction Modelling (GIM). The "variability" issue in native silks can be conveniently explained by the different degrees of structural disorder as revealed by DMTA. The new insights will facilitate a more comprehensive understanding of the structure-property relations for a wide range of biopolymers. PMID:27320178

  9. Impact of caramelization on the glass transition temperature of several caramelized sugars. Part II: Mathematical modeling.

    PubMed

    Jiang, Bin; Liu, Yeting; Bhandari, Bhesh; Zhou, Weibiao

    2008-07-01

    Further to part I of this study, this paper discusses mathematical modeling of the relationship between caramelization of several sugars including fructose, glucose, and sucrose and their glass transition temperatures ( T g). Differential scanning calorimetry (DSC) was used for creating caramelized sugar samples and determining their glass transition temperatures ( T g). UV-vis absorbance measurement and high-performance liquid chromatography (HPLC) analysis were used for quantifying the extent of caramelization. Specifically, absorbances at 284 and 420 nm were obtained from UV-vis measurement, and the contents of sucrose, glucose, fructose, and 5-hydroxymethyl-furfural (HMF) in the caramelized sugars were obtained from HPLC measurements. Results from the UV and HPLC measurements were correlated with the Tg values measured by DSC. By using both linear and nonlinear regressions, two sets of mathematical models were developed for the prediction of Tg values of sugar caramels. The first set utilized information obtained from both UV-vis measurement and HPLC analysis, while the second set utilized only information from the UV-vis measurement, which is much easier to perform in practice. As a caramelization process is typically characterized by two stages, separate models were developed for each of the stages within a set. Furthermore, a third set of nonlinear equations were developed, serving as criteria to decide at which stage a caramelized sample is. The models were evaluated through a validation process. PMID:18553880

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

    NASA Astrophysics Data System (ADS)

    Thiruvengadam, V.; Vitta, Satish

    2016-06-01

    The interparticle interactions in the magnetic nanocomposites play a dominant role in controlling phase transitions: superparamagnetic to superspin glass and to superferromagnetic. These interactions can be tuned by controlling the size and number density of nanoparticles. The aerogel composites, 0.3Ni-BC and 0.7Ni-BC, consisting of Ni nanoparticles distributed in the bacterial cellulose have been used as a model system to study these interactions. Contrary to conventional approach, size of Ni-nanoparticles is not controlled and allowed to form naturally in bacterial cellulose template. The uncontrolled growth of Ni results in the formation of nanoparticles with 3 different size distributions - <10 nm particles along the length of fibrils, 50 nm particles in the intermediate spaces between the fibrils, and >100 nm particles in voids formed by reticulate structure. At room temperature, the composites exhibit a weakly ferromagnetic behaviour with a coercivity of 40 Oe, which increases to 160 Oe at 10 K. The transition from weakly ferromagnetic state to superferromagnetic state at low temperatures is mediated by the superspin glass state at intermediate temperatures via the interparticle interactions aided by nanoparticles present along the length of fibres. A temperature dependent microstructural model has been developed to understand the magnetic behaviour of nanocomposite aerogels.

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

    NASA Astrophysics Data System (ADS)

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

    2012-03-01

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

  12. Glass Transition and Molecular Mobility in Styrene-Butadiene Rubber Modified Asphalt.

    PubMed

    Khabaz, Fardin; Khare, Rajesh

    2015-11-01

    Asphalt, a soft matter consisting of more than a thousand chemical species, is of vital importance for the transportation infrastructure, yet it poses significant challenges for microscopic theory and modeling approaches due to its multicomponent nature. Polymeric additives can potentially enhance the thermo-mechanical properties of asphalt, thus helping reduce the road repair costs; rational design of such systems requires knowledge of the molecular structure and dynamics of these systems. We have used molecular dynamics (MD) simulations to investigate the volumetric, structural, and dynamic properties of the neat asphalt as well as styrene-butadiene rubber (SBR) modified asphalt systems. The volume-temperature behavior of the asphalt systems exhibited a glass transition phenomenon, akin to that observed in experiments. The glass transition temperature, room temperature density, and coefficient of volume thermal expansion of the neat asphalt systems so evaluated were in agreement with experimental data when the effect of the high cooling rate used in simulations was accounted for. While the volumetric properties of SBR modified asphalt were found to be insensitive to the presence of the SBR additive, the addition of SBR led to an increase in the aggregation of asphaltene molecules. Furthermore, addition of SBR caused a reduction in the mobility of the constituent molecules of asphalt, with the reduction being more significant for the larger constituent molecules. Similar to other glass forming liquids, the reciprocal of the diffusion coefficient of the selected molecules was observed to follow the Vogel-Fulcher-Tammann (VFT) behavior as a function of temperature. These results suggest the potential for using polymeric additives for enhancing the dynamic mechanical properties of asphalt without affecting its volumetric properties. PMID:26451630

  13. Spectral studies of erbium doped soda lime silicate glasses in visible and near infrared regions

    NASA Astrophysics Data System (ADS)

    Sharma, Y. K.; Surana, S. S. L.; Singh, R. K.; Dubedi, R. P.

    2007-02-01

    Optical absorption and photoluminescence spectra of Er 3+ doped soda lime silicate glasses of the composition (in wt.%) 68.94SiO 2-22.55Na 2O-1.91CaO-4.96K 2O-0.85B 2O 3-0.29As 2O 3- xEr 2O 3 where x = 0.0, 0.2, 0.3 and 0.5 have been studied in the UV-VIS/NIR regions. From the measured intensities of the various absorption bands of these glasses, the Judd-Ofelt parameters Ω2, Ω4 and Ω6 have been evaluated. Judd-Ofelt theory has been successfully applied to characterize the absorption and luminescence spectra of these glasses. From this theory various radiative properties like spontaneous emission probability, radiative life time, fluorescence branching ratio and stimulated emission cross-section for various emission bands of these glasses in the visible and NIR spectral regions have been determined and reported. An attempt has been made to through some light on the environment of Er 3+ in this glass system. Radiative properties of fluorescence band at ˜1.54 μm suggest the suitability of this glass system for broadband amplifier in the third telecom window.

  14. Excess of low frequency vibrational modes and glass transition: A molecular dynamics study for soft spheres at constant pressure

    NASA Astrophysics Data System (ADS)

    Flores-Ruiz, Hugo M.; Naumis, Gerardo G.

    2009-10-01

    Using molecular dynamics at constant pressure, the relationship between the excess of low frequency vibrational modes (known as the boson peak) and the glass transition is investigated for a truncated Lennard-Jones potential. It is observed that the quadratic mean displacement is enhanced by such modes, as predicted using a harmonic Hamiltonian for metastable states. As a result, glasses loose mechanical stability at lower temperatures than the corresponding crystal, since the Lindemann criteria are observed, as is also deduced from density functional theory. Finally, we found that the average force and elastic constant are reduced in the glass due to such excess of modes. The ratio between average elastic constants can be approximated using the 2/3 rule between melting and glass transition temperatures.

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

    PubMed Central

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

    2015-01-01

    Liquid-liquid transition of water is an important concept in condensed-matter physics. Recently, it was claimed to have been confirmed in aqueous solutions based on annealing-induced upshift of glass-liquid transition temperature, . Here we report a universal water-content, , dependence of for aqueous solutions. Solutions with vitrify/devitrify at a constant temperature, , referring to freeze-concentrated phase with left behind ice crystallization. Those solutions with totally vitrify at under conventional cooling/heating process though, of the samples annealed at temperatures   to effectively evoke ice recrystallization is stabilized at . Experiments on aqueous glycerol and 1,2,4-butanetriol solutions in literature were repeated, and the same samples subject to other annealing treatments equally reproduce the result. The upshift of by annealing is attributable to freeze-concentrated phase of solutions instead of ‘liquid II phase of water’. Our work also provides a reliable method to determine hydration formula and to scrutinize solute-solvent interaction in solution. PMID:26503911

  16. Behavior of the low-frequency conductivity of silver iodide nanocomposites in the superionic phase transition region

    NASA Astrophysics Data System (ADS)

    Vergent'ev, T. Yu.; Koroleva, E. Yu.; Kurdyukov, D. A.; Naberezhnov, A. A.; Filimonov, A. V.

    2013-01-01

    The behavior of the specific conductivity of composites based on silver iodide embedded in porous glasses with an average pore diameter of 7 ± 1 nm and in artificial opals with a pore diameter of 40-100 nm has been investigated in the temperature range from 300 to 500 K. It has been shown that a decrease in the characteristic pore size does not lead to a change in the order of the phase transition and that the temperature of the transition to the superionic state of silver iodide in a porous glass and in an opal upon heating is close to the phase transition temperature T c in the bulk material (˜420 K). Upon cooling, the phase transition temperature T c significantly decreases, and the phase transition becomes diffuse. With a decrease in the pore size, the region of the temperature hysteresis of the phase transition increases. The dc conductivities of the composites have been estimated from the impedance diagrams. The temperature dependence of the dc conductivity of both composites has a thermally activated nature, and the slope of the curve σ(1/ T) changes near the phase transition, which indicates a change in the activation energy. The activation energies in the low-temperature and high-temperature phases have been estimated at ˜450-470 and ˜100 meV, respectively. The equivalent electrical circuit describing the charge transfer processes in the studied samples has been proposed.

  17. The Complex North Transition Region of Centaurus A: Radio Structure

    NASA Astrophysics Data System (ADS)

    Neff, Susan G.; Eilek, Jean A.; Owen, Frazer N.

    2015-04-01

    We present deep radio images of the inner ~50 kpc of Centaurus A, taken with the Karl G. Jansky Very Large Array at 90 cm. We focus on the Transition Regions between the inner galaxy—including the active nucleus, inner radio lobes, and star-forming disk—and the outer radio lobes. We detect previously unknown extended emission around the Inner Lobes, including radio emission from the star-forming disk. We find that the radio-loud part of the North Transition Region (NTR), known as the North Middle Lobe, is significantly overpressured relative to the surrounding interstellar medium. We see no evidence for a collimated flow from the active galactic nucleus through this region. Our images show that the structure identified by Morganti et al. as a possible large-scale jet appears to be part of a narrow ridge of emission within the broader, diffuse, radio-loud region. This knotty radio ridge is coincident with other striking phenomena: compact X-ray knots, ionized gas filaments, and streams of young stars. Several short-lived phenomena in the NTR, as well as the frequent re-energization required by the Outer Lobes, suggest that energy must be flowing through both Transition Regions at the present epoch. We suggest that the energy flow is in the form of a galactic wind.

  18. Kr II transition probability measurements for the UV spectral region

    NASA Astrophysics Data System (ADS)

    Belmonte, M. T.; Gavanski, L.; Peláez, R. J.; Aparicio, J. A.; Djurović, S.; Mar, S.

    2016-02-01

    The determination of radiative transition probabilities or oscillator strengths is of common interest in astrophysics. The analysis of the high-resolution stellar spectra is now available in order to estimate the stellar abundances. In this paper, 93 experimentally obtained transition probability values (Aki) for singly ionized krypton spectral lines belonging to the ultraviolet (UV) wavelength region (208-360) nm are presented. These data, expressed in absolute units, were derived from the measurements of relative spectral line intensities and the values of transition probability data taken from the literature. The results obtained extend considerably the transition probability data base. As a light source, a plasma from a low-pressure pulsed arc was used. Its electron density was in the range of (1.5-3.4) × 1022 m-3, while the temperature was between 28 000 and 35 000 K. A detailed analysis of the results is also given. Only a few relative and a few absolute transition probabilities from other authors, for the mentioned spectral region, are available in the literature.

  19. Estimating the Chromospheric Absorption of Transition Region Moss Emission

    NASA Astrophysics Data System (ADS)

    De Pontieu, Bart; Hansteen, Viggo H.; McIntosh, Scott W.; Patsourakos, Spiros

    2009-09-01

    Many models for coronal loops have difficulty explaining the observed EUV brightness of the transition region, which is often significantly less than theoretical models predict. This discrepancy has been addressed by a variety of approaches including filling factors and time-dependent heating, with varying degrees of success. Here, we focus on an effect that has been ignored so far: the absorption of EUV light with wavelengths below 912 Å by the resonance continua of neutral hydrogen and helium. Such absorption is expected to occur in the low-lying transition region of hot, active region loops that is colocated with cool chromospheric features and called "moss" as a result of the reticulated appearance resulting from the absorption. We use cotemporal and cospatial spectroheliograms obtained with the Solar and Heliospheric Observatory/SUMER and Hinode/EIS of Fe XII 1242 Å, 195 Å, and 186.88 Å, and compare the density determination from the 186/195 Å line ratio to that resulting from the 195/1242 Å line ratio. We find that while coronal loops have compatible density values from these two line pairs, upper transition region moss has conflicting density determinations. This discrepancy can be resolved by taking into account significant absorption of 195 Å emission caused by the chromospheric inclusions in the moss. We find that the amount of absorption is generally of the order of a factor of 2. We compare to numerical models and show that the observed effect is well reproduced by three-dimensional radiative MHD models of the transition region and corona. We use STEREO A/B data of the same active region and find that increased angles between line of sight and local vertical cause additional absorption. Our determination of the amount of chromospheric absorption of TR emission can be used to better constrain coronal heating models.

  20. ESTIMATING THE CHROMOSPHERIC ABSORPTION OF TRANSITION REGION MOSS EMISSION

    SciTech Connect

    De Pontieu, Bart; Hansteen, Viggo H.; McIntosh, Scott W.; Patsourakos, Spiros

    2009-09-10

    Many models for coronal loops have difficulty explaining the observed EUV brightness of the transition region, which is often significantly less than theoretical models predict. This discrepancy has been addressed by a variety of approaches including filling factors and time-dependent heating, with varying degrees of success. Here, we focus on an effect that has been ignored so far: the absorption of EUV light with wavelengths below 912 A by the resonance continua of neutral hydrogen and helium. Such absorption is expected to occur in the low-lying transition region of hot, active region loops that is colocated with cool chromospheric features and called 'moss' as a result of the reticulated appearance resulting from the absorption. We use cotemporal and cospatial spectroheliograms obtained with the Solar and Heliospheric Observatory/SUMER and Hinode/EIS of Fe XII 1242 A, 195 A, and 186.88 A, and compare the density determination from the 186/195 A line ratio to that resulting from the 195/1242 A line ratio. We find that while coronal loops have compatible density values from these two line pairs, upper transition region moss has conflicting density determinations. This discrepancy can be resolved by taking into account significant absorption of 195 A emission caused by the chromospheric inclusions in the moss. We find that the amount of absorption is generally of the order of a factor of 2. We compare to numerical models and show that the observed effect is well reproduced by three-dimensional radiative MHD models of the transition region and corona. We use STEREO A/B data of the same active region and find that increased angles between line of sight and local vertical cause additional absorption. Our determination of the amount of chromospheric absorption of TR emission can be used to better constrain coronal heating models.

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

    PubMed

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

    2014-07-21

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

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

    NASA Astrophysics Data System (ADS)

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

    2014-07-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2014-03-01

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

  4. Critical Properties of the Superfluid—Bose-Glass Transition in Two Dimensions

    NASA Astrophysics Data System (ADS)

    Álvarez Zúñiga, Juan Pablo; Luitz, David J.; Lemarié, Gabriel; Laflorencie, Nicolas

    2015-04-01

    We investigate the superfluid (SF) to Bose-glass (BG) quantum phase transition using extensive quantum Monte Carlo simulations of two-dimensional hard-core bosons in a random box potential. T =0 critical properties are studied by thorough finite-size scaling of condensate and SF densities, both vanishing at the same critical disorder Wc=4.80 (5 ) . Our results give the following estimates for the critical exponents: z =1.85 (15 ) , ν =1.20 (12 ) , η =-0.40 (15 ) . Furthermore, the probability distribution of the SF response P (ln ρSF) displays striking differences across the transition: while it narrows with increasing system sizes L in the SF phase, it broadens in the BG regime, indicating an absence of self-averaging, and at the critical point P (ln ρSF+z ln L ) is scale invariant. Finally, high-precision measurements of the local density rule out a percolation picture for the SF-BG transition.

  5. Understanding the ideal glass transition: lessons from an equilibrium study of hard disks in a channel.

    PubMed

    Godfrey, M J; Moore, M A

    2015-02-01

    We use an exact transfer-matrix approach to compute the equilibrium properties of a system of hard disks of diameter σ confined to a two-dimensional channel of width 1.95σ at constant longitudinal applied force. At this channel width, which is sufficient for next-nearest-neighbor disks to interact, the system is known to have a great many jammed states. Our calculations show that the longitudinal force (pressure) extrapolates to infinity at a well-defined packing fraction ϕ(K) that is less than the maximum possible ϕ(max), the latter corresponding to a buckled crystal. In this quasi-one-dimensional problem there is no question of there being any real divergence of the pressure at ϕ(K). We give arguments that this avoided phase transition is a structural feature, the remnant in our narrow channel system of the hexatic to crystal transition, but that it has the phenomenology of the (avoided) ideal glass transition. We identify a length scale ξ̃(3) as our equivalent of the penetration length for amorphous order: In the channel system, it reaches a maximum value of around 15σ at ϕ(K), which is larger than the penetration lengths that have been reported for three-dimensional systems. It is argued that the α-relaxation time would appear on extrapolation to diverge in a Vogel-Fulcher manner as the packing fraction approaches ϕ(K). PMID:25768471

  6. NEAR THE BOUNDARY OF THE HELIOSPHERE: A FLOW TRANSITION REGION

    SciTech Connect

    Opher, M.; Drake, J. F.; Velli, M.; Decker, R. B.; Toth, G.

    2012-06-01

    Since April of 2010, Voyager 1 has been immersed in a region of near zero radial flows, where the solar wind seems to have stopped. The existence of this region contradicts current models that predict that the radial flows will go to zero only at the heliopause. These models, however, do not include the sector region (or include it in a kinematic fashion), where the solar magnetic field periodically reverses polarity. Here we show that the presence of the sector region in the heliosheath, where reconnection occurs, fundamentally alters the flows, giving rise to a Flow Transition Region (FTR), where the flow abruptly turns and the radial velocity becomes near zero or negative. We estimate, based on a simulation, that at the Voyager 1 location, the thickness of the FTR is around 7-11 AU.

  7. Characteristic ion distributions in the dynamic auroral transition region

    NASA Astrophysics Data System (ADS)

    Zeng, W.; Horwitz, J. L.; Tu, J.-N.

    2006-04-01

    A Dynamic Fluid Kinetic (DyFK) simulation is conducted to study the H+/O+ flows and distribution functions in the high-latitude dynamic transition region, specifically from 1000 km to about 4000 km altitude. Here, the collisional-to-collisionless transition region is that region where Coulomb collisions have significant but not dominant effects on the ion distributions. In this study, a simulation flux tube, which extends from 120 km to 3 RE altitude, is assumed to experience a pulse of auroral effects for approximately 20 minutes, including both soft electron precipitation and transverse wave heating, and then according to different geophysical circumstances, either to relax following the cessation of such auroral effects or to be heated further continuously by waves with power at higher frequencies. Our principal purpose in this investigation is to elicit the characteristic ion distribution functions in the auroral transition region, where both collisions and kinetic processes play significant roles. The characteristics of the simulated O+ and H+ velocity distributions, such as kidney bean shaped H+ distributions, and O+ distributions having cold cores with upward folded conic wings, resemble those observed by satellites at similar altitudes and geographic conditions. From the simulated distribution function results under different geophysical conditions, we find that O+-O+ and O+-H+ collisions, in conjunction with the kinetic and auroral processes, are key factors in the velocity distributions up to 4000 km altitude, especially for the low speed portions, for both O+ and H+ ions.

  8. How melt stretching affect the brittle-ductile transition temperature of polymer glasses

    NASA Astrophysics Data System (ADS)

    Cheng, Shiwang; Wang, Shi-Qing

    2013-03-01

    Upon increasing temperature a brittle polymer glass can turn ductile. PMMA is a good example. For a while this brittle-ductile transition (BDT) was thought to be determined by the emergence of a secondary relaxation....1-3 On the other hand, it has been known for a long time...4-6 that predeformation in the melt state (e.g., melt stretching) can also make brittle glasses behave in a ductile manner. This transformation has recently received a satisfactory explanation based on a picture of structural hybrid for polymer glasses....7 It appears that BDT is dictated by the relative mechanical characteristics of the primary structure (due to the van der Waals bonds) and the chain network. The present work, based on conventional Instron tensile extension tests and DMA tests, shows that melt stretching does not alter the secondary relaxation behavior of PMMA and PC yet can turn them the brittle PMMA ductile and the ductile PC brittle. Moreover, sufficient melt stretching makes the brittle PS ductile although it does not produce any secondary relaxation process..1. Monnerie, L.; Laupretre, F.; Halary, J. L. Adv. Polym. Sci2005, 187, 35-213. 2. Monnerie, L.; Halary, J. L.; Kausch, H. Adv. Polym. Sci2005, 187, 215-364. 3. Wu, S. J. Appl. Polym. Sci.1992, 46, (4), 619-624. 4. Vincent, P. I. Polymer1960, 1, (0), 425-444. 5. Harris, J. S.; Ward, I. M. J. Mater. Sci.1970, 5, (7), 573-579. 6. Ender, D. H.; Andrews, R. D. J. Appl. Phys.1965, 36, (10), 3057-3062. 7. Zartman, G. D.; Cheng, S.; Li, X.; Lin, F.; Becker, M. L.; Wang, S.-Q. Macromolecules2012, 45, (16), 6719-6732.

  9. Light-scattering spectroscopy of the liquid-glass transition in CaKNO[sub 3] and in the molecular glass Salol: Extended-mode-coupling-theory analysis

    SciTech Connect

    Cummins, H.Z.; Du, W.M. ); Fuchs, M.; Goetze, W.; Hildebrand, S.; Latz, A. ); Li, G.; Tao, N.J. )

    1993-06-01

    Recently reported light-scattering studies of CaKNO[sub 3] and Salol are reanalyzed, using the extended version of the mode-coupling theory of the liquid-glass transition including activated transport or hopping effects. Problems found in the original fits due to the neglect of hopping terms are largely corrected, and quantitative predictions for the susceptibility minimum below the crossover temperature [ital T][sub [ital c

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

    PubMed Central

    Charoenrein, Sanguansri; Udomrati, Sunsanee

    2013-01-01

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

  11. NMR studies of Phase Transitions in Alkali Metal Films on Glass Substrates

    NASA Astrophysics Data System (ADS)

    Ishikawa, K.; Patton, B.; Jau, Y.-Y.; Happer, W.

    2006-05-01

    We report NMR spectra of thin ^87Rb films on glass in an investigation of the ``curing'' process which is commonly observed in alkali cells. The cells were cycled in temperature over a range of 5 C to 170 C and the rubidium solid-liquid phase transition was studied. The spectra of these two phases are resolvable at 9.4 T because of their different Knight shifts. Hysteresis in the observed phases confirmed reports of a curing phenomenon, and after time a supercooled liquid Rb peak could be detected at temperatures far below the predicted freezing point of 39 C. Moreover, a third NMR peak was observed at temperatures below the melting point whose frequency varied with temperature and spanned the solid and liquid frequency ranges. To our knowledge, this is the first study to characterize this additional resonance. We have also performed analogous measurements on ^133Cs films.

  12. Deviations of the glass transition temperature in amorphous conjugated polymer thin films.

    PubMed

    Liu, Dan; Osuna Orozco, Rodrigo; Wang, Tao

    2013-08-01

    The deviations of the glass transition temperature (T(g)) in thin films of an amorphous conjugated polymer poly(9,9-dioctylfluorene-co-N-(4-butylphenyl)diphenylamine) (TFB) are reported. Monotonic and nonmonotonic T(g) deviations are observed in TFB thin films supported on Si-SiOx and poly(3,4-ethylenedioxythiophene) poly(styrenesulfonate) (PEDOT:PSS), respectively. A three-layer model is developed to fit both monotonic and nonmonotonic T(g) deviations in these films. A 5-nm PEDOT:PSS capping layer was not found to be effective to remove the free-surface effect in Si-SiOx supported TFB films. PMID:24032856

  13. Spin-glass transition in Ni carbide single crystal nanoparticles with Ni3C - type structure

    NASA Astrophysics Data System (ADS)

    Fujieda, S.; Kuboniwa, T.; Shinoda, K.; Suzuki, S.; Echigoya, J.

    2016-05-01

    Hexagonal shaped nanoparticles about 60 nm in size were successfully synthesized in tetraethylene glycol solution containing polyvinylpyrrolidone. By the analysis of the electron diffraction pattern, these were identified as a single crystal of Ni carbide with Ni3C - type structure. Their magnetization curve at 5 K was not completely saturated under a magnetic field of 5 T. The thermomagnetization curves after zero-field cooling and after field cooling exhibited the magnetic cooling effect at low temperatures. Furthermore, the 2nd order nonlinear term of AC magnetic susceptibility exhibited a negative divergence at about 17 K. It is concluded that Ni carbide single crystal nanoparticles with the Ni3C - type structure exhibit spin-glass transition at low temperatures.

  14. Relaxation processes and glass transition in confined 1,4-polybutadiene films: A Molecular Dynamics study

    NASA Astrophysics Data System (ADS)

    Paul, Wolfgang; Solar, Mathieu

    We will present results from Molecular Dynamics simulations of a chemically realistic model of 1,4-polybutadiene (PB) chains confined by graphite walls. Relaxation processes in this system are heterogeneous and anisotropic. We will present evidence for a slow additional relaxation process related to chain desorption from the walls. We also study the structural relaxation resolved with respect to the distance from the graphite walls and show the influence of structural changes on the relaxation behavior. The temperature dependence of the dielectric relaxation in layers of different thickness near the walls shows no indication of a shift of Tg as a function of thickness when analyzed with a Vogel-Fulcher fit. We explain this by the importance of intramolecular dihedral barriers for the glass transition in PB which dominate over the density changes next to a wall except for a 1 nm thick layer directly at the wall.

  15. Effect of thermal history on mechanical properties of polyetheretherketone below the glass transition temperature

    NASA Technical Reports Server (NTRS)

    Cebe, Peggy; Chung, Shirley Y.; Hong, Su-Don

    1987-01-01

    The effect of thermal history on the tensile properties of polyetheretherketone neat resin films was investigated at different test temperatures (125, 25, and -100) using four samples: fast-quenched amorphous (Q); quenched, then crystallized at 180 C (C180); slowly cooled (for about 16 h) from the melt (SC); and air-cooled (2-3 h) from the melt (AC). It was found that thermal history significantly affects the tensile properties of the material below the glass transition. Fast quenched amorphous films were most tough, could be drawn to greatest strain before rupture, and undergo densification during necking; at the test temperature of -100 C, these films had the best ultimate mechanical properties. At higher temperatures, the semicrystalline films AC and C180 had properties that compared favorably with the Q films. The SC films exhibited poor mechanical properties at all test temperatures.

  16. Coupling of gelation and glass transition in a biphasic colloidal mixture-from gel-to-defective gel-to-glass.

    PubMed

    Jia, Di; Hollingsworth, Javoris V; Zhou, Zhi; Cheng, He; Han, Charles C

    2015-12-01

    The state transition from gel to glass is studied in a biphasic mixture of polystyrene core/poly(N-isopropylacrylamide) shell (CS) microgels and sulfonated polystyrene (PSS) particles. At 35 °C, the interaction between CS microgels is due to short-range van der Waals attraction, while that between PSS particles is from long-range electrostatic repulsion. During the variation of the relative ratio of the two species at a fixed apparent total volume fraction, the mixture exhibits a gel-to-defective gel-to-glass transition. When small amounts of PSS are introduced into the CS gel network, some of them are kinetically trapped, causing a change in its fractal structure, and act as defects to weaken the macroscopic gel strength. An increase of the PSS content in the mixture promotes the switch from the gel to the defective gel, e.g., the typical two-step yielding gel merges into one-step yielding. This phenomenon is an indication that inter-cluster bond breakage coincides with intra-cluster bond fracture. As the relative volume fraction of PSS exceeds a critical threshold, the gel network can no longer be formed; hence, the mixture exhibits characteristics of glass. A state diagram of the biphasic mixture is constructed, and the landscapes of the different transitions will be described in future studies. PMID:26394164

  17. Densification and depression in glass transition temperature in polystyrene thin films.

    PubMed

    Vignaud, G; S Chebil, M; Bal, J K; Delorme, N; Beuvier, T; Grohens, Y; Gibaud, A

    2014-10-01

    Ellipsometry and X-ray reflectivity were used to characterize the mass density and the glass transition temperature of supported polystyrene (PS) thin films as a function of their thickness. By measuring the critical wave vector (qc) on the plateau of total external reflection, we evidence that PS films get denser in a confined state when the film thickness is below 50 nm. Refractive indices (n) and electron density profiles measurements confirm this statement. The density of a 6 nm (0.4 gyration radius, Rg) thick film is 30% greater than that of a 150 nm (10Rg) film. A depression of 25 °C in glass transition temperature (Tg) was revealed as the film thickness is reduced. In the context of the free volume theory, this result seems to be in apparent contradiction with the fact that thinner films are denser. However, as the thermal expansion of thinner films is found to be greater than the one of thicker films, the increase in free volume is larger for thin films when temperature is raised. Therefore, the free volume reaches a critical value at a lower Tg for thinner films. This critical value corresponds to the onset of large cooperative movements of polymer chains. The link between the densification of ultrathin films and the drop in their Tg is thus reconciled. We finally show that at their respective Tg(h) all films exhibit a critical mass density of about 1.05 g/cm(3) whatever their thickness. The thickness dependent thermal expansion related to the free volume is consequently a key factor to understand the drop in the Tg of ultrathin films. PMID:25209183

  18. Ideal glass transitions, shear modulus, activated dynamics, and yielding in fluids of nonspherical objects.

    PubMed

    Yatsenko, Galina; Schweizer, Kenneth S

    2007-01-01

    An extension of naive ideal mode coupling theory (MCT) and its generalization to treat activated barrier hopping and glassy dynamics in fluids and suspensions composed of nonspherical hard core objects is proposed. An effective center-of-mass description is adopted. It corresponds to a specific type of pre-averaging of the dynamical consequences of orientational degrees of freedom. The simplest case of particles composed of symmetry-equivalent interaction sites is considered. The theory is implemented for a homonuclear diatomic shape of variable bond length. The naive MCT glass transition boundary is predicted to be a nonmonotonic function of the length-to-width or aspect ratio and occurs at a nearly unique value of the dimensionless compressibility. The latter quantifies the amplitude of long wavelength thermal density fluctuations, thereby (empirically) suggesting a tight connection between the onset of localization and thermodynamics. Localization lengths and elastic shear moduli for different aspect ratio and volume fraction systems approximately collapse onto master curves based on a reduced volume fraction variable that quantifies the distance from the ideal glass transition. Calculations of the entropic barrier height and hopping time, maximum restoring force, and absolute yield stress and strain as a function of diatomic aspect ratio and volume fraction have been performed. Strong correlations of these properties with the dimensionless compressibility are also found, and nearly universal dependences have been numerically identified based on property-specific nondimensionalizations. Generalization of the approach to rigid rods, disks, and variable shaped molecules is possible, including oriented liquid crystalline phases. PMID:17212498

  19. Glass transition measurements in mixed organic and organic/inorganic aerosol particles

    NASA Astrophysics Data System (ADS)

    Dette, Hans Peter; Qi, Mian; Schröder, David; Godt, Adelheid; Koop, Thomas

    2014-05-01

    The recent proposal of a semi-solid or glassy state of secondary organic aerosol (SOA) particles has sparked intense research in that area. In particular, potential effects of a glassy aerosol state such as incomplete gas-to-particle partitioning of semi-volatile organics, inhibited chemical reactions and water uptake, and the potential to act as heterogeneous ice nuclei have been identified so far. Many of these studies use well-studied proxies for oxidized organics such as sugars or other polyols. There are, however, few measurements on compounds that do exist in atmospheric aerosol particles. Here, we have performed studies on the phase state of organics that actually occur in natural SOA particles arising from the oxidation of alpha-pinene emitted in boreal forests. We have investigated the two marker compounds pinonic acid and 3-methylbutane-1,2,3-tricarboxylic acid (3-MBTCA) and their mixtures. 3-MBCTA was synthesized from methyl isobutyrate and dimethyl maleate in two steps. In order to transfer these substances into a glassy state we have developed a novel aerosol spray drying technique. Dilute solutions of the relevant organics are atomized into aerosol particles which are dried subsequently by diffusion drying. The dried aerosol particles are then recollected in an impactor and studied by means of differential scanning calorimetry (DSC), which provides unambiguous information on the aerosols' phase state, i.e. whether the particles are crystalline or glassy. In the latter case DSC is used to determine the glass transition temperature Tg of the investigated samples. Using the above setup we were able to determine Tg of various mixtures of organic aerosol compounds as a function of their dry mass fraction, thus allowing to infer a relation between Tg and the O:C ratio of the aerosols. Moreover, we also studied the glass transition behavior of mixed organic/inorganic aerosol particles, including the effects of liquid-liquid phase separation upon drying.

  20. Manifestation of random first-order transition theory in Wigner glasses.

    PubMed

    Kang, Hongsuk; Kirkpatrick, T R; Thirumalai, D

    2013-10-01

    We use Brownian dynamics simulations of a binary mixture of highly charged spherical colloidal particles to test some of the predictions of the random first-order transition (RFOT) theory [Phys. Rev. Lett. 58, 2091 (1987); Phys. Rev. A 40, 1045 (1989)]. In accord with mode-coupling theory and RFOT, we find that as the volume fraction of the colloidal particles ϕ approaches the dynamical transition value ϕ(A), three measures of dynamics show an effective ergodic to nonergodic transition. First, there is a dramatic slowing down of diffusion, with the translational diffusion constant decaying as a power law as ϕ→ϕ(A)(-). Second, the energy metric, a measure of ergodicity breaking in classical many-body systems, shows that the system becomes effectively nonergodic as ϕ(A) is approached. Finally, the time t(*), at which the four-point dynamical susceptibility achieves a maximum, also increases as a power law near ϕ(A). Remarkably, the translational diffusion coefficients, ergodic diffusion coefficient, and (t(*))(-) all vanish as (ϕ(-1)-ϕ(A)(-1))(γ) with both ϕ(A)(≈0.1) and γ being the roughly the same for all three quantities. Above ϕ(A), transport involves crossing free energy barriers. In this regime, the density-density correlation function decays as a stretched exponential [exp-(t/τ(α))(β)] with β≈0.45. The ϕ dependence of the relaxation time τ(α) could be fit using the Vogel-Tamman-Fulcher law with the ideal glass transition at ϕ(K)≈0.47. By using a local entropy measure, we show that the law of large numbers is not obeyed above ϕ(A), and gives rise to subsample to subsample fluctuations in all physical observables. We propose that dynamical heterogeneity is a consequence of violation of law of large numbers. PMID:24229173

  1. Wave propagation in the chromosphere and transition region

    NASA Technical Reports Server (NTRS)

    Steffens, S.; Deubner, F.-L.; Fleck, B.; Wilhelm, K.; Harrison, R.; Gurman, J.

    1997-01-01

    The results from a joint observing program involving the solar ultraviolet measurement of emitted radiation (SUMER), the coronal diagnostic spectrometer (CDS) and the extreme-ultraviolet imaging telescope (EIT) onboard the Solar and Heliospheric Observatory (SOHO) are presented. These operations were coordinated with ground-based observations at the vacuum tower telescope at Izana (Tenerife). The purpose was to characterize the wave propagation properties in the solar atmosphere, from the photosphere through the chromosphere into the transition region.

  2. Combustion characteristics in the transition region of liquid fuel sprays

    NASA Technical Reports Server (NTRS)

    Cernansky, N. P.; Namer, I.; Tidona, R. J.; Sarv, H.

    1984-01-01

    A monodisperse aerosol generator was modified to study ignition requirements, flammability limits, and flame speeds in the transition region. An ignition system was developed and tested. The fabrication of an optical drop sizing system is nearly complete. Preliminary measurements of droplet size effects on the minimum ignition energy for n-heptane sprays performed. Parameteric studies of droplet size effects on minimum ignition energies of various fuels including alcohols are in progress.

  3. Transitional modes of motion and capture regions of vibroshock systems

    NASA Technical Reports Server (NTRS)

    Ragulskene, V. L.

    1973-01-01

    A numerical analysis of the transitional modes of motion for a vibroshock system was conducted. The capture regions of the system are emphasized. The three initial parameters for a nonautonomous vibroshock system with one degree of freedom are identified as: (1) coordinates, (2) velocity, and (3) time. Mathematical models are developed to show the relationship of the parameters. Graphs are included to show the nature of the capture regions and to portray the trajectory of motion of mass with time, by solution of differential equations during increase and decrease in time.

  4. Fine Structure and Optical Depth in the Solar Transition Region

    NASA Astrophysics Data System (ADS)

    Plovanic, Jacob; Kankelborg, C. C.; Williamson, K.

    2011-05-01

    Unresolved fine structure in the solar transition region (TR) has long been inferred from measurements of density-sensitive line pairs showing low filling factor (< 0.01). Low filling factor models for the structure of the He II source region, however, have not been well studied. We propose a highly structured model of the lower atmosphere in which He II is formed at low filling factors, leading to high emission measure and an optically thin He II line. This transparent TR material is juxtaposed with absorbing chromospheric structures, leading to the nearly uniform center to limb behavior of the He II line as observed.

  5. Influence of crosslinker and ionic comonomer concentration on glass transition and demixing/mixing transition of copolymers poly(N-isopropylacrylamide) and poly(sodium acrylate) hydrogels.

    PubMed

    Zarzyka, Iwona; Pyda, Marek; Di Lorenzo, Maria Laura

    2014-01-01

    Hydrogels based on N-isopropylacrylamide and sodium acrylate as ionic comonomer were synthesized by free radical polymerization in water using N,N'-methylenebisacrylamide as crosslinker and ammonium persulfate as initiator. The glass transition of dried copolymers poly(N-isopropylacrylamide) (PNIPA) and poly(sodium acrylate) (SA) gels and demixing/mixing transition of PNIPA-SA hydrogels swollen with increasing amounts of water were studied using conventional differential scanning calorimetry. In the crosslinked polymers, the glass transition linearly increases, and the transition range becomes broader, with increasing crosslinker content. Increasing content of ionic comonomer also produces an increase of glass transition temperature, which moves to higher temperatures with higher sodium acrylate fraction. The influence of chemical structure of PNIPA-SA hydrogels on the lower critical solution temperature (LCST) of PNIPA-SA/water mixtures during heating and cooling was quantified as function of the content of the crosslinker and the ionic comonomer, as well as water content of the hydrogel in the range from 95 to 70 wt%. At parity of water content, the LCST occurs at higher temperatures for gels containing higher amounts of sodium acrylate. Similarly, the introduction of N,N'-methylenebisacrylamide causes an increase of the LCST, which grows with increasing of crosslinking degree of the hydrogel. PMID:24511175

  6. Computational study of structural change through the glass transition in an amorphous and liquid Zr-Ni alloy

    SciTech Connect

    Aihara, Tomoyasu Jr.; Aoki, Kiyoshi; Masumoto, Tsuyoshi )

    1993-04-15

    Amorphous alloys are experimentally or industrially produced by rapid quenching (RQ) from the melt. If a liquid alloy is rapidly cooled at a rate on the order of 10[sup 6]Ks[sup [minus]1], it enters the supercooled liquid regime and its viscosity increases. Finally, the system reaches a state of frozen random structure, which is called the amorphous state. In the attempt to control the properties of amorphous alloys, it is important to understand their structural changes through the glass transition. By a laboratory experiment, however, it is usually difficult to obtain information about the glass transition and supercooled state of an amorphous alloy because of competitive crystallization. Molecular dynamics (MD) simulation, a numerical experiment to solve the N-body problem of Newtonian mechanics, has been performed to investigate the structure of solid and liquid. As the MD simulation can be carried out on the order of picoseconds, one can detect the glass transition without crystallization during RQ. Thus, the authors performed the MD simulation for the production of an amorphous Zr-Ni alloy by RQ and detected static structure and thermodynamic changes through the glass transition. Both properties are related with interatomic potentials.

  7. Time dependent physical properties of semicrystalline poly(arylene ether ether ketone) (PEEK) above its glass transition temperature: Physical aging vs. secondary crystallization

    SciTech Connect

    Velikov, V.; Verma, R.; marand, H.

    1995-12-01

    We monitored the change in small strain short term isothermal creep compliance of semicrystalline. PEEK (T{sub g} {approx} 150{degrees}C - 165{degrees}C) at various temperatures from 120{degrees}C to 260{degrees}C. With increase of aging times creep curves are shifted to longer times, implying slowing down of the mechanical relaxation of the polymer. The isothermal horizontal shift rate is close to unity below and above T{sub g} and exhibits significant drop in the glass transition region.

  8. Topological characteristics of bonds in SiO{sub 2} and GeO{sub 2} oxide systems upon a glass-liquid transition

    SciTech Connect

    Ozhovan, M. I.

    2006-11-15

    Using the Angell model of broken bonds (configurons), configuron clustering in a topologically disordered lattice (network) of amorphous SiO{sub 2} and GeO{sub 2} upon a glass-liquid transition is considered. It is shown that the glass-liquid transition is accompanied by the formation of a macroscopic (percolation) configuron cluster penetrating the entire bulk of the material and possessing fractal geometry. The glass-liquid (overcooled liquid) percolation phase transition in the amorphous substance is accompanied by a change in the Hausdorff dimension of the bond network structure for configurons from the three-dimensional Euclidean dimension in the glassy state to a fractal dimension of 2.55 {+-} 0.05 in the liquidlike state. Contrary to the kinetic character of the liquid-glass transition, the glass-transition temperature is a thermodynamic parameter of the amorphous substance, depending parametrically on the cooling rate.

  9. Origins of the two simultaneous mechanisms causing glass transition temperature reductions in high molecular weight freestanding polymer films

    SciTech Connect

    Prevosto, Daniele E-mail: Prevosto@df.unipi.it; Capaccioli, Simone; Ngai, K. L. E-mail: Prevosto@df.unipi.it

    2014-02-21

    From ellipsometry measurements, Pye and Roth [Phys. Rev. Lett. 107, 235701 (2011)] presented evidence of the presence of two glass transitions originating from two distinctly different and simultaneous mechanisms to reduce the glass transition temperature within freestanding polystyrene films with thickness less than 70 nm. The upper transition temperature T{sub g}{sup u}(h) is higher than the lower transition temperature T{sub g}{sup l}(h) in the ultrathin films. After comparing their data with the findings of others, using the same or different techniques, they concluded that new theoretical interpretation is needed to explain the two transitions and the different dependences of T{sub g}{sup u}(h) and T{sub g}{sup l}(h) on film thickness and molecular weight. We address the problem based on advance in delineating the different viscoelastic mechanisms in the glass-rubber transition zone of polymers. Theoretical considerations as well as experiments have shown in time-scales immediately following the segmental α-relaxation are the sub-Rouse modes with longer length scale but shorter than that of the Rouse modes. The existence of the sub-Rouse modes in various polymers including polystyrene has been repeatedly confirmed by experiments. We show that the sub-Rouse modes can account for the upper transition and the properties observed. The segmental α-relaxation is responsible for the lower transition. This is supported by the fact that the segmental α-relaxation in ultrathin freestanding PS films had been observed by dielectric relaxation measurements and photon correlation spectroscopy. Utilizing the temperature dependence of the segmental relaxation times from these experiments, the glass transition temperature T{sub g}{sup α} associated with the segmental relaxation in the ultrathin film is determined. It turns out that T{sub g}{sup α} is nearly the same as T{sub g}{sup l}(h) of the lower transition, and hence definitely segmental α-relaxation is the

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

    DOE PAGESBeta

    Reig-i-Plessis, D.; Casavant, D.; Garlea, Vasile O.; Aczel, Adam A.; Feygenson, Mikhail; Neuefeind, Joerg C.; Zhou, H. D.; Nagler, Stephen E.; MacDougall, Gregory J.

    2016-01-25

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

  11. Multichannel transition emissions of Dy{sup 3+} in fiber-adaptive germanium tellurite glasses

    SciTech Connect

    Li, Y. H.; Chen, B. J.; Lin, H.; Pun, E. Y. B.

    2013-03-28

    Multichannel transition visible and near-infrared (NIR) fluorescences have been captured in Dy{sup 3+}-doped fiber-adaptive Na{sub 2}O-ZnO-PbO-GeO{sub 2}-TeO{sub 2} glasses. The maximum stimulated emission cross-sections {sigma}{sub em-max} were derived to be 0.33 Multiplication-Sign 10{sup -21}, 3.66 Multiplication-Sign 10{sup -21}, and 0.67 Multiplication-Sign 10{sup -21} cm{sup 2} for conventional visible emissions assigned to {sup 4}F{sub 9/2}{yields}{sup 6}H{sub J} (J = 15/2, 13/2, and 11/2) transitions, respectively. Infrequent multi-peak NIR emissions were recorded in the spectral range of 900-1500 nm, among which the values of {sigma}{sub em-max} were solved to be 1.05 Multiplication-Sign 10{sup -22} and 1.56 Multiplication-Sign 10{sup -22} cm{sup 2} for {approx}1.02 and {approx}1.18 {mu}m emission bands. Internal quantum efficiency for the {sup 4}F{sub 9/2} level and external quantum yield for visible emissions of Dy{sup 3+} were determined to be 88.44% and 12.38%, severally. Effective multichannel radiative emissions reveal a potential in developing fiber-lighting sources, tunable lasers, and NIR optical amplifiers.

  12. Waveguides and nonlinear index of refraction of borate glass doped with transition metals

    NASA Astrophysics Data System (ADS)

    Almeida, Juliana M. P.; Fonseca, Ruben D.; De Boni, Leonardo; Diniz, Andre Rosa S.; Hernandes, Antonio C.; Ferreira, Paulo H. D.; Mendonca, Cleber R.

    2015-04-01

    The ability to write 3D waveguides by femtosecond laser micromachining and the nonlinear refractive index (n2) spectrum of a new borate glass matrix, containing zinc and lead oxides - (BZP) have been investigated. The transparent matrix was doped with transition metals (CdCl2, Fe2O3, MnO2 and CoO) in order to introduce electronic transitions in visible spectrum, aiming to evaluate their influence on the waveguides and n2 spectrum. We observed that n2 is approximately constant from 600 to 1500 nm, exhibiting an average value of 4.5 × 10-20 m2/W, which is about twice larger than the one for fused silica. The waveguide profile is influenced by the self-focusing effect of the matrix owing to its positive nonlinear index of refraction in the wavelength used for micromachining. A decrease in the waveguide loss of approximately four times was observed for the sample doped with Fe in comparison to the other ones, which may be associated with the change in the optical gap energy.

  13. On the Active Region Bright Grains Observed in the Transition Region Imaging Channels of IRIS

    NASA Astrophysics Data System (ADS)

    Skogsrud, H.; Rouppe van der Voort, L.; De Pontieu, B.

    2016-02-01

    The Interface Region Imaging Spectrograph (IRIS) provides spectroscopy and narrow band slit-jaw (SJI) imaging of the solar chromosphere and transition region at unprecedented spatial and temporal resolutions. Combined with high-resolution context spectral imaging of the photosphere and chromosphere as provided by the Swedish 1 m Solar Telescope (SST), we can now effectively trace dynamic phenomena through large parts of the solar atmosphere in both space and time. IRIS SJI 1400 images from active regions, which primarily sample the transition region with the Si iv 1394 and 1403 Å lines, reveal ubiquitous bright “grains” which are short-lived (two to five minute) bright roundish small patches of sizes 0.″5-1.″7 that generally move limbward with velocities up to about 30 km s-1. In this paper, we show that many bright grains are the result of chromospheric shocks impacting the transition region. These shocks are associated with dynamic fibrils (DFs), most commonly observed in Hα. We find that the grains show the strongest emission in the ascending phase of the DF, that the emission is strongest toward the top of the DF, and that the grains correspond to a blueshift and broadening of the Si iv lines. We note that the SJI 1400 grains can also be observed in the SJI 1330 channel which is dominated by C ii lines. Our observations show that a significant part of the active region transition region dynamics is driven from the chromosphere below rather than from coronal activity above. We conclude that the shocks that drive DFs also play an important role in the heating of the upper chromosphere and lower transition region.

  14. Evidence of liquid–liquid transition in glass-forming La50Al35Ni15 melt above liquidus temperature

    PubMed Central

    Xu, Wei; Sandor, Magdalena T.; Yu, Yao; Ke, Hai-Bo; Zhang, Hua-Ping; Li, Mao-Zhi; Wang, Wei-Hua; Liu, Lin; Wu, Yue

    2015-01-01

    Liquid–liquid transition, a phase transition of one liquid phase to another with the same composition, provides a key opportunity for investigating the relationship between liquid structures and dynamics. Here we report experimental evidences of a liquid–liquid transition in glass-forming La50Al35Ni15 melt above its liquidus temperature by 27Al nuclear magnetic resonance including the temperature dependence of cage volume fluctuations and atomic diffusion. The observed dependence of the incubation time on the degree of undercooling is consistent with a first-order phase transition. Simulation results indicate that such transition is accompanied by the change of bond-orientational order without noticeable change in density. The temperature dependence of atomic diffusion revealed by simulations is also in agreement with experiments. These observations indicate the need of two-order parameters in describing phase transitions of liquids. PMID:26165855

  15. Evidence of liquid-liquid transition in glass-forming La50Al35Ni15 melt above liquidus temperature

    NASA Astrophysics Data System (ADS)

    Xu, Wei; Sandor, Magdalena T.; Yu, Yao; Ke, Hai-Bo; Zhang, Hua-Ping; Li, Mao-Zhi; Wang, Wei-Hua; Liu, Lin; Wu, Yue

    2015-07-01

    Liquid-liquid transition, a phase transition of one liquid phase to another with the same composition, provides a key opportunity for investigating the relationship between liquid structures and dynamics. Here we report experimental evidences of a liquid-liquid transition in glass-forming La50Al35Ni15 melt above its liquidus temperature by 27Al nuclear magnetic resonance including the temperature dependence of cage volume fluctuations and atomic diffusion. The observed dependence of the incubation time on the degree of undercooling is consistent with a first-order phase transition. Simulation results indicate that such transition is accompanied by the change of bond-orientational order without noticeable change in density. The temperature dependence of atomic diffusion revealed by simulations is also in agreement with experiments. These observations indicate the need of two-order parameters in describing phase transitions of liquids.

  16. Titan Ion Composition at Magnetosphere-Ionosphere Transition Region

    NASA Technical Reports Server (NTRS)

    Sittler, Edward C.; Hartle, R. E.; Shappirio, M.; Simpson, D. J.; COoper, J. F.; Burger, M. H.; Johnson, R. E.; Bertucci, C.; Luhman, J. G.; Ledvina, S. A.; Szego, K.; Coates, A. J.; Young, D. T.

    2006-01-01

    Using Cassini Plasma Spectrometer (CAPS) Ion Mass Spectrometer (IMS) ion composition data, we will investigate the compositional changes at the transition region between Saturn's magnetospheric flow and Titan's upper ionosphere. It is this region where scavenging of Titan's upper ionosphere can occur, where it is then dragged away by the magnetospheric flow as cold plasma for Saturn's magnetosphere. This cold plasma may form plumes as originally proposed by (1) during the Voyager 1 epoch. This source of cold plasma may have a unique compositional signature such as methane group ions. Water group ions that are observed in Saturn's outer magnetosphere (2,3) are relatively hot and probably come from the inner magnetosphere where they are born from fast neutrals escaping Enceladus (4) and picked up in the outer magnetosphere as hot plasma (5). This scenario will be complicated by pickup methane ions within Titan's mass loading region, as originally predicted by (6) based on Voyager 1 data and observationally confirmed by (3,7) using CAPS IMS data. But, CH4(+) ions or their fragments can only be produced as pickup ions from Titan's exosphere which can extend beyond the transition region of concern here, while CH5(+) ions can be scavenged from Titan's ionosphere. We will investigate these possibilities.

  17. Thermodynamic calculation and interatomic potential to predict the favored composition region for the Cu-Zr-Al metallic glass formation.

    PubMed

    Cui, Y Y; Wang, T L; Li, J H; Dai, Y; Liu, B X

    2011-03-01

    For the Cu-Zr-Al system, the glass forming compositions were firstly calculated based on the extended Miedema's model, suggesting that the amorphous phase could be thermodynamically favored over a large composition region. An n-body potential was then constructed under the smoothed and long-range second-moment-approximation of tight-binding formulism. Applying the constructed Cu-Zr-Al potential, molecular dynamics simulations were conducted using solid solution models to compare relative stability of crystalline solid solution versus its disordered counterpart. Simulations reveal that the physical origin of metallic glass formation is crystalline lattice collapsing while solute concentration exceeding the critical value, thus predicting a hexagonal composition region, within which the Cu-Zr-Al ternary metallic glass formation is energetically favored. The molecular dynamics simulations predicted composition region is defined as the quantitative glass-forming-ability or glass-forming-region of the Cu-Zr-Al system. PMID:21229150

  18. Effect of sugar addition on glass transition temperatures of cassava starch with low to intermediate moisture contents.

    PubMed

    Figueroa, Yetzury; Guevara, Marvilan; Pérez, Adriana; Cova, Aura; Sandoval, Aleida J; Müller, Alejandro J

    2016-08-01

    This work studies how sucrose (S) addition modifies the thermal properties of cassava starch (CS). Neat CS and CS-S blends with 4, 6 and 8% sugar contents (CS-S-4%, CS-S-6% and CS-S-8%) were prepared and analyzed by differential scanning calorimetry (DSC) and dynamic mechanical thermal analysis (DMTA), in a wide range of moisture levels (2-20%). In equilibrated samples with moisture contents lower than 10%, twoendothermic steps were observed during first DSC heating scans and two corresponding relaxation maxima in tan δ were detected by DMTA. The first transition, detected at around 45-55°C by both DSC and DMTA, is frequently found in starchy foods, while the second observed at higher temperatures is associated to the glass transition temperature of the blends. At higher moisture contents, only one thermal transition was observed. Samples analyzed immediately after cooling from the melt (i.e., after erasing their thermal history), exhibited a single glass transition temperature, regardless of their moisture content. Addition of sugar promotes water plasticization of CS only at high moisture contents. In the low moisture content range, anti-plasticization was observed for both neat and sugar-added CS samples. Addition of sugar decreases the moisture content needed to achieve the maximum value of the glass transition temperature before plasticization starts. The results of this work may be valuable for the study of texture establishment in low moisture content extruded food products. PMID:27112870

  19. Transitions between refrigeration regions in extremely short quantum cycles.

    PubMed

    Feldmann, Tova; Kosloff, Ronnie

    2016-05-01

    The relation between the geometry of refrigeration cycles and their performance is explored. The model studied is based on a coupled spin system. Small cycle times, termed sudden refrigerators, develop coherence and inner friction. We explore the interplay between coherence and energy of the working medium employing a family of sudden cycles with decreasing cycle times. At the point of maximum coherence the cycle changes geometry. This region of cycle times is characterized by a dissipative resonance where heat is dissipated both to the hot and cold baths. We rationalize the change of geometry of the cycle as a result of a half-integer quantization which maximizes coherence. From this point on, increasing or decreasing the cycle time, eventually leads to refrigeration cycles. The transition point between refrigerators and short circuit cycles is characterized by a transition from finite to singular dynamical temperature. Extremely short cycle times reach a universal limit where all cycles types are equivalent. PMID:27300872

  20. Transitions between refrigeration regions in extremely short quantum cycles

    NASA Astrophysics Data System (ADS)

    Feldmann, Tova; Kosloff, Ronnie

    2016-05-01

    The relation between the geometry of refrigeration cycles and their performance is explored. The model studied is based on a coupled spin system. Small cycle times, termed sudden refrigerators, develop coherence and inner friction. We explore the interplay between coherence and energy of the working medium employing a family of sudden cycles with decreasing cycle times. At the point of maximum coherence the cycle changes geometry. This region of cycle times is characterized by a dissipative resonance where heat is dissipated both to the hot and cold baths. We rationalize the change of geometry of the cycle as a result of a half-integer quantization which maximizes coherence. From this point on, increasing or decreasing the cycle time, eventually leads to refrigeration cycles. The transition point between refrigerators and short circuit cycles is characterized by a transition from finite to singular dynamical temperature. Extremely short cycle times reach a universal limit where all cycles types are equivalent.

  1. Scaling behavior of domain walls at the T = 0 ferromagnet to spin-glass transition

    NASA Astrophysics Data System (ADS)

    Melchert, O.; Hartmann, A. K.

    2009-01-01

    Using mappings to combinatorial optimization problems, one can often study physical systems better by means of sophisticated algorithms from computer science. Here, we study the geometric properties of domain-wall excitations in a two-dimensional random-bond Ising spin system, where each realization of the disorder consists of a random fraction ρ of ferromagnetic bonds and a fraction (1-ρ) of bonds drawn from a Gaussian distribution with zero mean and unit width. We formulate an auxiliary graph theoretical problem in which domain walls are given by undirected shortest paths with possibly negative distances [O. Melchert and A.K. Hartmann Phys. Rev. B 76, 174411 (2007)]. Due to the details of the mapping, standard shortest path algorithms (e.g. the Dijkstra algorithm) cannot be applied. To solve such shortest path problems it requires minimum weight perfect matching algorithms. We first locate the critical point ρc, where the ferromagnet (large ρ) to spin-glass transition occurs. For certain values of ρ close to the critical point we investigate the stiffness exponent θ and the fractal dimension df that describe the scaling of the average domain-wall energy and length, respectively. Performing a finite-size scaling analysis we find that both exponents remain constant in the spin-glass phase, i.e. θ~-0.28 and df~1.275. This is consistent with conformal field theory, where it seems to be possible [C. Amoruso et al. Phys. Rev. Lett. 97, 267202 (2006)] to relate the exponents via df-1 = 3/[4(3+θ)].

  2. Winter/summer transition in the Antarctic mesopause region

    NASA Astrophysics Data System (ADS)

    Lübken, F.-J.; Höffner, J.; Viehl, T. P.; Becker, E.; Latteck, R.; Kaifler, B.; Murphy, D. J.; Morris, R. J.

    2015-12-01

    A new set of temperature data with unprecedented resolution and accuracy has been obtained from Fe lidar measurements at Davis, Antarctica (69°S). Here we concentrate on the months of the winter/summer transition (November to February) where we have collected a total of 1305 h of observations in the three seasons 2010/2011, 2011/2012, and 2012/2013. The temporal development of temperatures around the mesopause in 2012/2013 is rather similar to the Northern Hemisphere (NH), whereas the other seasons are significantly different, exhibiting, e.g., an unusual higher and colder mesopause around solstice (elevated summer mesopause). During this exceptional period mean daily mesopause heights and temperatures are approximately 92.0 ± 0.5 km and 125 K, respectively. The seasonal variation of temperatures in the mesopause region is closely related to the circulation in the stratosphere which exhibits an early (late) vortex breakdown in 2012/2013 (2010/2011). The situation is more complicated in 2011/2012. The early (late) transition in the mesopause region is accompanied by an early (late) appearance of polar mesosphere summer echoes. Zonal winds as measured by an MF radar also show systematic differences with westward winds reaching up to very high altitudes (nearly 100 km) for the late transition in 2010/2011 and to more common heights (˜90 km) for the early transition in 2012/2013. A mesopause being higher and colder compared to the NH (as occasionally observed at Davis) cannot be achieved by standard models. More sophisticated characterization of gravity wave forcing might be required.

  3. Fluid dynamics at transition regions of enhanced heat transfer channels

    NASA Astrophysics Data System (ADS)

    Case, Jennifer C.; Pohlman, Nicholas A.

    2012-11-01

    Helical wire coil inserts are used to enhance heat transfer in high heat flux cooling channels. Past research using temperature probes has sufficiently proven that wire coils increase heat transfer by factors of three to five through the disruption of the boundary layer in the channels. The coils are passive devices that are inexpensive to manufacture and easily integrate into existing heat exchangers given the limited pressure drop they produce. Most of the fluid mechanics research in flow over helical coils has focused on the dynamics and vortex structure in fully developed regions rather than the short transition region where the enhanced heat transfer is often expected. Understanding how the development of the flow occurs over the axial length of the cooling channel will determine minimum dimensions necessary for enhanced heat transfer. Results of particle-shadow velocimetry (PSV) measurements report on the flow velocities and turbulence that occurs in the transition regions at the beginning of wire coil inserts. The ability to relate parameters such as flow rate, wire diameter, coil pitch, and the total tube length will increase fundamental knowledge and will allow for more efficient heat exchanger designs. Funding provided by NIU's Undergraduate Special Opportunities in Artistry & Research grant program.

  4. Transition Region and Chromospheric Signatures of Impulsive Heating Events

    NASA Astrophysics Data System (ADS)

    Warren, Harry; Reep, Jeffrey; Crump, Nicholas

    2016-05-01

    We exploit the high spatial resolution and high cadence of the Interface Region Imaging Spectrograph (IRIS) to investigate the response of the transition region and chromosphere to energy deposition during several small flares. We find that during the impulsive phase of these events the intensities of the C II 1334.535 and Si IV 1402.770 A emission lines are characterized by numerous, small-scale impulsive bursts typically lasting 60 s or less followed by a slower decay over several minutes. These variations in intensity are usually accompanied by impulsive redshifts of 20–40 km/s, although some blueshifted profiles are also observed. For one particularly well observed event we combine the IRIS observations with co-temporal measurements of hard X-ray emission from RHESSSI, transition region density from EIS, and high-temperature coronal loops with XRT and AIA to constrain 1D hydrodynamic models of loop evolution. Many aspects of the observations can be explained with simple heating scenarios, but some cannot. The simulated Doppler shifts, for example, show very short-duration redshifts during the initial phase of the heating while the observed redshifts persist over several minutes.

  5. Oxidation induced amorphous stabilization of the subsurface region in Zr-Cu metallic glass

    SciTech Connect

    Lim, K. R.; Park, J. M.; Park, S. H.; Na, M. Y.; Kim, K. C.; Kim, D. H.; Kim, W. T.

    2014-01-20

    In the present study, we demonstrate that selective surface oxidation of Zr{sub 70}Cu{sub 30} metallic glass can stabilize the amorphous structure in the subsurface region of the matrix. The oxidation proceeds by selective oxidation of Zr, forming monoclinic ZrO{sub 2} layer on the surface, and the subsurface layer becomes Cu-enriched due to back diffusion of Cu atoms from the oxide layer. Interestingly, in this system, the composition change in the subsurface region leads to enhancement of glass stability, forming of a double layered surface structure consisted of inner amorphous layer and outer monoclinic ZrO{sub 2} layer even when the remaining matrix is completely crystallized.

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

    NASA Astrophysics Data System (ADS)

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

    2016-01-01

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

  7. Low transition-region characteristics of equatorial coronal holes

    NASA Technical Reports Server (NTRS)

    Patsourakos, S.; Bocchialini, K.; Vial, J.-C.

    1997-01-01

    The results of observations concerning the low transition region of equatorial coronal holes, performed by the Solar and Heliospheric Observatory (SOHO), are discussed. A study performed by other authors led to the conclusion that the chromospheric network corresponding to an equatorial hole is brighter in some lines than the one corresponding to the quiet sun. A statistical study on equatorial holes using the Lyman beta lines from the solar ultraviolet measurements of emitted radiation (SUMER), onboard SOHO, is presented. The mean profiles of cell, network and bright points in and out of the coronal holes are discussed, together with the possible implications of the observations.

  8. Manifestation of random first-order transition theory in Wigner glasses

    NASA Astrophysics Data System (ADS)

    Kang, Hongsuk; Kirkpatrick, T. R.; Thirumalai, D.

    2013-10-01

    We use Brownian dynamics simulations of a binary mixture of highly charged spherical colloidal particles to test some of the predictions of the random first-order transition (RFOT) theory [Phys. Rev. Lett.PRLTAO0031-900710.1103/PhysRevLett.58.2091 58, 2091 (1987); Phys. Rev. A1050-294710.1103/PhysRevA.40.1045 40, 1045 (1989)]. In accord with mode-coupling theory and RFOT, we find that as the volume fraction of the colloidal particles ϕ approaches the dynamical transition value ϕA, three measures of dynamics show an effective ergodic to nonergodic transition. First, there is a dramatic slowing down of diffusion, with the translational diffusion constant decaying as a power law as ϕ→ϕA-. Second, the energy metric, a measure of ergodicity breaking in classical many-body systems, shows that the system becomes effectively nonergodic as ϕA is approached. Finally, the time t*, at which the four-point dynamical susceptibility achieves a maximum, also increases as a power law near ϕA. Remarkably, the translational diffusion coefficients, ergodic diffusion coefficient, and (t*)-1 all vanish as (ϕ-1-ϕA-1)γ with both ϕA(≈0.1) and γ being the roughly the same for all three quantities. Above ϕA, transport involves crossing free energy barriers. In this regime, the density-density correlation function decays as a stretched exponential [exp-((t)/(τα))β] with β≈0.45. The ϕ dependence of the relaxation time τα could be fit using the Vogel-Tamman-Fulcher law with the ideal glass transition at ϕK≈0.47. By using a local entropy measure, we show that the law of large numbers is not obeyed above ϕA, and gives rise to subsample to subsample fluctuations in all physical observables. We propose that dynamical heterogeneity is a consequence of violation of law of large numbers.

  9. Magnetic ordering in the ilmenite-hematite solid solution: A computational study of the low-temperature spin glass region

    NASA Astrophysics Data System (ADS)

    Harrison, Richard J.

    2009-02-01

    Magnetic ordering in the ilmenite-hematite solid solution (Fe2-xTixO3) has been investigated using Monte Carlo simulations, with particular emphasis on the low-temperature spin glass region of the phase diagram. Complex magnetic behavior is observed due to the presence of two competing magnetic order parameters: a "hematite-like" ordering with a two-layer repeat (Q2) and an "ilmenite-like" ordering with a four-layer repeat (Q4). The susceptibility and degree of magnetic order were calculated from the Fourier transform of the layer-averaged spin distribution, allowing long-range and short-range contributions from Q2 and Q4 to be analyzed separately. For x < 0.8, the ferrimagnetic (FM) phase remains stable down to 0 K. For x ≥ 0.8 a heterogeneous FM phase (HFM) followed by a modulated FM phase (MFM) develops. There is an increasing contribution from Q4 with increasing x, and a pronounced cusp in both Q2 and Q4 susceptibilities develops at 30 K. The superposition of Q2 and Q4 leads to frustrated layers containing dynamically disordered spins. Freezing of this spin disorder below 30 K is responsible for the cusp in susceptibility, which can be classified as a reentrant spin glass (RSG) transition. A gradual loss of long-range FM order occurs as the percolation threshold is approached, resulting in a conventional spin glass (CSG) with no long-range order below 30 K for x ≥ 0.92. For x > 0.95, a transition to an antiferromagnetic (AF) phase occurs at 40-55 K, followed by an RSG transition at 20-30 K. Changes to the phase diagram caused by chemical clustering are determined using a preannealing algorithm. Clustering expands the AF field to x > 0.9 and the HFM field to x ≥ 0.55. The topology of the simulated phase diagram compares favorably with experiments but suggests that the nature of some phase boundaries should be reexamined from both experimental and computational perspectives.

  10. CIV VUV FPI Interferometer for Transition Region Magnetography

    NASA Technical Reports Server (NTRS)

    Gary, G. A.

    2005-01-01

    Much in the same way photonics harnesses light for engineering and technology applications, solar physics harnesses light for the remote sensing of the sun. In photonics the vacuum ultraviolet region offers shorter wavelength and higher energies per photon, while in solar physics the VUV allows the remote sensing of the upper levels of the solar atmosphere where magnetic fields dominate the physics. Understanding solar magnetism is a major aim for astrophysics and for understanding solar-terrestrial interaction. The poster is on our instrument development program for a high-spectral-resolution, high-finesse, Vacuum Ultraviolet Fabry-Perot Interferometer (VUV FPI) for obtaining narrow-passband images, magnetograms, and Dopplergrams of the transition region emission line of CIV (155nm). The poster will cover how the V W interferometer will allow us to understand solar magnetism, what is special about the MSFC VUV FPI, and why the University of Toronto F2 eximer has been of particular value to this program.

  11. On the Magnetic Structure of the Solar Transition Region

    NASA Astrophysics Data System (ADS)

    Judge, Philip; Centeno, Rebecca

    2008-11-01

    We examine the hypothesis that cool loops dominate emission from solar transition region plasma below temperatures of 2 × 105 K. We compare published VAULT images of H Lyα, a lower transition region line, with nearly contemporaneous magnetograms from Kitt Peak, obtained during the second flight (VAULT-2) on 2002 June 14. The measured surface fields and potential extrapolations suggest that there are too few short loops and that Lyα emission is associated with the base regions of longer, coronal loops. VAULT-2 data of network boundaries have an asymmetry on scales larger than supergranules, also indicating an association with long loops. We complement the Kitt Peak data with very sensitive vector polarimetric data from the spectropolarimeter on board Hinode to determine the influence of very small magnetic concentrations on our analysis. From these data, two classes of behavior are found. Within the cores of strong magnetic flux concentrations (>5 × 1018 Mx) associated with active network and plage, small-scale mixed fields are absent, and any short loops can connect just the peripheries of the flux to cell interiors. Core fields return to the surface via longer, most likely coronal, loops. In weaker concentrations, short loops can connect concentrations and produce mixed fields within network boundaries, as suggested by Dowdy and colleagues. The VAULT-2 data that we examined are associated with strong concentrations. We conclude that the cool-loop model applies only to a small fraction of the VAULT-2 emission, but we cannot discount a significant role for cool loops in quieter regions. We suggest a physical picture for how network Lyα emission may occur through the cross-field diffusion of neutral atoms from chromospheric into coronal plasma.

  12. The structure of the static corona and transition region

    NASA Technical Reports Server (NTRS)

    Antiochos, S. K.; Noci, G.

    1986-01-01

    Static models of coronal loops are investigated. For loops that are low-lying with heights above the chromosphere below about 5000 km, it is shown that a new type of solution appears to the static equations, in addition to the well-known coronal loop solution. The new solution is characterized by a maximum plasma temperature less than about 100,000 K. The structure and properties of these cool solutions are discussed. The differential emission measure Q(T) expected for a magnetic arcade, which must naturally contain both hot and cool loops, is calculated. It is shown that the cool loops have a dramatic effect on the form of Q(T) in the lower transition region. In particular, they can account for the observed rise in Q at low T, which has long been thought to be incompatible with the static-loop model. Finally, the implications of the cool loops on other observations of both the solar and stellar coronae and transition regions are discussed.

  13. TRANSITION REGION EMISSION FROM SOLAR FLARES DURING THE IMPULSIVE PHASE

    SciTech Connect

    Johnson, H.; Raymond, J. C.; Murphy, N. A.; Suleiman, R.; Giordano, S.; Ko, Y.-K.; Ciaravella, A.

    2011-07-10

    There are relatively few observations of UV emission during the impulsive phases of solar flares, so the nature of that emission is poorly known. Photons produced by solar flares can resonantly scatter off atoms and ions in the corona. Based on off-limb measurements by the Solar and Heliospheric Observatory/Ultraviolet Coronagraph Spectrometer, we derive the O VI {lambda}1032 luminosities for 29 flares during the impulsive phase and the Ly{alpha} luminosities of 5 flares, and we compare them with X-ray luminosities from GOES measurements. The upper transition region and lower transition region luminosities of the events observed are comparable. They are also comparable to the luminosity of the X-ray emitting gas at the beginning of the flare, but after 10-15 minutes the X-ray luminosity usually dominates. In some cases, we can use Doppler dimming to estimate flow speeds of the O VI emitting gas, and five events show speeds in the 40-80 km s{sup -1} range. The O VI emission could originate in gas evaporating to fill the X-ray flare loops, in heated chromospheric gas at the footpoints, or in heated prominence material in the coronal mass ejection. All three sources may contribute in different events or even in a single event, and the relative timing of UV and X-ray brightness peaks, the flow speeds, and the total O VI luminosity favor each source in one or more events.

  14. Measuring the glass transition temperature of EPDM roofing materials: Comparison of DMA, TMA, and DSC techniques

    SciTech Connect

    Paroli, R.M.; Penn, J.

    1994-09-01

    Two ethylene-propylene-diene monomer (EPDM) roofing membranes were aged at 100 C for 7 and 28 days. The T{sub g} of these membranes was then determined by dynamic mechanical analysis (DMA), thermomechanical analysis (TMA), and differential scanning calorimetry (DSC) and the results compared. It was found that: (1) T{sub g} data can be obtained easily using the DMA and TMA techniques. The DSC method requires greater care due to the broad step change in the baseline which is associated with heavily plasticized materials. (2) The closest correspondence between techniques was for TMA and DSC (half-height). The latter, within experimental error, yielded the same glass transition temperature before and after heat-aging. (3) The peak maxima associated with tan{delta} and E{double_prime} measurements should be cited with T{sub g} values as significant differences can exist. (4) The T{sub g}(E{double_prime}) values were closer to the T{sub g}(TMA) and T{sub g}(DSC) data than were the T{sub g}(tan{delta}) values. Data obtained at 1 Hz (or possibly less) should be used when making comparisons based on various techniques. An assessment of T{sub g} values indicated that EPDM 112 roofing membrane is more stable than the EPDM 111 membrane. The T{sub g} for EPDM 112 did not change significantly with heat-aging for 28 days at 130 C.

  15. Study of glass transition temperature (Tg) of novel stress-sensitive composites using molecular dynamic simulation

    NASA Astrophysics Data System (ADS)

    Koo, B.; Liu, Y.; Zou, J.; Chattopadhyay, A.; Dai, L. L.

    2014-09-01

    This study investigates the glass transition temperature (Tg) of novel stress-sensitive composites capable of detecting a damage precursor using molecular dynamics (MD) simulations. The molecular structures of a cross-linked epoxy network (which consist of epoxy resin, hardener and stress-sensitive material) have been simulated and experimentally validated. The chemical constituents of the molecular structures are di-glycidyl ether of bisphenol F (DGEBF: epoxy resin), di-ethylene tri-amine (DETA: hardener) and tris-(cinnamoyloxymethyl)-ethane (TCE: stress-sensitive material). The cross-linking degree is varied by manipulating the number of covalent bonds through tuning a cutoff distance between activated DGEBF and DETA during the non-equilibrium MD simulation. A relationship between the cross-linking degree and Tgs has been studied numerically. In order to validate a proposed MD simulation framework, MD-predicted Tgs of materials used in this study have been compared to the experimental results obtained by the differential scanning calorimetry (DSC). Two molecular models have been constructed for comparative study: (i) neat epoxy (epoxy resin with hardener) and (ii) smart polymer (neat epoxy with stress-sensitive material). The predicted Tgs show close agreement with the DSC results.

  16. Low-Cost, High Glass-Transition Temperature, Thermosetting Polyimide Developed

    NASA Technical Reports Server (NTRS)

    Chuang, Kathy C.

    1999-01-01

    PMR-15 polyimide, developed in the mid-1970's at the NASA Lewis Research Center, is recognized as a state-of-the-art high-temperature resin for composite applications in the temperature range of 500 to 550 F (260 to 288 C). PMR-15 offers easy processing and good property retention at a reasonable cost. For these reasons, it is widely used in both military and commercial aircraft engine components. Traditionally, polyimide composites have been designed for long-term use at 500 to 600 F over thousands of hours. However, new applications in reusable launch vehicles (RLV's) require lightweight materials that can perform for short times (tens of hours) at temperatures between 800 and 1000 F (425 and 538 C). Current efforts at Lewis are focused on raising the use temperature of polyimide composites by increasing the glass-transition temperature of the matrix resins. Achieving this dramatic increase in the upper use temperature without sacrificing polymer and composite processability is a major technical challenge.

  17. Length Scales of Local Glass Transition Temperature Gradients Near Soft and Hard Polymer-Polymer Interfaces

    NASA Astrophysics Data System (ADS)

    Baglay, Roman; Roth, Connie

    Polymer-polymer interfaces are ubiquitous in polymer blends and block copolymers, while opening up another avenue for the study of interfacial perturbations to the local glass transition temperature Tg(z). We have previously reported the full local Tg(z) profile across a glassy-rubbery polymer interface between polystyrene (PS) and poly(n-butyl methacrylate) (PnBMA), an 80 K difference in bulk Tg [Baglay & Roth, J Chem Phys 2015, 143, 111101]. By using local fluorescence measurements, we revealed how the Tg(z) profile extends hundreds of nanometers away from the interface showing an asymmetric behavior penetrating deeper into the glassy PS side relative to the composition profile. Here, we extend these measurements to investigate how the local Tg profile in PS varies when in contact with a variety of immiscible polymers whose Tgs vary between +90 K and -80 K relative to the bulk Tg of PS, so-called hard vs. soft confinement. The data reveal that the onset of local Tg deviation from bulk in PS occurs at two distinct length scales, which depend on whether PS is the low Tg component (hard confinement) or the high Tg component (soft confinement). In addition, we explore the influence of finite system size on the range of dynamics by the introduction of periodic boundary conditions, as is commonly encountered in computer simulations or block copolymer systems.

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

    NASA Astrophysics Data System (ADS)

    Qin, Hui; Liu, Dan; Wang, Tao

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

  19. Using Combined Computational Techniques to Predict the Glass Transition Temperatures of Aromatic Polybenzoxazines

    PubMed Central

    Mhlanga, Phumzile; Wan Hassan, Wan Aminah; Hamerton, Ian; Howlin, Brendan J.

    2013-01-01

    The Molecular Operating Environment software (MOE) is used to construct a series of benzoxazine monomers for which a variety of parameters relating to the structures (e.g. water accessible surface area, negative van der Waals surface area, hydrophobic volume and the sum of atomic polarizabilities, etc.) are obtained and quantitative structure property relationships (QSPR) models are formulated. Three QSPR models (formulated using up to 5 descriptors) are first used to make predictions for the initiator data set (n = 9) and compared to published thermal data; in all of the QSPR models there is a high level of agreement between the actual data and the predicted data (within 0.63–1.86 K of the entire dataset). The water accessible surface area is found to be the most important descriptor in the prediction of Tg. Molecular modelling simulations of the benzoxazine polymer (minus initiator) carried out at the same time using the Materials Studio software suite provide an independent prediction of Tg. Predicted Tg values from molecular modelling fall in the middle of the range of the experimentally determined Tg values, indicating that the structure of the network is influenced by the nature of the initiator used. Hence both techniques can provide predictions of glass transition temperatures and provide complementary data for polymer design. PMID:23326419

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

    PubMed

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

    2014-01-01

    The purpose of this paper was to investigate the relaxation behavior of amorphous hesperetin (HRN), using dielectric spectroscopy, and assessment of its crystallization kinetics above glass transition temperature (Tg ). Amorphous HRN exhibited both local (β-) and global (α-) relaxations. β-Relaxation was observed below Tg , whereas α-relaxation prominently emerged above Tg . β-Relaxation was found to be of Johari-Goldstein type and was correlated with α-process by coupling model. Secondly, isothermal crystallization experiments were performed at 363 K (Tg + 16.5 K), 373 K (Tg + 26.5 K), and 383 K (Tg + 36.5 K). The kinetics of crystallization, obtained from the normalized dielectric strength, was modeled using the Avrami model. Havriliak-Negami (HN) shape parameters, αHN and αHN .βHN , were analyzed during the course of crystallization to understand the dynamics of amorphous phase during the emergence of crystallites. HN shape parameters indicated that long range (α-like) were motions affected to a greater extent than short range (β-like) motions during isothermal crystallization studies at all temperature conditions. The variable behavior of α-like motions at different isothermal crystallization temperatures was attributed to evolving crystallites with time and increase in electrical conductivity with temperature. PMID:24186540

  1. A novel powder sample holder for the determination of glass transition temperatures by DMA.

    PubMed

    Mahlin, Denny; Wood, John; Hawkins, Nicholas; Mahey, Jas; Royall, Paul G

    2009-04-17

    The use of a new sample holder for dynamic mechanical analysis (DMA) as a means to characterise the Tg of powdered hydroxypropyl methyl cellulose (HPMC) has been investigated. A sample holder was constructed consisting of a rectangular stainless steel container and a lid engineered to fit exactly within the walls of the container when clamped within a TA instruments Q800 DMA in dual cantilever configuration. Physical mixtures of HPMC (E4M) and aluminium oxide powders were placed in the holder and subjected to oscillating strains (1 Hz, 10 Hz and 100 Hz) whilst heated at 3 degrees C/min. The storage and loss modulus signals showed a large reduction in the mechanical strength above 150 degrees C which was attributed to a glass transition. Optimal experimental parameters were determined using a design of experiment procedure and by analysing the frequency dependence of Tg in Arrhenius plots. The parameters were a clamping pressure of 62 kPa, a mass ratio of 0.2 HPMC in aluminium oxide, and a loading mass of either 120 mg or 180 mg. At 1 Hz, a Tg of 177+/-1.2 degrees C (n=6) for powdered HPMC was obtained. In conclusion, the new powder holder was capable of measuring the Tg of pharmaceutical powders and a simple optimization protocol was established, useful in further applications of the DMA powder holder. PMID:19167475

  2. Ionic liquids and their bases: Striking differences in the dynamic heterogeneity near the glass transition

    PubMed Central

    Grzybowska, K.; Grzybowski, A.; Wojnarowska, Z.; Knapik, J.; Paluch, M.

    2015-01-01

    Ionic liquids (ILs) constitute an active field of research due to their important applications. A challenge for these investigations is to explore properties of ILs near the glass transition temperature Tg, which still require our better understanding. To shed a new light on the issues, we measured ILs and their base counterparts using the temperature modulated calorimetry. We performed a comparative analysis of the dynamic heterogeneity at Tg for bases and their salts with a simple monoatomic anion (Cl–). Each pair of ionic and non-ionic liquids is characterized by nearly the same chemical structure but their intermolecular interactions are completely different. We found that the size of the dynamic heterogeneity of ILs near Tg is considerably smaller than that established for their dipolar counterparts. Further results obtained for several other ILs near Tg additionally strengthen the conclusion about the relatively small size of the dynamic heterogeneity of molecular systems dominated by electrostatic interactions. Our finding opens up new perspectives on designing different material properties depending on intermolecular interaction types. PMID:26582136

  3. Linking high-pressure structure and density of albite liquid near the glass transition

    NASA Astrophysics Data System (ADS)

    Gaudio, Sarah J.; Lesher, Charles E.; Maekawa, Hideki; Sen, Sabyasachi

    2015-05-01

    The pressure-induced densification of NaAlSi3O8 liquid is determined following annealing immediately above the glass transition and upon quenching from superliquidus temperatures. High-field 27Al magic-angle-spinning NMR spectroscopy is used to investigate the corresponding changes in Al coordination environment that accompany the densification. We show that samples synthesized by quenching from superliquidus temperatures record lower fictive pressures (Pf) than annealed samples at the same nominal load and have lower recovered densities and average Al coordination number. Accounting for differences in Pf brings melt-quench and annealed samples into excellent agreement. The proportion of [5]Al increases from ∼3% to 29% and [6]Al from 0% to 8% between 1.8 and 7.2 GPa. The production of high-coordinated Al ([5]Al + [6]Al) with pressure is most dramatic above 3 GPa. Changes in network topology and structural disorder as revealed by the high-field 27Al NMR spectra provide new insights into the structural mechanisms of densification of the albite liquid. We posit that it is an overall weakening of the network structure on compression that is largely responsible for the anomalous pressure dependence of the transport properties observed for this liquid below ∼5 GPa.

  4. Effect of Hydrogenation on the Glass Transition Temperatures of Novel Ring-Opened Polynorbornenes

    NASA Astrophysics Data System (ADS)

    Burns, Adam; Li, Sheng; Register, Richard

    2013-03-01

    Ring-opening metathesis polymerization (ROMP) of norbornene-type monomers has been demonstrated as a facile way to produce block copolymers incorporating semicrystalline, glassy, and rubbery blocks. Of particular interest are block copolymers, made by ROMP, with thermoplastic elastomeric properties. For this application we seek blocks with glass transition temperatures (Tg) in excess of 100 oC. To this end, novel substituted norbornene-type monomers with large, rigid substituents have been investigated. A key consequence of the ROMP mechanism is that unsaturation in the monomer is preserved in the polymer. Unsaturation in the polymer backbone is susceptible to degradation; therefore, hydrogenation is required to enhance the long-term stability of these polymers. Hydrogenation can also have a significant impact on the thermal behavior. To investigate this, we have synthesized ROMP polymers of 5-phenyl-2-norbornene and 5-cyclohexyl-2-norbornene. Hydrogenation yielded derivatives with saturated backbones. This series of polymers provides a systematic study on the influence of hydrogenation on the Tg of glassy ROMP polymers. We find that saturation of the side group increases the Tg by 14 oC, irrespective of backbone saturation. Conversely, saturation of the backbone reduces Tg by 17 oC for both aromatic and cycloaliphatic side groups. When compared to analogous studies on other ROMP polymers, it becomes clear that these trends are difficult to predict, highlighting the importance of experimental measurements.

  5. Structure-to-glass transition temperature relationships in high temperature stable condensation polyimides

    NASA Technical Reports Server (NTRS)

    Alston, W. B.; Gratz, R. F.

    1985-01-01

    The presence of a hexafluoroisopropylidene (6F) connecting group in aryl dianhydrides used to prepare aromatic condensation polyimides provides high glass transition temperature (T sub g) polyimides with excellent thermo-oxidative stability. The purpose of this study was to determine if a trifluorophenyl-ethylidene (3F) connecting group would have a similar effect on the T sub g of aromatic condensation polyimides. A new dianhydride containing the 3F connecting group was synthesized. This dianhydride and an aromatic diamine also containing the 3F connecting group were used together and in various combinations with known diamines or known dianhydrides, respectively, to prepare new 3F containing condensation polyimides. Known polyimides, including some with the 6F connecting linkage, were also prepared for comparison purposes. The new 3F containing polymers and the comparison polymers were prepared by condensation polymerization via the traditional amic-acid polymerization method in N,N-dimethylacetamide solvent. The solutions were characterized by determining their inherent viscosities and then were thermally converted into polyimide films under nitrogen atmosphere at 300 to 500 C, usually 350 C. The T sub g's of the films and resin discs were then determined by thermomechanical analysis and were correlated as a function of the final processing temperatures of the films and resin discs. The results showed that similarities existed in the T sub g's depending on the nature of the connecting linkage in the monomers used to prepare the condensation polyimides.

  6. Glass Transition of Polystyrene Thin Films on Silicon Wafer Measured by Dynamic Mechanical Analysis and Ellipsometry

    NASA Astrophysics Data System (ADS)

    Jackson, Catheryn; Lan, Tian; Caporale, Stefan; Torkelson, John

    Measuring the glass transition temperature, Tg, of polymer films in the thickness range of 20-500 nm is non-routine but commercially important for polymer films used in applications such as membranes and electronic circuit boards. Various specialized methods have been used or developed to determine Tg in thin films, including thermal ellipsometry and many others. Differential scanning calorimetry (DSC) is a more conventional method that has been used to measure Tg, but since the thin films must be scraped from the wafer, consolidation and annealing can occur in the pan and may negate effects due to film thickness. Here we report results for polystyrene (PS) spin coated on silicon wafers in the range of 20-500 nm using a benchtop dynamic mechanical analyzer (DMA) in the 3-point bending mode. For the DMA, the peak tan δ temperature is related to the polymer Tg and effects due to confinement as a function of film thickness are compared to literature values. We use thermal ellipsometry as a control method to measure film thickness and Tg in parallel. Low level additives present in commercial PS were observed to strongly affect the results for thin films and are described.

  7. Morphology and Mechanical Properties of Poly(Ethylene Terephthalate) Stretched Above the Glass Transition Temperature

    NASA Astrophysics Data System (ADS)

    Todorov, Lyudmil V.; Viana, Júlio C.

    2007-04-01

    This study presents an experimental investigation into the development of the strain-induced morphology of amorphous poly(ethylene terephthalate), PET, stretched above its glass transition temperature. The present work aims at: i) defining the most important processing parameters that govern the structure formation and its significance; ii) characterising the mechanical properties of uniaxial stretched glassy PET, as an approach for industrial stretch-blow moulding techniques; iii) establishing structure-properties relationships. Compression moulded amorphous PET was uniaxial stretched with variations of following stretching parameters: stretching temperature, Tst, stretching velocity, Vst, and stretching ratio, λst, that were varied in two levels according to a L8 Taguchi orthogonal array. The developed morphologies were observed by differential scanning calorimetry (DSC), birefringence and Wide-Angle X-ray Scattering (WAXS). The mechanical behaviour was assessed in tensile testing at 15 mm.min-1 and room temperature. The results were treated by a statistical ANOVA tool. A strong thermal and mechanical coupling is evidenced in the stretching process, significantly influencing the morphology development. The main stretching parameters controlling microstructure formation were defined. The relationships between the microstructure and mechanical properties were established too.

  8. Ionic liquids and their bases: Striking differences in the dynamic heterogeneity near the glass transition

    NASA Astrophysics Data System (ADS)

    Grzybowska, K.; Grzybowski, A.; Wojnarowska, Z.; Knapik, J.; Paluch, M.

    2015-11-01

    Ionic liquids (ILs) constitute an active field of research due to their important applications. A challenge for these investigations is to explore properties of ILs near the glass transition temperature Tg, which still require our better understanding. To shed a new light on the issues, we measured ILs and their base counterparts using the temperature modulated calorimetry. We performed a comparative analysis of the dynamic heterogeneity at Tg for bases and their salts with a simple monoatomic anion (Cl-). Each pair of ionic and non-ionic liquids is characterized by nearly the same chemical structure but their intermolecular interactions are completely different. We found that the size of the dynamic heterogeneity of ILs near Tg is considerably smaller than that established for their dipolar counterparts. Further results obtained for several other ILs near Tg additionally strengthen the conclusion about the relatively small size of the dynamic heterogeneity of molecular systems dominated by electrostatic interactions. Our finding opens up new perspectives on designing different material properties depending on intermolecular interaction types.

  9. Self-similar magnetic structures during the vortex-glass to vortex-liquid transition of type II superconductors

    NASA Astrophysics Data System (ADS)

    Krasnyuk, I. B.; Taranets, R. M.; Yurchenko, V. M.

    2011-04-01

    We examine the response to an external magnetic field by a multi-layer superconductor with an electrical resistance ρff(b)αbσ, where b is the dimensionless magnetic induction and σ is a parameter characterizing the ratio of the pinning activation energy to the energy of thermal fluctuations. When σ > 1 the sample is in the vortex glass phase, when 0 < σ < 1, it is in the vortex liquid phase, and a vortex glass to vortex liquid phase transition takes place at σ = 1. In the vortex glass phase, the magnetic field penetrates into the superconductor in the form of a self-similar wave. At all times it penetrates to a finite depth and its front moves at a finite velocity which depends on the parameters of the problem, such as the rate of pumping by the external magnetic field. In the vortex liquid phase the magnetic field penetrates to an infinite depth. Thus, the magnetic field penetrates to an infinite depth in the superconductor during a transition from the vortex glass phase into the vortex liquid phase.

  10. Experimental search for the chiral glass transition in a ceramic Bi2 Sr2 Ca Cu2 O8 sample

    NASA Astrophysics Data System (ADS)

    Papadopoulou, E. L.; Nordblad, P.; Svedlindh, P.

    2004-08-01

    The nonlinear susceptibility of a melt-cast Bi2Sr2CaCu2O8 sample, displaying both the paramagnetic Meissner effect and magnetic aging, has been studied experimentally. The presence of magnetic aging in this sample proves that the spontaneous orbital magnetic moments exhibit correlated and frustrated dynamics at low temperatures. The possible existence of a chiral-glass phase transition was investigated by extracting a quantity corresponding to the order parameter susceptibility of the glass phase. It is shown that the expected divergent behavior of this quantity is hampered by relaxation effects and that the sample is out-of-equilibrium already at temperatures slightly below the superconducting transition temperature (Tc) . Time dependent magnetization experiments indicate that the magnetic relaxation at temperatures close to but below Tc is due to isolated orbital magnetic moments, not yet being part of the collective orbital moment state that develops at slightly lower temperatures.

  11. Structural features of single crystals of LuB12 upon a transition to the cage-glass phase

    NASA Astrophysics Data System (ADS)

    Bolotina, N. B.; Verin, I. A.; Shitsevalova, N. Yu.; Filippov, V. B.; Sluchanko, N. E.

    2016-03-01

    The unit-cell parameters of dodecaboride LuB12, which undergoes a transition to the cage-glass phase, have been determined for the first time in the temperature range of 50-75 K by X-ray diffraction, and the single-crystal structure of this compound is established at 50 K. Nonlinear changes in the unit-cell parameters correspond to anomalies in the physical properties near the glass-transition temperature T* ~ 50-70 K. This compound has cubic symmetry at room temperature, and it is reduced to tetragonal symmetry at lower temperatures. Based on the X-ray diffraction data and relying on the physical properties of the crystals, the structure model, in which a small part (~15%) of Lu atoms are displaced from the 2 a sites at the centers of the B24 cuboctahedra to the 16 n sites of sp. gr. I4/ mmm, seems preferable.

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

    NASA Astrophysics Data System (ADS)

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

    2014-03-01

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

  13. Glass electrolyte composition

    DOEpatents

    Kucera, Gene H.; Roche, Michael F.

    1985-01-01

    An ionically conductive glass is disclosed for use as electrolyte in a high temperature electrochemical cell, particularly a cell with sodium anode and sulfur cathode. The glass includes the constituents Na.sub.2 O, ZrO.sub.2, Al.sub.2 O.sub.3 and SiO.sub.2 in selected proportions to be a single phase solid solution substantially free of crystalline regions and undissolved constituents. Other advantageous properties are an ionic conductivity in excess of 2.times.10.sup.-3 (ohm-cm).sup.-1 at 300.degree. C. and a glass transition temperature in excess of 500.degree. C.

  14. Glass electrolyte composition

    DOEpatents

    Kucera, G.H.; Roche, M.F.

    1985-01-08

    An ionically conductive glass is disclosed for use as electrolyte in a high temperature electrochemical cell, particularly a cell with sodium anode and sulfur cathode. The glass includes the constituents Na/sub 2/O, ZrO/sub 2/, Al/sub 2/O/sub 3/ and SiO/sub 2/ in selected proportions to be a single phase solid solution substantially free of crystalline regions and undissolved constituents. Other advantageous properties are an ionic conductivity in excess of 2 x 10/sup -3/ (ohm-cm)/sup -1/ at 300/sup 0/C and a glass transition temperature in excess of 500/sup 0/C.

  15. Physical factors affecting the storage stability of freeze-dried interleukin-1 receptor antagonist: glass transition and protein conformation.

    PubMed

    Chang, B S; Beauvais, R M; Dong, A; Carpenter, J F

    1996-07-15

    The effects of glass transition of, and protein conformation in, the dried solid on the storage stability of freeze-dried recombinant human interleukin-1 receptor antagonist (rhIL-1ra) were examined. Glass transition is a temperature-dependent phenomenon. Amorphous materials become hard and brittle at temperatures below their characteristic glass transition temperatures (Tg) such that diffusion of molecules along the matrix is not sufficient to cause large-scale structural changes. To ascertain the importance of the glass transition in protein storage stability, we compared 10 different lyophilized rhIL-1ra formulations, with Tgs ranging from 20 to 56 degrees C, during several weeks of storage at temperatures above and below the samples' Tgs. Protein degradation, both deamidation and aggregation, was greatly accelerated at temperatures above Tg, but for some formulations also arose below Tg. Thus, storage of dried proteins below the Tg is necessary but not sufficient to ensure long-term stability. To examine the effects of protein structure in the dried solid, we prepared formulations with various sucrose concentrations, all of which had a Tg = 66 +/- 2.5 degrees C. With infrared spectroscopy, we determined that the protein lyophilized with /=5% sucrose, conformational change was inhibited during lyophilization. When stored at 50 degrees C, degradation of the freeze-dried protein varied inversely with sucrose concentration. These results indicate that structural changes arising during the lyophilization process led to damage during subsequent storage, even if the storage temperature was less than the Tg. Together the results of these studies document that to obtain optimum stability of dried rhIL-1ra it was necessary to inhibit conformational change during lyophilization and to store at temperatures below the Tg of the dried formulation. PMID:8660705

  16. 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

  17. Coupling of gelation and glass transition in a biphasic colloidal mixture--from gel-to-defective gel-toglass

    NASA Astrophysics Data System (ADS)

    Cheng, He; Jia, Di; Han, Charles

    The state transition from gel to glass is studied in a biphasic mixture of polystyrene core/poly (N-isopropylacrylamide) shell (CS) microgels and sulfonated polystyrene (PSS) particles. At 35 °C, the interaction between CS is due to short-range Van der Waals attraction while that between PSS is from long-range electrostatic repulsion. During variation of the relative ratio of the two species at a fixed apparent total volume fraction, the mixture exhibits a gel-to-defective gel-to-glass transition. When small amounts of PSS are introduced into the CS gel network, some of them are kinetically trapped, causing a change in its fractal structure, and act as defects to weaken the macroscopic gel strength. An increase of PSS content in the mixture promotes the switch from gel to defective gel, e . g . , the typical two-step yielding gel merges into one-step yielding. This phenomenon is an indication that inter-cluster bond breakage coincides with intra-cluster bond fracture. As the relative volume fraction of PSS exceeds a critical threshold, the gel network can no longer be formed; hence, the mixture exhibits characteristics of glass. A state diagram of the biphasic mixture is constructed, and the landscape of the different transitions will be described in future studies The financial support from the National Basic Research Program of China (973 Program, 2012CB821500) is gratefully acknowledged.

  18. Effect of polymer-nanoparticle interactions on the glass transition dynamics and the conductivity mechanism in polyurethane titanium dioxide nanocomposites

    SciTech Connect

    Polyzos, Georgios; Tuncer, Enis; Agapov, Alexander L; Stevens, Derrick; Sokolov, Alexei P; Kidder, Michelle; Jacobs,; Koerner, Hilmar; Vaia, Richard; More, Karren Leslie; Sauers, Isidor

    2012-01-01

    We report on the glass transition dynamics and the conductivity properties of a nanodielectric system composed of pre-synthesized TiO{sub 2} nanoparticles embedded in thermoplastic polyurethane. Increase of TiO{sub 2} loading results in enhanced segmental mobility of the composites and less steep temperature dependence, i.e., lower fragility index. The decrease in the fragility index and glass transition temperature is discussed based on the FTIR results. We observe different behavior of conductivity for temperatures above and below the glass transition temperature. At high temperatures the composites exhibit conductivity values more than 2 orders of magnitude higher than those in the pristine matrix. At the same time, at sub-Tg temperatures composites are characterized by superior electrical insulation properties compared to pristine matrix material. Such drastic temperature dependence of the conductivity/insulating ability of the flexible and light-weight, low-Tg composite material can be utilized in various applications including sensing and temperature switching materials.

  19. Glass-Transition Temperature Profile Measured in a Wood Cell Wall Using Scanning Thermal Expansion Microscope (SThEM)

    NASA Astrophysics Data System (ADS)

    Antoniow, J. S.; Maigret, J.-E.; Jensen, C.; Trannoy, N.; Chirtoc, M.; Beaugrand, J.

    2012-11-01

    This study aims to assess the in situ spatial distribution of glass-transition temperatures ( T g) of the main lignocellulosic biopolymers of plant cell walls. Studies are conducted using scanning thermal expansion microscopy to analyze the cross-section of the cell wall of poplar. The surface topography is mapped over a range of probe-tip temperatures to capture the change of thermal expansion on the sample surface versus temperature. For different temperature values chosen between 20 °C and 250 °C, several quantitative mappings were made to show the spatial variation of the thermal expansion. As the glass transition affects the thermal expansion coefficient and elastic modulus considerably, the same data line of each topography image was extracted to identify specific thermal events in their topographic evolution as a function of temperature. In particular, it is shown that the thermal expansion of the contact surface is not uniform across the cell wall and a profile of the glass-transition temperature could thus be evidenced and quantified corresponding to the mobility of lignocellulosic polymers having a role in the organization of the cell wall structures.

  20. The use of transition region characteristics to improve the numerical simulation of heat transfer in bypass transitional flows

    NASA Technical Reports Server (NTRS)

    Simon, Frederick F.

    1993-01-01

    A method is presented for improving the numerical prediction of bypass transition heat transfer on a flat plate in a high-disturbance environment with zero or favorable pressure gradient. The method utilizes low Reynolds number k-epsilon turbulence models in combination with the characteristic parameters of the transition region. The parameters representing the characteristics of the transition region used are the intermittency, transition length and turbulent spot properties. An analysis is made of the transition length in terms of turbulent spot variables. The nondimensional spot formation rate, required for the prediction of the transition length, is shown by the analysis to be a function of the spot spreading angle, the dimensionless spot velocity ratio and the dimensionless spot area ratio. The intermittency form of the k-epsilon equations were derived from conditionally averaged equations which have been shown to be an improvement over global-time-averaged equations for the numerical calculation of the transition region. The numerical predictions are in general good agreement with the experimental data and indicate the potential use of the method in accelerating flows. Turbulence models of the k-epsilon type are known to underpredict the transition length. The present work demonstrates how incorporating transition region characteristics improves the ability of two-equation turbulence models to simulate bypass transition for flat plates with potential application to turbine vanes and blades.

  1. Dissolved, Exsolved and Re-dissolved H2O in Volcanology: Rheology, Glass Transition, and Thermodynamics

    NASA Astrophysics Data System (ADS)

    Russell, K.; kennedy, B.; Giordano, D.; Friedlander, E. A.

    2012-12-01

    All natural magmas originate with dissolved H2O. All such magmas degas during transport and eruption. The presence, abundance, and state of H2O in magmas control phase relations and the transport properties of melts and magmas. For example, dissolved H2O lowers viscosity, lowers glass transition temperatures (Tg), and controls the temperature and nature of crystallization. The effects of exsolved water are also substantial in terms of modifying the bulk transport properties of the magma, facilitating egress of volatiles and, thus, promoting crystallization. Of great interest is the coupling this component (H2O) creates between the thermodynamic processes (i.e. cooling, crystallization, vesiculation) and the properties (i.e. density, viscosity) controlling the mechanical behaviour (i.e. flow and fracture) of magma during transport and eruption. The coupling allows for strong feedbacks between system variables. The component H2O also has a retrograde solubility in silicate melts wherein H2O solubility in the melt increases with decreasing T. Here, we explore some of the consequences of retrograde solubility of H2O for volcanic systems using a new preliminary experimental dataset. These data establish the 1-atmosphere solubility limits of H2O in silicic melt at volcanic temperatures and are complementary to the growing literature on the low pressure (<50 MPa) solubility of volatiles in silicate melts (e.g., Behrens et al. 2009; DiMatteo et al. 2004; Liu et al. 2005; Zhang 1999). We specifically look at the implications of these data, especially the retrograde solubility limits, for welding of pyroclastic deposits (e.g. ignimbrites, conduit fill, fall out). The cessation of welding and compaction processes in pyroclastic deposits is reached when deposits cool below Tg. However, the fact that H2O has a retrograde solubility means that inter- and intraclast water will be resorbed by vitric pyroclasts as the deposit cools (regardless of load). This has the immediate

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

    NASA Astrophysics Data System (ADS)

    Kern, Kristen Tulloch

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

  3. Shikimic acid ozonolysis kinetics of the transition from liquid aqueous solution to highly viscous glass.

    PubMed

    Steimer, Sarah S; Berkemeier, Thomas; Gilgen, Anina; Krieger, Ulrich K; Peter, Thomas; Shiraiwa, Manabu; Ammann, Markus

    2015-12-14

    Ageing of particulate organic matter affects the composition and properties of atmospheric aerosol particles. Driven by temperature and humidity, the organic fraction can vary its physical state between liquid and amorphous solid, or rarely even crystalline. These transitions can influence the reaction kinetics due to limitations of mass transport in such (semi-) solid states, which in turn may influence the chemical ageing of particles containing such compounds. We have used coated wall flow tube experiments to investigate the reaction kinetics of the ozonolysis of shikimic acid, which serves as a proxy for oxygenated, water-soluble organic matter and can form a glass at room temperature. Particular attention was paid to how the presence of water influences the reaction, since it acts a plasticiser and thereby induces changes in the physical state. We analysed the results by means of a traditional resistor model, which assumes steady-state conditions. The ozonolysis rate of shikimic acid is strongly increased in the presence of water, a fact we attribute to the increased transport of O3 and shikimic acid through the condensed phase at lower viscosities. The analysis using the resistor model suggests that the system undergoes both surface and bulk reaction. The second-order rate coefficient of the bulk reaction is 3.7 (+1.5/-3.2) × 10(3) L mol(-1) s(-1). At low humidity and long timescales, the resistor model fails to describe the measurements appropriately. The persistent O3 uptake at very low humidity suggests contribution of a self-reaction of O3 on the surface. PMID:26536455

  4. Localization and elasticity in entangled polymer liquids as a mesoscopic glass transition

    NASA Astrophysics Data System (ADS)

    Schweizer, Kenneth

    2010-03-01

    The reptation-tube model is widely viewed as the correct zeroth order model for entangled linear polymer dynamics under quiescent conditions. Its key ansatz is the existence of a mesoscopic dynamical length scale that prohibits transverse chain motion beyond a tube diameter of order 3-10 nm. However, the theory is phenomenological and lacks a microscopic foundation, and many fundamental questions remain unanswered. These include: (i) where does the confining tube field come from and can it be derived from statistical mechanics? (ii) what is the microscopic origin of the magnitude, and power law scaling with concentration and packing length, of the plateau shear modulus? (iii) is the tube diameter time-dependent? (iv) does the confinement field contribute to elasticity ? (v) do entanglement constraints have a finite strength? Building on our new force-level theories for the dynamical crossover and activated barrier hopping in glassy colloidal suspensions and polymer melts, a first principles self-consistent theory has been developed for entangled polymers. Its basic physical elements, and initial results that address the questions posed above, will be presented. The key idea is that beyond a critical degree of polymerization, the chain connectivity and excluded volume induced intermolecular correlation hole drives temporary localization on an intermediate length scale resulting in a mesoscopic ``ideal kinetic glass transition.'' Large scale isotropic motion is effectively quenched due to the emergence of chain length dependent entropic barriers. However, the barrier height is not infinite, resulting in softening of harmonic localization at large displacements, temporal increase of the confining length scale, and a finite strength of entanglement constraints which can be destroyed by applied stress.

  5. Computational modelling of large deformations in layered-silicate/PET nanocomposites near the glass transition

    NASA Astrophysics Data System (ADS)

    Figiel, Łukasz; Dunne, Fionn P. E.; Buckley, C. Paul

    2010-01-01

    Layered-silicate nanoparticles offer a cost-effective reinforcement for thermoplastics. Computational modelling has been employed to study large deformations in layered-silicate/poly(ethylene terephthalate) (PET) nanocomposites near the glass transition, as would be experienced during industrial forming processes such as thermoforming or injection stretch blow moulding. Non-linear numerical modelling was applied, to predict the macroscopic large deformation behaviour, with morphology evolution and deformation occurring at the microscopic level, using the representative volume element (RVE) approach. A physically based elasto-viscoplastic constitutive model, describing the behaviour of the PET matrix within the RVE, was numerically implemented into a finite element solver (ABAQUS) using an UMAT subroutine. The implementation was designed to be robust, for accommodating large rotations and stretches of the matrix local to, and between, the nanoparticles. The nanocomposite morphology was reconstructed at the RVE level using a Monte-Carlo-based algorithm that placed straight, high-aspect ratio particles according to the specified orientation and volume fraction, with the assumption of periodicity. Computational experiments using this methodology enabled prediction of the strain-stiffening behaviour of the nanocomposite, observed experimentally, as functions of strain, strain rate, temperature and particle volume fraction. These results revealed the probable origins of the enhanced strain stiffening observed: (a) evolution of the morphology (through particle re-orientation) and (b) early onset of stress-induced pre-crystallization (and hence lock-up of viscous flow), triggered by the presence of particles. The computational model enabled prediction of the effects of process parameters (strain rate, temperature) on evolution of the morphology, and hence on the end-use properties.

  6. An Ultrasonic Study on the Polyamorphic Transition in La/Ce-based Bulk Metallic Glass to 12 GPa

    NASA Astrophysics Data System (ADS)

    Qi, X.; Wang, X.; Chen, T.; Welch, D. O.; Jiang, J.; Li, B.

    2015-12-01

    Bulk metallic glasses (BMGs), also known as amorphous alloys, are one of the most promising materials in the 21st century. With their unique structures, BMGs are at the cutting edge of materials study for both commercial applications and fundamental studies. In the light of engineering applications, some metal-metal alloy BMGs are stronger than steels but able to be shaped and molded like plastics. As a new member of glass family, metallic glasses are also good models for studies of fundamental problems in condensed matter physics. Pressure-induced polyamorphism in Ce-based bulk metallic glasses have attracted interest in recent years. Ultrasonic measurements of the compressional and shear wave velocities not only provide critical information about their interatomic forces, but also offer a unique approach for precise determination of mass densities under pressure that are quite difficult to access by other methods. In this study, the acoustic velocities of La32Ce32Al16Ni5Cu15 bulk metallic glass were measured up to 12.3 GPa using ultrasonic interferometry in a multi-anvil apparatus at room temperature. Both compressional and shear waves exhibited softening behaviors at 0-4 GPa, followed by a continuous increase (stiffening) with pressures. Measurements under decompression exhibit a hysteretic behavior compared to that on compression. The mass density as a function of pressure revealed three different amorphous states and the transition pressures were accompanied by distinct changes in the pressure derivatives of elastic moduli. The interpretation of the residual densification and the softening/stiffening across the polyamorphic transition can be sought via the topological rearrangement of the solute-centered clusters in medium-range order and the possibility of 4f electron localization/delocalization in Ce.

  7. Comparison of some lead and non-lead based glass systems, standard shielding concretes and commercial window glasses in terms of shielding parameters in the energy region of 1 keV-100 GeV: A comparative study

    NASA Astrophysics Data System (ADS)

    Kurudirek, Murat; Özdemir, Yüksel; Şimşek, Önder; Durak, Rıdvan

    2010-12-01

    The effective atomic numbers, Z eff of some glass systems with and without Pb have been calculated in the energy region of 1 keV-100 GeV including the K absorption edges of high Z elements present in the glass. Also, these glass systems have been compared with some standard shielding concretes and commercial window glasses in terms of mean free paths and total mass attenuation coefficients in the continuous energy range. Comparisons with experiments were also provided wherever possible for glasses. It has been observed that the glass systems without Pb have higher values of Z eff than that of Pb based glasses at some high energy regions even if they have lower mean atomic numbers than Pb based glasses. When compared with some standard shielding concretes and commercial window glasses, generally it has been shown that the given glass systems have superior properties than concretes and window glasses with respect to the radiation-shielding properties, thus confirming the availability of using these glasses as substitutes for some shielding concretes and commercial window glasses to improve radiation-shielding properties in the continuous energy region.

  8. Spin-glass phase transition and behavior of nonlinear susceptibility in the Sherrington-Kirkpatrick model with random fields

    NASA Astrophysics Data System (ADS)

    Morais, C. V.; Zimmer, F. M.; Lazo, M. J.; Magalhães, S. G.; Nobre, F. D.

    2016-06-01

    The behavior of the nonlinear susceptibility χ3 and its relation to the spin-glass transition temperature Tf in the presence of random fields are investigated. To accomplish this task, the Sherrington-Kirkpatrick model is studied through the replica formalism, within a one-step replica-symmetry-breaking procedure. In addition, the dependence of the Almeida-Thouless eigenvalue λAT (replicon) on the random fields is analyzed. Particularly, in the absence of random fields, the temperature Tf can be traced by a divergence in the spin-glass susceptibility χSG, which presents a term inversely proportional to the replicon λAT. As a result of a relation between χSG and χ3, the latter also presents a divergence at Tf, which comes as a direct consequence of λAT=0 at Tf. However, our results show that, in the presence of random fields, χ3 presents a rounded maximum at a temperature T* which does not coincide with the spin-glass transition temperature Tf (i.e., T*>Tf for a given applied random field). Thus, the maximum value of χ3 at T* reflects the effects of the random fields in the paramagnetic phase instead of the nontrivial ergodicity breaking associated with the spin-glass phase transition. It is also shown that χ3 still maintains a dependence on the replicon λAT, although in a more complicated way as compared with the case without random fields. These results are discussed in view of recent observations in the LiHoxY1 -xF4 compound.

  9. Limb-specific autonomic dysfunction in complex regional pain syndrome modulated by wearing prism glasses.

    PubMed

    Moseley, G Lorimer; Gallace, Alberto; Di Pietro, Flavia; Spence, Charles; Iannetti, Gian Domenico

    2013-11-01

    In unilateral upper-limb complex regional pain syndrome (CRPS), the temperature of the hands is modulated by where the arms are located relative to the body midline. We hypothesized that this effect depends on the perceived location of the hands, not on their actual location, nor on their anatomical alignment. In 2 separate cross-sectional randomized experiments, 10 (6 female) unilateral CRPS patients wore prism glasses that laterally shifted the visual field by 20°. Skin temperature was measured before and after 9-minute periods in which the position of one hand was changed. Placing the affected hand on the healthy side of the body midline increased its temperature (Δ°C=+0.47 ± 0.14°C), but not if prism glasses made the hand appear to be on the body midline (Δ°C=+0.07 ± 0.06°C). Similarly, when prism glasses made the affected hand appear to be on the healthy side of the body midline, even though it was not, the affected hand warmed up (Δ°C=+0.28 ± 0.14°C). When prism glasses made the healthy hand appear to be on the affected side of the body midline, even though it was not, the healthy hand cooled down (Δ°C=-0.30 ± 0.15°C). Friedman's analysis of variance and Wilcoxon pairs tests upheld the results (P<0.01 for all). We conclude that, in CRPS, cortical mechanisms responsible for encoding the perceived location of the limbs in space modulate the temperature of the hands. PMID:23886518

  10. DEVELOPMENT OF GLASS COMPOSITIONS TO IMMOBILIZE ALKALI, ALKALINE EARTH, LANTHANIDE AND TRANSITION METAL FISSION PRODUCTS FROM NUCLEAR FUEL REPROCESSING

    SciTech Connect

    Marra, J.; Billings, A.

    2009-06-24

    The Advanced Fuel Cycle Initiative (AFCI) waste management strategy revolves around specific treatment of individual or groups of separated waste streams. A goal for the separations processes is to efficiently manage the waste to be dispositioned as high level radioactive waste. The Advanced Fuel Cycle Initiative (AFCI) baseline technology for immobilization of the lanthanide (Ln) and transition metal fission product (TM) wastes is vitrification into a borosilicate glass. A current interest is to evaluate the feasibility of vitrifying combined waste streams to most cost effectively immobilize the wastes resulting from aqueous fuel reprocessing. Studies showed that high waste loadings are achievable for the Ln only (Option 1) stream. Waste loadings in excess of 60 wt % (on a calcined oxide basis) were demonstrated via a lanthanide borosilicate (LaBS) glass. The resulting glasses had excellent relative durability as determined by the Product Consistency Test (PCT). For a combined Ln and TM waste stream glass (Option 2), noble metal solubility was found to limit waste loading. However, the measured PCT normalized elemental releases for this glass were at least an order of magnitude below that of Environmental Assessment (EA) glass. Current efforts to evaluate the feasibility of vitrifying combined Ln, TM, alkali (Cs is the primary radionuclide of concern) and alkaline earth (Sr is the primary radionuclide of concern) wastes (Option 3) have shown that these approaches are feasible. However, waste loading limitations with respect to heat load (Cs/Sr loading), molybdenum solubility and/or noble metal solubility will likely be realized and must be considered in determining the cost effectiveness of these approaches.

  11. Chaotic state to self-organized critical state transition of serrated flow dynamics during brittle-to-ductile transition in metallic glass

    NASA Astrophysics Data System (ADS)

    Wang, C.; Sun, B. A.; Wang, W. H.; Bai, H. Y.

    2016-02-01

    We study serrated flow dynamics during brittle-to-ductile transition induced by tuning the sample aspect ratio in a Zr-based metallic glass. The statistical analysis reveals that the serrated flow dynamics transforms from a chaotic state characterized by Gaussian-distribution serrations corresponding to stick-slip motion of randomly generated and uncorrelated single shear band and brittle behavior, into a self-organized critical state featured by intermittent scale-free distribution of shear avalanches corresponding to a collective motion of multiple shear bands and ductile behavior. The correlation found between serrated flow dynamics and plastic deformation might shed light on the plastic deformation dynamic and mechanism in metallic glasses.

  12. Molecular weight dependence of surface flow near the bulk glass transition temperature

    NASA Astrophysics Data System (ADS)

    Chai, Yu; Salez, Thomas; Benzaquen, Michael; Raphael, Elie; Forrest, James A.

    2014-03-01

    We present the study on molecular weight dependent sub-Tg surface dynamics of polymer thin films by using the Nano-step experiment [McGraw et al. Soft Matter 7, 7832 (2011)]. By varying the molecular weight, we are able to probe the surface dynamics of the free surface below Tg with the polymer size comparable to the surface depth. In particular, we define and use a correlation function to compare measured and calculated profiles to analyze the transition from the bulk flow to flow restricted to the surface region. Surprisingly, even for the polymers with Mw = 22,000 surface flow is still observed below the bulk Tg value. A numerical simulation of random walk is used to find the fraction of polymer of which all of the polymer segments are located in the free surface region. The simulation results indicate that there are still a significant fraction of polymer molecules where all segments are in the near free surface region. These molecules can undergo flow consistent with the experimental results.

  13. Enthalpy relaxation kinetics of Ge20Te(80-y)Sey far-infrared glasses in the glass transition range

    NASA Astrophysics Data System (ADS)

    Svoboda, Roman; Málek, Jiří

    2016-06-01

    Differential scanning calorimetry was used to study enthalpy relaxation kinetics of the Ge20Te(80-y)Sey infrared chalcogenide glasses for the compositional range y = 0-8. The relaxation behaviour was described in terms of the phenomenological Tool-Narayanaswamy-Moynihan (TNM) model. The direct curve-fitting procedure was used to determine the values of TNM parameters. Compositional evolution of the TNM parameters was interpreted with respect to the involved structural entities and their motions. Based on the joint Raman scattering study, the addition of Se leads to increased amount of edge-shared GeTe4-xSex tetrahedra. While the primary structural basis for the relaxation movements appears not to be affected by addition of Se (constant value of non-linearity), changes of the non-exponentiality parameter indicate increased structural variability occurring within the groups of directly interlinked tetrahedra, which were found to carry the main portion of relaxation movements. Increased activation energy was explained by the presence of significantly stronger Ge-Se bonds and increased amount of edge-shared tetrahedra.

  14. Glass transition and composite formation in InF3-containing oxyfluoroniobate system

    NASA Astrophysics Data System (ADS)

    Savchenko, N. N.; Ignatieva, L. N.; Marchenko, Yu. V.; Bouznik, V. M.

    2016-05-01

    The glasses in the system MnNbOF5-BaF2-InF3 have been firstly synthesized and studied. The thermal parameters of these glasses are analyzed. It was stated that glass of the composition 40MnNbOF5-40BaF2-20InF3 is the most thermal stable in the system under study. By X-ray analysis the compositions of the crystalline phases obtained at the glass thermal treatment were determined: the main phases are Ba3In2F12 and BaNbOF5. By Raman and IR spectra analysis it was stated that the networks of glasses in the system are built by the structural type of the glasses in NbO2F-BaF2 system: (NbOnFm) polyhedra joined oxygen bridges. Indium trifluoride forms InF6 polyhedra, which are embeded between oxyfluoroniobate ions, forming a common networks or forms its own layers from InF6 polyhedra. IR-spectroscopy method showed that at devitrification of the sample 30MnNbOF5-50BaF2-20InF3 the band position and shape change in going from glass state to crystalline. The bands in the range 900-700 cm-1 shift into the low-frequency range and transformed into narrow peaks characteristic for the crystalline state. It was determined that for this sample the IR-spectroscopy method fixes the presence of the crystalline phases at 340°C without time of exposure, despite the fact that X-ray analysis shows an amorphous state for this sample at the same temperature. It was suggested, that controlling the composition and conditions of annealing of the glasses it can be obtain the transparent glass-ceramics of definite composition.

  15. Fluctuating mobility generation and transport in glasses

    NASA Astrophysics Data System (ADS)

    Wisitsorasak, Apiwat; Wolynes, Peter G.

    2013-08-01

    In the context of the random first order transition theory we use an extended mode coupling theory of the glass transition that includes activated events to account for spatiotemporal structures in rejuvenating glasses. We numerically solve fluctuating dynamical equations for mobility and fictive temperature fields which capture both mobility generation through activated events and facilitation effects. Upon rejuvenating, a source of high mobility at a glass surface initiates a growth front of mobility which propagates into the unstable low mobility region. The speed of the front quantitatively agrees with experiments on the rejuvenation of ultrastable glasses, which “melt” from their surface.

  16. Photospheric electric current and transition region brightness within an active region

    NASA Technical Reports Server (NTRS)

    Deloach, A. C.; Hagyard, M. J.; Rabin, D.; Moore, R. L.; Smith, B. J., Jr.; West, E. A.; Tandberg-Hanssen, E.

    1984-01-01

    Distributions of vertical electrical current density J(z) calculated from vector measurements of the photospheric magnetic field are compared with ultraviolet spectroheliograms to investigate whether resistive heating is an important source of enhanced emission in the transition region. The photospheric magnetic fields in Active Region 2372 were measured on April 6 and 7, 1980 with the Marshall Space Flight Center vector magnetograph; ultraviolet wavelength spectroheliograms (L-alpha and N V 1239 A) were obtained with the UV Spectrometer and Polarimeter experiment aboard the Solar Maximum Mission satellite. Spatial registration of the J(z) (5 arcsec resolution) and UV (3 arcsec resolution) maps indicates that the maximum current density is cospatial with a minor but persistent UV enhancement, but there is little detected current associated with other nearby bright areas. It is concluded that, although resistive heating may be important in the transition region, the currents responsible for the heating are largely unresolved in the present measurements and have no simple correlation with the residual current measured on 5-arcsec scales.

  17. Humidity-dependent compression-induced glass transition of the air-water interfacial Langmuir films of poly(D,L-lactic acid-ran-glycolic acid) (PLGA).

    PubMed

    Kim, Hyun Chang; Lee, Hoyoung; Jung, Hyunjung; Choi, Yun Hwa; Meron, Mati; Lin, Binhua; Bang, Joona; Won, You-Yeon

    2015-07-28

    Constant rate compression isotherms of the air-water interfacial Langmuir films of poly(D,L-lactic acid-ran-glycolic acid) (PLGA) show a distinct feature of an exponential increase in surface pressure in the high surface polymer concentration regime. We have previously demonstrated that this abrupt increase in surface pressure is linked to the glass transition of the polymer film, but the detailed mechanism of this process is not fully understood. In order to obtain a molecular-level understanding of this behavior, we performed extensive characterizations of the surface mechanical, structural and rheological properties of Langmuir PLGA films at the air-water interface, using combined experimental techniques including the Langmuir film balance, X-ray reflectivity and double-wall-ring interfacial rheometry methods. We observed that the mechanical and structural responses of the Langmuir PLGA films are significantly dependent on the rate of film compression; the glass transition was induced in the PLGA film only at fast compression rates. Surprisingly, we found that this deformation rate dependence is also dependent on the humidity of the environment. With water acting as a plasticizer for the PLGA material, the diffusion of water molecules through the PLGA film seems to be the key factor in the determination of the glass transformation properties and thus the mechanical response of the PLGA film against lateral compression. Based on our combined results, we hypothesize the following mechanism for the compression-induced glass transformation of the Langmuir PLGA film; (1) initially, a humidified/non-glassy PLGA film is formed in the full surface-coverage region (where the surface pressure shows a plateau) during compression; (2) further compression leads to the collapse of the PLGA chains and the formation of new surfaces on the air side of the film, and this newly formed top layer of the PLGA film is transiently glassy in character because the water evaporation rate

  18. Current-voltage characteristics and quasi-two-dimensional vortex-glass transition in epitaxial Bi 2Sr 2Ca 2Cu 3O x films

    NASA Astrophysics Data System (ADS)

    Yamasaki, H.; Endo, K.; Kosaka, S.; Umeda, M.; Yoshida, S.; Kajimura, K.

    1995-04-01

    The existence of a quasi-two-dimensional vortex-glass-liquid transition has been demonstrated in the scaling analysis of non-linear current-voltage characteristics in epitaxial Bi 2Sr 2Ca 2Cu 3O x films in magnetic fields applied parallel to the c-axis. In the vortex-glass regime below the vortex-glass-liquid transition temperature Tg, the linear resistivity ϱ lin = ( E/J) J → 0 appears to vanish, while in the vortex-liquid regime the log Eversus log J curve shows systematic upward curvature and a finite linear resistivity is observed. At Tg a power-law relation E ≈ J6.5 is seen. The irreversibility fields B ∗ determined by transport measurements are much higher than the vortex-glass transition fields Bg, implying that finite critical current densities are defined by conventional criteria in the pinned vortex-liquid regime.

  19. ON REDSHIFTS AND BLUESHIFTS IN THE TRANSITION REGION AND CORONA

    SciTech Connect

    Hansteen, V. H.; Carlsson, M.; Hara, H.; De Pontieu, B. E-mail: mats.carlsson@astro.uio.n E-mail: bdp@lmsal.co

    2010-08-01

    Emission lines formed in the transition region (TR) of the Sun have long been known to show pervasive redshifts. Despite a variety of proposed explanations, these TR downflows (and the slight upflows in the low corona) remain poorly understood. We present results from comprehensive three-dimensional MHD models that span the upper convection zone up to the corona, 15 Mm above the photosphere. The TR and coronal heating in these models is caused by the stressing of the magnetic field by photospheric and convection 'zone dynamics', but also in some models by the injection of emerging magnetic flux. We show that rapid, episodic heating, at low heights of the upper chromospheric plasma to coronal temperatures naturally produces downflows in TR lines, and slight upflows in low coronal lines, with similar amplitudes to those observed with EUV/UV spectrographs. We find that TR redshifts naturally arise in episodically heated models where the average volumetric heating scale height lies between that of the chromospheric pressure scale height of 200 km and the coronal scale height of 50 Mm.

  20. Transition Region Abundance Measurements During Impulsive Heating Events

    NASA Astrophysics Data System (ADS)

    Warren, Harry P.; Brooks, David H.; Doschek, George A.; Feldman, Uri

    2016-06-01

    It is well established that elemental abundances vary in the solar atmosphere and that this variation is organized by first ionization potential (FIP). Previous studies have shown that in the solar corona, low-FIP elements such as Fe, Si, Mg, and Ca, are generally enriched relative to high-FIP elements such as C, N, O, Ar, and Ne. In this paper we report on measurements of plasma composition made during impulsive heating events observed at transition region temperatures with the Extreme Ultraviolet Imaging Spectrometer (EIS) on Hinode. During these events the intensities of O iv, v, and vi emission lines are enhanced relative to emission lines from Mg v, vi, and vii and Si vi and vii, and indicate a composition close to that of the photosphere. Long-lived coronal fan structures, in contrast, show an enrichment of low-FIP elements. We conjecture that the plasma composition is an important signature of the coronal heating process, with impulsive heating leading to the evaporation of unfractionated material from the lower layers of the solar atmosphere and higher-frequency heating leading to long-lived structures and the accumulation of low-FIP elements in the corona.

  1. MHD Modeling of Coronal Loops: the Transition Region Throat

    NASA Technical Reports Server (NTRS)

    Guarrasi, M.; Reale, F.; Orlando, S.; Mignone, A.; Klimchuk, J. A.

    2014-01-01

    Context. The expansion of coronal loops in the transition region may considerably influence the diagnostics of the plasma emission measure. The cross-sectional area of the loops is expected to depend on the temperature and pressure, and might be sensitive to the heating rate. Aims. The approach here is to study the area response to slow changes in the coronal heating rate, and check the current interpretation in terms of steady heating models. Methods. We study the area response with a time-dependent 2D magnetohydrodynamic (MHD) loop model, including the description of the expanding magnetic field, coronal heating and losses by thermal conduction, and radiation from optically thin plasma. We run a simulation for a loop 50 Mm long and quasi-statically heated to about 4 millikelvin. Results. We find that the area can change substantially with the quasi-steady heating rate, e.g., by approx. 40% at 0.5 millikelvin as the loop temperature varies between 1 millikelvin and 4 millikelvin, and, therefore, affects the interpretation of the differential emission measure vs. temperature (DEM(T)) curves.

  2. Role of entropy in the thermodynamic evolution of the time scale of molecular dynamics near the glass transition

    NASA Astrophysics Data System (ADS)

    Grzybowska, K.; Grzybowski, A.; Pawlus, S.; Pionteck, J.; Paluch, M.

    2015-06-01

    In this paper, we investigate how changes in the system entropy influence the characteristic time scale of the system molecular dynamics near the glass transition. Independently of any model of thermodynamic evolution of the time scale, against some previous suppositions, we show that the system entropy S is not sufficient to govern the time scale defined by structural relaxation time τ. In the density scaling regime, we argue that the decoupling between τ and S is a consequence of different values of the scaling exponents γ and γS in the density scaling laws, τ =f (ργ/T ) and S =h (ργS/T ) , where ρ and T denote density and temperature, respectively. It implies that the proper relation between τ and S requires supplementing with a density factor, u (ρ), i.e., τ =g ( u (ρ )w (S ) ) . This meaningful finding additionally demonstrates that the density scaling idea can be successfully used to separate physically relevant contributions to the time scale of molecular dynamics near the glass transition. The relation reported by us between τ and S constitutes a general pattern based on nonconfigurational quantities for describing the thermodynamic evolution of the characteristic time scale of molecular dynamics near the glass transition in the density scaling regime, which is a promising alternative to the approaches based as the Adam-Gibbs model on the configurational entropy that is difficult to evaluate in the entire thermodynamic space. As an example, we revise the Avramov entropic model of the dependence τ(T ,ρ), giving evidence that its entropic basis has to be extended by the density dependence of the maximal energy barrier for structural relaxation. We also discuss the excess entropy Sex, the density scaling of which is found to mimic the density scaling of the total system entropy S .

  3. Stability of anthocyanins in frozen and freeze-dried raspberries during long-term storage: in relation to glass transition.

    PubMed

    Syamaladevi, Roopesh M; Sablani, Shyam S; Tang, Juming; Powers, Joseph; Swanson, Barry G

    2011-08-01

    Anthocyanins, natural plant pigments in the flavonoid group, are responsible for the red color and some of the nutraceutical benefits of raspberries. This study explores anthocyanin degradation in frozen and freeze-dried raspberries during storage in relation to glass transition temperatures. Frozen raspberries were stored at -80, -35, and -20 °C, while freeze-dried raspberries were stored at selected water activity (a(w)) values ranging from 0.05 to 0.75 at room temperature (23 °C) for more than a year. The characteristic glass transition temperatures (T'(g)) of raspberries with high water content and glass transition temperature (T(g)) of raspberries with small water content were determined using a differential scanning calorimeter. The pH differential method was used to determine the quantity of anthocyanins in frozen and freeze-dried raspberries at selected time intervals. The total anthocyanins in raspberries fluctuated during 378 d of storage at -20 and -35, and -80 °C. Anthocyanin degradation in freeze-dried raspberries ranged from 27% to 32% and 78% to 89% at a(w) values of 0.05 to 0.07 and 0.11 to 0.43, respectively, after 1 y. Anthocyanins were not detectable in freeze-dried raspberries stored at a(w) values of 0.53 to 0.75 after 270 d. First order and Weibull equations were used to fit the anthocyanin degradation in freeze-dried raspberries. The 1(st)-order rate constant (k) of anthocyanin degradation ranged from 0.003 to 0.023 days⁻¹ at the selected water activities. Significant anthocyanin degradation occurred in both the glassy and rubbery states of freeze-dried raspberries during long-term storage. However, the rate of anthocyanin degradation in freeze-dried raspberries stored in the glassy state was significantly smaller than the rate of anthocyanin degradation in the rubbery state. PMID:22417493

  4. Fragile-to-fragile liquid transition at Tg and stable-glass phase nucleation rate maximum at the Kauzmann temperature TK

    NASA Astrophysics Data System (ADS)

    Tournier, Robert F.

    2014-12-01

    An undercooled liquid is unstable. The driving force of the glass transition at Tg is a change of the undercooled-liquid Gibbs free energy. The classical Gibbs free energy change for a crystal formation is completed including an enthalpy saving. The crystal growth critical nucleus is used as a probe to observe the Laplace pressure change Δp accompanying the enthalpy change -Vm×Δp at Tg where Vm is the molar volume. A stable glass-liquid transition model predicts the specific heat jump of fragile liquids at T≤Tg, the Kauzmann temperature TK where the liquid entropy excess with regard to crystal goes to zero, the equilibrium enthalpy between TK and Tg, the maximum nucleation rate at TK of superclusters containing magic atom numbers, and the equilibrium latent heats at Tg and TK. Strong-to-fragile and strong-to-strong liquid transitions at Tg are also described and all their thermodynamic parameters are determined from their specific heat jumps. The existence of fragile liquids quenched in the amorphous state, which do not undergo liquid-liquid transition during heating preceding their crystallization, is predicted. Long ageing times leading to the formation at TK of a stable glass composed of superclusters containing up to 147 atom, touching and interpenetrating, are evaluated from nucleation rates. A fragile-to-fragile liquid transition occurs at Tg without stable-glass formation while a strong glass is stable after transition.

  5. Atomistic simulation based prediction of the solvent effect on the molecular mobility and glass transition of poly (methyl methacrylate)

    NASA Astrophysics Data System (ADS)

    Mishra, Shawn; Keten, Sinan

    2013-01-01

    We present an investigation of the retained solvent effect on the glass transition temperature (Tg) of poly(methyl methacrylate) (PMMA) through all-atom molecular dynamics simulations. Addition of a weakly interactive solvent, tetrahydrofuran (THF), causes a depression of the PMMA Tg that can be identified through an analysis of the mean squared displacement of the polymer chains from atomistic trajectories. Our results are in very good agreement with an atomistically informed theoretical model based on free volume theory and demonstrate the applicability of molecular simulation to discern solvent effects on polymer thermomechanical behavior in silico.

  6. Thermal stress modification in regenerated fiber Bragg grating via manipulation of glass transition temperature based on CO₂-laser annealing.

    PubMed

    Lai, Man-Hong; Lim, Kok-Sing; Gunawardena, Dinusha S; Yang, Hang-Zhou; Chong, Wu-Yi; Ahmad, Harith

    2015-03-01

    In this work, we have demonstrated thermal stress relaxation in regenerated fiber Bragg gratings (RFBGs) by using direct CO₂-laser annealing technique. After the isothermal annealing and slow cooling process, the Bragg wavelength of the RFBG has been red-shifted. This modification is reversible by re-annealing and rapid cooling. It is repeatable with different cooling process in the subsequent annealing treatments. This phenomenon can be attributed to the thermal stress modification in the fiber core by means of manipulation of glass transition temperature with different cooling rates. This finding in this investigation is important for accurate temperature measurement of RFBG in dynamic environment. PMID:25723423

  7. Correlated vortex pinning in slightly orthorhombic twinned Ba(Fe1-xCox)2As2 single crystals: Possible shift of the vortex-glass/liquid transition

    SciTech Connect

    Bermudez, M. Marziali; Pasquini, G.; Budko, Sergey L.; Canfield, Paul C.

    2013-02-28

    The interest in twin-boundary (TB) planes as a source of vortex pinning has been recently renewed with the discovery of the new iron-arsenide pnictide superconductors. In the family of compounds Ba(Fe1-xCox)2As2 a structural transition from a tetragonal to orthorhombic lattice takes place for compounds with xtransition, in good-quality single crystals. Using a scaling approach we are able to determine the angular regions where correlated or uncorrelated disorder prevails. In the tetragonal samples (x>xcr) there is no twinning and we find good agreement with the expected scaling function under uncorrelated disorder, with small anisotropy values similar to those reported in the literature. We show that in the orthorhombic samples (xglass transition temperature.

  8. Correlated vortex pinning in slightly orthorhombic twinned Ba(Fe1-xCox)2As2 single crystals: Possible shift of the vortex-glass/liquid transition

    NASA Astrophysics Data System (ADS)

    Marziali Bermúdez, M.; Pasquini, G.; Bud'ko, S. L.; Canfield, P. C.

    2013-02-01

    The interest in twin-boundary (TB) planes as a source of vortex pinning has been recently renewed with the discovery of the new iron-arsenide pnictide superconductors. In the family of compounds Ba(Fe1-xCox)2As2 a structural transition from a tetragonal to orthorhombic lattice takes place for compounds with xtransition, in good-quality single crystals. Using a scaling approach we are able to determine the angular regions where correlated or uncorrelated disorder prevails. In the tetragonal samples (x>xcr) there is no twinning and we find good agreement with the expected scaling function under uncorrelated disorder, with small anisotropy values similar to those reported in the literature. We show that in the orthorhombic samples (xglass transition temperature.

  9. Orange glass - Evidence for regional deposits of pyroclastic origin on the moon

    NASA Technical Reports Server (NTRS)

    Adams, J. B.; Pieters, C.; Mccord, T. B.

    1974-01-01

    Crystallized spheres of orange glass from Shorty Crater at the Apollo 17 site are shown by spectral reflectance data to be the characteristic ingredient of the dark mantling deposit of the Taurus-Littrow region. This deposit, mapped on spectral vidicon images taken using earth-based telescopes, apparently is thickest 50 km northwest of the Apollo 17 landing area, and has a gradational contact with the surrounding materials. The irregular areal distribution of the dark-mantle deposit and the gradational borders support conclusions based on laboratory studies of the orange soils that these are volcanic pyroclastic materials. Similar deposits are identified by spectral reflectance properties near Rima Bode, Schroeter W, Fauth H, and Higinus W. The same material is likely to occur at Sulpucius Gallus based on visual and photographic observations of orange soil. The apparently restricted occurrence of the orange-glass deposits in a belt along the edges of major mare basins implies structural control of volcanic vents and a possible deep-seated origin.

  10. Different routes to the glass transition: A comparison between chemical and physical vitrification

    NASA Astrophysics Data System (ADS)

    Caponi, Silvia; Corezzi, Silvia

    2012-07-01

    Despite the differences in the molecular processes involved in chemical and physical vitrification, surprising similarities are observed in the dynamics and in the thermodynamical properties of the resulting glasses. We report on a systematic study of reactive glass-formers undergoing a process of progressive polymerization of the constituent molecules via the formation of irreversible chemical bonds. The formation of most of the materials used in engineering plastics and the hardening of natural and synthetic resins, including epoxy resins, are based on chemical vitrification. The clear analogies characterizing the dynamic evolution of physical and chemical glass-formers, on the time scale of the structural and the low-frequency vibrational dynamics, are briefly reviewed.

  11. Beyond Solar-B: MTRAP, the Magnetic Transition Region Probe

    NASA Technical Reports Server (NTRS)

    Davis, John M.; Moore, Ronald L.; Hathaway, David H.

    2003-01-01

    The next generation of solar missions will reveal and measure fine-scale solar magnetic fields and their effects in the solar atmosphere at heights, small scales, sensitivities, and fields of view well beyond the reach of Solar-B. The necessity for, and potential of, such observations for understanding solar magnetic fields, their generation in and below the photosphere, and their control of the solar atmosphere and heliosphere, were the focus of a science definition workshop, 'High-Resolution Solar Magnetography from Space: Beyond Solar-B,' held in Huntsville Alabama in April 2001. Forty internationally prominent scientists active in solar research involving fine-scale solar magnetism participated in this Workshop and reached consensus that the key science objective to be pursued beyond Solar-B is a physical understanding of the fine-scale magnetic structure and activity in the magnetic transition region, defined as the region between the photosphere and corona where neither the plasma nor the magnetic field strongly dominates the other. The observational objective requires high cadence (less than 10s) vector magnetic field maps, and spatially resolved spectra from the IR, visible, vacuum UV, to the EUV at high resolution (less than 50km) over a large FOV (approximately 140,000 km). A polarimetric resolution of one part in ten thousand is required to measure transverse magnetic fields of less than 30G. The latest SEC Roadmap includes a mission identified as MTRAP to meet these requirements. Enabling technology development requirements include large, lightweight, reflecting optics, large format sensors (16K x 16K pixels) with high QE at 150 nm, and extendable spacecraft structures. The Science Organizing Committee of the Beyond Solar-B Workshop recommends that: (1) Science and Technology Definition Teams should be established in FY04 to finalize the science requirements and to define technology development efforts needed to ensure the practicality of MTRAP

  12. Highly sensitive pseudo-differential ac-nanocalorimeter for the study of the glass transition

    SciTech Connect

    Laarraj, Mohcine; Adhiri, Rahma; Moussetad, Mohamed; Ouaskit, Said; Guttin, Christophe; Richard, Jacques; Garden, Jean-Luc

    2015-11-15

    We present a nanocalorimeter designed for the measurement of the dynamic heat capacity of thin films. The microfabricated sensor, the thermal conditioning of the sensor, as well as the highly stable and low noise electronic chain allow measurements of the real and imaginary parts of the complex specific heat with a resolution Δ C/C of about 10{sup −5}. The performances of this quasi-differential nanocalorimeter were tested on a model of polymeric glass-former, the polyvinyl acetate (PVAc). The high stability and low noise of the device are essential for accurate studies on non-equilibrium slow relaxing systems such as glasses.

  13. A new method for separating first row transition metals and actinides from synthetic melt glass

    DOE PAGESBeta

    Roman, Audrey Rae; Bond, Evelyn M.

    2016-01-14

    A new method was developed for separating Co, Fe, and Sc from complex debris matrices using the extraction chromatography resin DGA. The activation products Co-58, Mn-54, and Sc-46 were used to characterize the separation of the synthetic melt glass solutions. In the separation scheme that was developed, Au, Co, Cu, Fe, Sc, and Ti were separated from the rest of the sample constituents. In this paper, the synthetic melt glass separation method, efficiency, recoveries, and the length of procedure will be discussed. In conclusion, batch contact adsorption studies for Na and Sc for DGA resin are discussed as well.

  14. Global Natural Disaster Risk Hotspots: Transition to a Regional Approach

    NASA Astrophysics Data System (ADS)

    Lerner-Lam, A.; Chen, R.; Dilley, M.

    2005-12-01

    economic losses, are also limited. On one hand the data are adequate for general identification of areas of the globe that are at relatively higher single- or multiple-hazard risk than other areas. On the other hand they are inadequate for understanding the absolute levels of risk posed by any specific hazard or combination of hazards. Nevertheless it is possible to assess in general terms the exposure and potential magnitude of losses to people and their assets in these areas. Such information, although not ideal, can still be very useful for informing a range of disaster prevention and preparedness measures, including prioritization of resources, targeting of more localized and detailed risk assessments, implementation of risk-based disaster management and emergency response strategies, and development of long-term plans for poverty reduction and economic development. In addition to summarizing the results of the Hotspots Project, we discuss data collection issues and suggest methodological approaches for making the transition to more detailed regional and national studies. Preliminary results for several regional case studies will be presented.

  15. Optical transitions and visible upconversion in Er3+ doped niobic tellurite glass

    NASA Astrophysics Data System (ADS)

    Lin, Hai; Meredith, Gerald; Jiang, Shibin; Peng, Xiang; Luo, Tao; Peyghambarian, Nasser; Pun, Edwin Yue-Bun

    2003-01-01

    Er3+ doped Nb2O5-TeO2 (NT) glass suitable for developing optical fiber laser and amplifier has been fabricated and characterized. Intense and broad 1.53 μm infrared fluorescence and visible upconversion luminescence were observed under 975 nm diode laser and 798 nm laser excitation. For 1.53 μm emission band, the full width at half-maximum is 51 nm, the fluorescence lifetime is 2.6 ms, and the quantum efficiency is ˜100%. The maximum emission cross section is 8.52×10-21 cm2 at 1.532 μm, and is higher than the values in silicon and phosphate glasses. Under 798 nm excitation, efficient 531, 553, and 670 nm upconversion emissions are due to two-photon absorption processes. The "standardized" efficiency for the green upconversion light is 9.5×10-4, and this value is comparable to that reported for Er3+/Yb3+ codoped fluoride glasses. Intense visible upconversion fluorescence in Er3+ doped NT glass can be used in color display, undersea communication, and infrared sensor.

  16. Specific features of the glass transition in C60 fullerite saturated with carbon monoxide molecules: Photoluminescence studies

    NASA Astrophysics Data System (ADS)

    Zinoviev, P. V.; Zoryansky, V. N.; Stetsenko, Yu. E.; Danchuk, V. V.

    2016-02-01

    Low temperature (20-230 K) spectral-luminescence studies were conducted on C60 fullerite saturated with carbon monoxide in a physisorption regime. Substantial changes in the photoluminescence characteristics of C60-CO solutions with different impurity concentrations were found already for short intercalation times. Strong dependence of the CO solubility on the saturation temperature was revealed by analyzing the contribution of "deep X-traps" to the luminescence. Furthermore, it was found that filling of the octahedral voids by CO molecules occurs with a lower gradient of the impurity distribution into the bulk C60 crystals as compared with N2. The temperature dependences of the integral emission intensity for the samples with different concentrations of carbon monoxide were studied. For the first time, using the spectral-luminescence method, it was revealed that CO molecules, in contrast to H2 and N2, exhibit a significant effect on the formation of the orientational glass and the rotational dynamics of C60 molecules. Within the model of the transfer of electronic excitation in C60 crystals, the effect of polar CO molecules on the reorientation of C60 molecules and the change in the nature of their rotation in concentrated C60-CO solutions, leading to the observed strong shift of the temperatures of orientational Tc and glass Tg transitions to lower temperatures accompanied by "blurring" of the transition boundaries, were explained.

  17. Understanding the dynamics of glass-forming liquids with random pinning within the random first order transition theory

    NASA Astrophysics Data System (ADS)

    Chakrabarty, Saurish; Das, Rajsekhar; Karmakar, Smarajit; Dasgupta, Chandan

    2016-07-01

    Extensive computer simulations are performed for a few model glass-forming liquids in both two and three dimensions to study their dynamics when a randomly chosen fraction of particles are frozen in their equilibrium positions. For all the studied systems, we find that the temperature-dependence of the α relaxation time extracted from an overlap function related to the self-part of the density autocorrelation function can be explained within the framework of the Random First Order Transition (RFOT) theory of the glass transition. We propose a scaling description to rationalize the simulation results and show that our data for the α relaxation time for all temperatures and pin concentrations are consistent with this description. We find that the fragility parameter obtained from fits of the temperature dependence of the α relaxation time to the Vogel-Fulcher-Tammann form decreases by almost an order of magnitude as the pin concentration is increased from zero. Our scaling description relates the fragility parameter to the static length scale of RFOT and thus provides a physical understanding of fragility within the framework of the RFOT theory. Implications of these findings for the values of the exponents appearing in the RFOT theory are discussed.

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

    SciTech Connect

    Clark, E; Marie Kane, M

    2008-12-12

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

  19. Mobility of Supercooled liquid Toluene, Ethylbenzene, and Benzene near their Glass Transition Temperatures Investigated using Inert Gas Permeation

    SciTech Connect

    May, Robert A.; Smith, R. Scott; Kay, Bruce D.

    2013-11-21

    We investigate the mobility of supercooled liquid toluene, ethylbenzene, and benzene near their respective glass transition temperatures (Tg). The permeation rate of Ar, Kr, and Xe through the supercooled liquid created when initially amorphous overlayers heated above their glass transition temperature is used to determine the diffusivity. Amorphous benzene crystallizes at temperatures well below its Tg and as a result the inert gas underlayer remains trapped until the onset of benzene desorption. In contrast, for toluene and ethylbenzene the onset of inert gas permeation is observed at temperatues near Tg. The inert gas desorption peak temperature as a function of the heating rate and overlayer thickness is used to quantify the diffusivity of supercooled liquid toluene and ethylbenzene from 115 K to 135 K. In this temperature range, diffusivities are found to vary across five orders of magnitude (~10-14 to 10-9 cm2/s). These data are compared to viscosity measurements and used to determine the low temperature fractional Stokes-Einstein exponent. Efforts to determine the diffusivity of a mixture of benzene and ethylbenzene are detailed, and the effect of mixing these materials on benzene crystallization is explored using infrared spectroscopy.

  20. Understanding the dynamics of glass-forming liquids with random pinning within the random first order transition theory.

    PubMed

    Chakrabarty, Saurish; Das, Rajsekhar; Karmakar, Smarajit; Dasgupta, Chandan

    2016-07-21

    Extensive computer simulations are performed for a few model glass-forming liquids in both two and three dimensions to study their dynamics when a randomly chosen fraction of particles are frozen in their equilibrium positions. For all the studied systems, we find that the temperature-dependence of the α relaxation time extracted from an overlap function related to the self-part of the density autocorrelation function can be explained within the framework of the Random First Order Transition (RFOT) theory of the glass transition. We propose a scaling description to rationalize the simulation results and show that our data for the α relaxation time for all temperatures and pin concentrations are consistent with this description. We find that the fragility parameter obtained from fits of the temperature dependence of the α relaxation time to the Vogel-Fulcher-Tammann form decreases by almost an order of magnitude as the pin concentration is increased from zero. Our scaling description relates the fragility parameter to the static length scale of RFOT and thus provides a physical understanding of fragility within the framework of the RFOT theory. Implications of these findings for the values of the exponents appearing in the RFOT theory are discussed. PMID:27448896

  1. Development of DMBZ-15 High-Glass-Transition-Temperature Polyimides as PMR-15 Replacements Given R&D 100 Award

    NASA Technical Reports Server (NTRS)

    Chuang, Kathy

    2004-01-01

    PMR-15, a high-temperature polyimide developed in the mid-1970s at the NASA Lewis Research Center,1 offers the combination of low cost, easy processing, and good high-temperature performance and stability. It has been recognized as the leading polymer matrix resin for carbon-fiber-reinforced composites used in aircraft engine components. The state-of-the-art PMR-15 polyimide composite has a glass-transition temperature (Tg) of 348 C (658 F). Since composite materials must be used at temperatures well below their glass-transition temperature, the long-term use temperatures of PMR-15 composites can be no higher than 288 C (550 F). In addition, PMR-15 is made from methylene dianiline (MDA), a known liver toxin. Concerns about the safety of workers exposed to MDA during the fabrication of PMR-15 components and about the environmental impact of PMR-15 waste disposal have led to the industry-wide implementation of special handling procedures to minimize the health risks associated with this material. These procedures have increased manufacturing and maintenance costs significantly and have limited the use of PMR-15 in commercial aircraft engine components.

  2. Preparation of a series of model poly(n-alkyl styrene)s and their viscoelasticity and glass transition temperatures

    NASA Astrophysics Data System (ADS)

    Matsushima, Satoru; Takano, Atsushi; Takahashi, Yoshiaki; Matsushita, Yushu

    Viscoelasticity and glass transition temperatures for linear polymers of many species have been investigated so far, and it is well-known that the melt viscosity for the linear polymers varies with molecular weight in essentially the same manner such as packing length theory. It is important to understand the relationship between the viscosity and the molecular structure of various kinds of linear polymers. To investigate the relationship deeply, viscoelastic measurements using linear polymer analogues which the molecular structure is systematically varied should be useful. For example, poly(n-alkyl-substituted polymers) such as poly(n-alkyl methacrylate)s are one of the good candidate. In this study, a series of poly(n-alkyl styrene)s with the different number of carbon atoms(n) in the side alkyl groups (n =1, 2, 3, 4, 6, 8, 10 and 12) were carefully synthesized by an anionic polymerization technique, and the viscoelasticity and the glass transition temperatures of the poly(n-alkyl styrene)s with high molecular weight (Mw >=4Me) and narrow molecular weight distribution (Mw/Mn <=1.1) were discussed.

  3. Synthesis and properties of ferromagnetic Fe-based (Fe, Ni, Co)-Mo-P-C-B bulk metallic glasses with large supercooled liquid region

    NASA Astrophysics Data System (ADS)

    Jia, Xingjie; Li, Yanhui; Wang, Hao; Xie, Guoqiang; Yamaura, Shinichi; Zhang, Wei

    2015-11-01

    New ferromagnetic Fe-based (Fe, Co, Ni)67.5Mo7.5P10C10B5 bulk metallic glasses have been developed based on an Fe75P10C10B5 alloy. These alloys exhibit large supercooled liquid region of 97-102 K, low glass transition temperature of 727-738 K, high glass-forming ability (GFA) with critical sample diameters of 3-4 mm, and low viscosity values on the order of 107 Pa s in the supercooled liquid state. The magnetic and mechanical measurements reveal that the alloys also possess good soft magnetic and mechanical properties, i.e., low coercive force of 3.04-4.37 A/m, rather high saturation magnetization of 0.77-0.83 T, high yield strength of 3344-3463 MPa, and large plastic strain of 0.6-1.1%. In addition, the effects of Mo, Co and Ni addition on the stabilization of supercooled liquid and GFA in the Fe-P-C-B alloy system have been discussed.

  4. The relationship of dynamical heterogeneity to the Adam-Gibbs and random first-order transition theories of glass formation

    PubMed Central

    Starr, Francis W.; Douglas, Jack F.; Sastry, Srikanth

    2013-01-01

    We carefully examine common measures of dynamical heterogeneity for a model polymer melt and test how these scales compare with those hypothesized by the Adam and Gibbs (AG) and random first-order transition (RFOT) theories of relaxation in glass-forming liquids. To this end, we first analyze clusters of highly mobile particles, the string-like collective motion of these mobile particles, and clusters of relative low mobility. We show that the time scale of the high-mobility clusters and strings is associated with a diffusive time scale, while the low-mobility particles' time scale relates to a structural relaxation time. The difference of the characteristic times for the high- and low-mobility particles naturally explains the well-known decoupling of diffusion and structural relaxation time scales. Despite the inherent difference of dynamics between high- and low-mobility particles, we find a high degree of similarity in the geometrical structure of these particle clusters. In particular, we show that the fractal dimensions of these clusters are consistent with those of swollen branched polymers or branched polymers with screened excluded-volume interactions, corresponding to lattice animals and percolation clusters, respectively. In contrast, the fractal dimension of the strings crosses over from that of self-avoiding walks for small strings, to simple random walks for longer, more strongly interacting, strings, corresponding to flexible polymers with screened excluded-volume interactions. We examine the appropriateness of identifying the size scales of either mobile particle clusters or strings with the size of cooperatively rearranging regions (CRR) in the AG and RFOT theories. We find that the string size appears to be the most consistent measure of CRR for both the AG and RFOT models. Identifying strings or clusters with the “mosaic” length of the RFOT model relaxes the conventional assumption that the “entropic droplets” are compact. We also confirm

  5. The relationship of dynamical heterogeneity to the Adam-Gibbs and random first-order transition theories of glass formation.

    PubMed

    Starr, Francis W; Douglas, Jack F; Sastry, Srikanth

    2013-03-28

    We carefully examine common measures of dynamical heterogeneity for a model polymer melt and test how these scales compare with those hypothesized by the Adam and Gibbs (AG) and random first-order transition (RFOT) theories of relaxation in glass-forming liquids. To this end, we first analyze clusters of highly mobile particles, the string-like collective motion of these mobile particles, and clusters of relative low mobility. We show that the time scale of the high-mobility clusters and strings is associated with a diffusive time scale, while the low-mobility particles' time scale relates to a structural relaxation time. The difference of the characteristic times for the high- and low-mobility particles naturally explains the well-known decoupling of diffusion and structural relaxation time scales. Despite the inherent difference of dynamics between high- and low-mobility particles, we find a high degree of similarity in the geometrical structure of these particle clusters. In particular, we show that the fractal dimensions of these clusters are consistent with those of swollen branched polymers or branched polymers with screened excluded-volume interactions, corresponding to lattice animals and percolation clusters, respectively. In contrast, the fractal dimension of the strings crosses over from that of self-avoiding walks for small strings, to simple random walks for longer, more strongly interacting, strings, corresponding to flexible polymers with screened excluded-volume interactions. We examine the appropriateness of identifying the size scales of either mobile particle clusters or strings with the size of cooperatively rearranging regions (CRR) in the AG and RFOT theories. We find that the string size appears to be the most consistent measure of CRR for both the AG and RFOT models. Identifying strings or clusters with the "mosaic" length of the RFOT model relaxes the conventional assumption that the "entropic droplets" are compact. We also confirm the

  6. The relationship of dynamical heterogeneity to the Adam-Gibbs and random first-order transition theories of glass formation

    NASA Astrophysics Data System (ADS)

    Starr, Francis W.; Douglas, Jack F.; Sastry, Srikanth

    2013-03-01

    We carefully examine common measures of dynamical heterogeneity for a model polymer melt and test how these scales compare with those hypothesized by the Adam and Gibbs (AG) and random first-order transition (RFOT) theories of relaxation in glass-forming liquids. To this end, we first analyze clusters of highly mobile particles, the string-like collective motion of these mobile particles, and clusters of relative low mobility. We show that the time scale of the high-mobility clusters and strings is associated with a diffusive time scale, while the low-mobility particles' time scale relates to a structural relaxation time. The difference of the characteristic times for the high- and low-mobility particles naturally explains the well-known decoupling of diffusion and structural relaxation time scales. Despite the inherent difference of dynamics between high- and low-mobility particles, we find a high degree of similarity in the geometrical structure of these particle clusters. In particular, we show that the fractal dimensions of these clusters are consistent with those of swollen branched polymers or branched polymers with screened excluded-volume interactions, corresponding to lattice animals and percolation clusters, respectively. In contrast, the fractal dimension of the strings crosses over from that of self-avoiding walks for small strings, to simple random walks for longer, more strongly interacting, strings, corresponding to flexible polymers with screened excluded-volume interactions. We examine the appropriateness of identifying the size scales of either mobile particle clusters or strings with the size of cooperatively rearranging regions (CRR) in the AG and RFOT theories. We find that the string size appears to be the most consistent measure of CRR for both the AG and RFOT models. Identifying strings or clusters with the "mosaic" length of the RFOT model relaxes the conventional assumption that the "entropic droplets" are compact. We also confirm the

  7. An Observational Test of Transition Region Lines as a Pressure Gauge

    NASA Technical Reports Server (NTRS)

    Siegmund, Oswald H. W.

    1999-01-01

    The objective of this research project was to use high resolution spectroscopic observations from the SUMER (Solar Ultraviolet Measurements of Emitted Radiation) instrument on SOHO (Solar and Heliospheric Observatory) to study the structure of the solar transition region. Our main focus in this grant was to study the variation in density and emission across the quiet Sun transition region.

  8. Transition metal and rare earth quad-doped photovoltaic phosphate glasses toward raising a-SiC:H solar cell performance

    NASA Astrophysics Data System (ADS)

    Song, P.; Zhang, C. M.; Zhu, P. F.

    2016-01-01

    Efficiency enhancement of a hydrogenated amorphous-silicon carbide (a-SiC:H) solar cell using downshifting and upconversion of photovoltaic (PV) glasses doped with transition metal (TM) ions and rare earth (RE) ions are investigated. P2O5-Li2O-Al2O3-Sb2O3-MnO-Yb2O3-Er2O3 glass doped with Sb3+-Mn2+-Yb3+-Er3+ ions is prepared and the PV glass is placed on an a-SiC:H solar cell. The performance of the cell in combination with the PV glass is simulated and measured, and the results show that the theoretical and experimental efficiencies are both enhanced compared to the bare one. The potential of TM-RE quad-doped glasses for improving the efficiency of a-SiC:H PV modules are explored.

  9. The structure and heating of the chromosphere-corona transition region

    NASA Technical Reports Server (NTRS)

    Moore, R. L.

    1972-01-01

    The structure and heating (or energy balance) of the transition region and the role of the transition region in the structure and heating of the solar atmosphere as a whole are investigated. The features of the structure of the atmosphere and radiative energy losses of the atmosphere are summarized. A static, planar model of the solar temperature which has a temperature profile representative of the actual solar atmosphere is considered. Then a static, planar model of the transition region which is heated by thermal conduction from the corona and cooled by radiative losses is developed. A general conclusion is that the temperature profile of the transition region and lower corona results primarily from the energy balance of the corona, while the number density is determined by the energy balance of the transition region.

  10. Heating the sun's lower transition region with fine-scale electric currents

    NASA Technical Reports Server (NTRS)

    Rabin, D.; Moore, R.

    1984-01-01

    Analytical and observational data are presented to show that the lower transition zone, a 100 km thick region at 10,000-200,000 K between the solar chromosphere and corona, is heated by local electric currents. The study was spurred by correlations between the enhanced atmospheric heating and magnetospheric flux in the chromospheric network and active regions. Field aligned current heated flux loops are asserted to mainly reside in and make up most of the transition region. It is shown that thermal conduction from the sides of hot gas columns generated by the current dissipation is the source of the observed temperature distribution in the transition regions.

  11. Validation of Force Fields of Rubber through Glass-Transition Temperature Calculation by Microsecond Atomic-Scale Molecular Dynamics Simulation.

    PubMed

    Sharma, Pragati; Roy, Sudip; Karimi-Varzaneh, Hossein Ali

    2016-02-25

    Microsecond atomic-scale molecular dynamics simulation has been employed to calculate the glass-transition temperature (Tg) of cis- and trans-1,4-polybutadiene (PB) and 1,4-polyisoprene (PI). Both all-atomistic and united-atom models have been simulated using force fields, already available in literature. The accuracy of these decade old force fields has been tested by comparing calculated glass-transition temperatures to the corresponding experimental values. Tg depicts the phase transition in elastomers and substantially affects various physical properties of polymers, and hence the reproducibility of Tg becomes very crucial from a thermodynamic point of view. Such validation using Tg also evaluates the ability of these force fields to be used for advanced materials like rubber nanocomposites, where Tg is greatly affected by the presence of fillers. We have calculated Tg for a total of eight systems, featuring all-atom and united-atom models of cis- and trans-PI and -PB, which are the major constituents of natural and synthetic rubber. Tuning and refinement of the force fields has also been done using quantum-chemical calculations to obtain desirable density and Tg. Thus, a set of properly validated force fields, capable of reproducing various macroscopic properties of rubber, has been provided. A novel polymer equilibration protocol, involving potential energy convergence as the equilibration criterion, has been proposed. We demonstrate that not only macroscopic polymer properties like density, thermal expansion coefficient, and Tg but also local structural characteristics like end-to-end distance (R) and radius of gyration (Rg) and mechanical properties like bulk modulus have also been equilibrated using our strategy. Complete decay of end-to-end vector autocorrelation function with time also supports proper equilibration using our strategy. PMID:26836395

  12. Universality behaviour in ‘ideal’ dynamical arrest transitions of a lattice glass model

    NASA Astrophysics Data System (ADS)

    Dawson, Kenneth A.; Lawlor, Aonghus; de Gregorio, Paolo; McCullagh, Gavin D.; Zaccarelli, Emanuela; Tartaglia, Piero

    2002-12-01

    Using dynamically available volume (DAV) as an order parameter, we study the ideal dynamical arrest for some simple lattice glass models. For these models the dynamically available volume is expressed as holes, or vacant sites into which particles can move. We find that on approach to the arrest the holes, which are the only mediators of transport, become increasingly rare. Near the arrest, dynamical quantities can be expanded in a series of hole density, in which the leading term is found to quadratic, as opposed to unfrustrated systems which have a linear dependence. Dynamical quantities for the models we have studied show universal behaviour when expressed in terms of the hole density. The dynamically available volume is shown to be a useful characterisation of the slow aging in lattice glasses.

  13. Characterization of structural relaxation in inorganic glasses using length dilatometry

    NASA Astrophysics Data System (ADS)

    Koontz, Erick

    The processes that govern how a glass relaxes towards its thermodynamic quasi-equilibrium state are major factors in understanding glass behavior near the glass transition region, as characterized by the glass transition temperature (Tg). Intrinsic glass properties such as specific volume, enthalpy, entropy, density, etc. are used to map the behavior of the glass network below in and near the transition region. The question of whether a true thermodynamic second order phase transition takes place in the glass transition region is another pending question. Linking viscosity behavior to entropy, or viewing the glass configuration as an energy landscape are just a couple of the most prevalent methods used for attempting to understand the glass transition. The structural relaxation behavior of inorganic glasses is important for more than scientific reasons, many commercial glass processing operations including glass melting and certain forms of optical fabrication include significant time spent in the glass transition region. For this reason knowledge of structural relaxation processes can, at a minimum, provide information for annealing duration of melt-quenched glasses. The development of a predictive model for annealing time prescription has the potential to save glass manufacturers significant time and money as well as increasing volume throughput. In optical hot forming processes such as precision glass molding, molded optical components can significantly change in shape upon cooling through the glass transition. This change in shape is not scientifically predictable as of yet though manufacturers typically use empirical rules developed in house. The classification of glass behavior in the glass transition region would allow molds to be accurately designed and save money for the producers. The work discussed in this dissertation is comprised of the development of a dilatometric measurement and characterization method of structural relaxation. The measurement and

  14. Beating the bulk: Bypassing the bulk glass transition by fast heating

    NASA Astrophysics Data System (ADS)

    Gonzalez-Silveira, Marta; Rodriguez-Tinoco, Cristian; Rafols-Ribe, Joan; Lopeandia, Aitor F.; Clavaguera-Mora, Maria Teresa; Rodriguez-Viejo, Javier

    2015-03-01

    Transformation into the supercooled liquid via propagating fronts has been thoroughly studied in several ultrastable thin film glasses. In this work we show that the transformation mechanism in vapor deposited films of IMC has profound implications in the analysis of the specific heat curves. We propose an ad-hoc surface normalization of the heat capacity data that yields curves which collapse into a single one irrespective of their thickness. The surface-normalized specific heat curves are fitted with a heterogeneous transformation model to evaluate the velocity of the growth front over a much wider temperature interval than previously reported. In addition, we evaluate the transformation rate in films with lower stability. Interestingly, the transformation via parallel fronts is not an exclusive characteristic of ultrastable glasses. We observe how fast heating rates can induce this type of transformation in glassy films whose stabilities are close to the conventional glass. Although the absolute velocity of the growth front depends on stability, no change is observed in the relation between velocity and relaxation time as a function of stability.

  15. Structural phase transitions of barium halide nanocrystals in fluorozirconate glasses studied by Raman spectroscopy

    NASA Astrophysics Data System (ADS)

    Pfau, C.; Bohley, C.; Miclea, P.-T.; Schweizer, S.

    2011-04-01

    Rare-earth-doped fluorochlorozirconate (FCZ) and fluorobromozirconate (FBZ) glasses developed for fluorescence applications are analyzed, with particular attention paid to their phonon energy spectra. After thermal processing of as-made Eu-doped FCZ and FBZ glasses, Raman measurements show additional phonon bands at low phonon energies, indicating the formation of BaCl2 and BaBr2 nanocrystals, respectively. The phonon bands can be assigned to hexagonal, orthorhombic, or a mixture of both phases of BaCl2 and BaBr2 depending on the annealing conditions. Apart from line broadening, the Raman spectra of the orthorhombic nanocrystals agree well with those of BaCl2 and BaBr2 bulk crystals, while the metastable hexagonal phases of BaCl2 and BaBr2 are investigated only in appropriately treated FCZ and FBZ glasses, respectively. The experimental Raman spectra are compared to first principle studies of the phonon frequencies of the hexagonal and orthorhombic phases of both barium halides, showing good agreement.

  16. Salient properties of glassforming liquids close to the glass transitionPropriétés spécifiques des liquides au voisinage de la transition vitreuse

    NASA Astrophysics Data System (ADS)

    Alba-Simionesco, C.

    2001-03-01

    This article is focused on the dramatic increase of the viscosity, or on the relaxation time of supercooled molecular liquids, and on the dynamical arrest observed when the temperature is cooled down to the glass transition temperature T g at atmospheric pressure and under pressure. After an introduction of the fragility concept due to Angell, the particular super-Arrhenius behavior of the so-called fragile liquids is shown to be temperature rather than density driven. The non-exponential behavior of structural relaxation as a function of time, and the existence of dynamical heterogeneities are presented, whose emergence is related to the possible manifestation of polyamorphism. Some theories of deeply supercooled liquids are tested.

  17. Yield stress in metallic glasses: The jamming-unjamming transition studied through Monte Carlo simulations based on the activation-relaxation technique

    SciTech Connect

    Rodney, David; Schuh, Christopher A.

    2009-11-01

    A Monte Carlo approach allowing for stress control is employed to study the yield stress of a two-dimensional metallic glass in the limit of low temperatures and long (infinite) time scales. The elementary thermally activated events are determined using the activation-relaxation technique (ART). By tracking the minimum-energy state of the glass for various applied stresses, we find a well-defined jamming-unjamming transition at a yield stress about 30% lower than the steady-state flow stress obtained in conventional strain-controlled quasistatic simulations. ART is then used to determine the evolution of the distribution of thermally activated events in the glass microstructure both below and above the yield stress. We show that aging below the yield stress increases the stability of the glass, both thermodynamically (the internal potential energy decreases) and dynamically (the aged glass is surrounded by higher-energy barriers than the initial quenched configuration). In contrast, deformation above the yield stress brings the glass into a high internal potential energy state that is only marginally stable, being surrounded by a high density of low-energy barriers. The strong influence of deformation on the glass state is also evidenced by the microstructure polarization, revealed here through an asymmetry of the distribution of thermally activated inelastic strains in glasses after simple shear deformation.

  18. Final Report on DE-FG02-04ER46107: Glasses, Noise and Phase Transitions

    SciTech Connect

    Yu, Clare C.

    2011-12-31

    We showed that noise has distinct signatures at phase transitions in spin systems. We also studied charge noise, critical current noise, and flux noise in superconducting qubits and Josephson junctions.

  19. Isothermal transformation of supercooled liquid n -butanol near the glass transition: Polyamorphic transitions in molecular liquids investigated using Raman scattering

    NASA Astrophysics Data System (ADS)

    Wypych, Aleksandra; Guinet, Yannick; Hédoux, Alain

    2007-10-01

    Raman investigations were carried out during an isothermal transformation of deeply supercooled liquid n -butanol, recently interpreted as a polyamorphic transition. Raman spectra indicate that the newly emerging state is a mixed crystal-liquid state, and not another amorphous state. The long-range order in crystallites was identified as reflecting that of the crystal. The time dependence of the O-H stretch spectrum indicates that the transformation is driven by the formation of a two-dimensional H-bonded network, according to the archetypal-layered structures of normal alcohols. The origin of the frustration of the crystallization in n -butanol can be explained from the consideration that the rearrangement of the hydrogen-bonded molecules is unavoidably prevented by the very low molecular mobility of the system only two degrees above Tg .

  20. Glass transition and fragility in the simple molecular glassformer CS2 from CS2-S2Cl2 solution studies

    NASA Astrophysics Data System (ADS)

    Zhao, Zuofeng; Huang, Wei; Richert, Ranko; Angell, C. Austen

    2010-04-01

    With an interest in finding the fragility for a simple, single component, molecular glassformer, we have determined the dielectric relaxation and glass transition behavior for a series of glasses in the CS2-S2Cl2 and CS2-toluene systems. Crystallization of CS2 can be completely avoided down to the composition 20 mol% second component, and the fragility proves almost independent of CS2 content in each system. Since the glass temperature Tg obtained from both thermal studies and from dielectric relaxation (using Tg,diel=Tτ =100 s) is quite linear over the whole composition range in each system, and since relaxation time data for pure CS2 fall on the same master plot when scaled by the linearly extrapolated Tg value, we deduce that pure CS2 has the same high fragility as the binary solutions. The value is m =86, as for ortho-terphenyl (OTP). Based on observations of independent studies for the vibrational density of states (VDoS) (of inherent structures for OTP and instantaneous, at-temperature structures for CS2), we attribute the high fragility to an excess vibrational heat capacity (defined by Cp (vib, excess)=dS(vib, excess)/d ln T) originating in the behavior of the low frequency modes of the VDoS (the boson peak modes). Both low frequency DoS and anharmonicity increase with increasing temperature, augmenting the configurational entropy drive to the top of the system energy landscape. The surprising implication is that fragility is determined in the vibrational, not configurational, manifold of microstates.