Sample records for ideal glass transition

  1. Ideal glass transitions in thin films: An energy landscape perspective

    NASA Astrophysics Data System (ADS)

    Truskett, Thomas M.; Ganesan, Venkat

    2003-07-01

    We introduce a mean-field model for the potential energy landscape of a thin fluid film confined between parallel substrates. The model predicts how the number of accessible basins on the energy landscape and, consequently, the film's ideal glass transition temperature depend on bulk pressure, film thickness, and the strength of the fluid-fluid and fluid-substrate interactions. The predictions are in qualitative agreement with the experimental trends for the kinetic glass transition temperature of thin films, suggesting the utility of landscape-based approaches for studying the behavior of confined fluids.

  2. Transition in coupled replicas may not imply a finite-temperature ideal glass transition in glass-forming systems.

    PubMed

    Garrahan, Juan P

    2014-03-01

    A key open question in the glass transition field is whether a finite temperature thermodynamic transition to the glass state exists or not. Recent simulations of coupled replicas in atomistic models have found signatures of a static transition as a function of replica coupling. This can be viewed as evidence of an associated thermodynamic glass transition in the uncoupled system. We demonstrate here that a different interpretation is possible. We consider the triangular plaquette model, an interacting spin system which displays (East model-like) glassy dynamics in the absence of any static transition. We show that when two replicas are coupled, there is a curve of equilibrium phase transitions, between phases of small and large overlap, in the temperature-coupling plane (located on the self-dual line of an exact temperature-coupling duality of the system) which ends at a critical point. Crucially, in the limit of vanishing coupling the finite temperature transition disappears, and the uncoupled system is in the disordered phase at all temperatures. We discuss an interpretation of atomistic simulations in light of this result.

  3. Liquid-glass transition in equilibrium

    NASA Astrophysics Data System (ADS)

    Parisi, G.; Seoane, B.

    2014-02-01

    We show in numerical simulations that a system of two coupled replicas of a binary mixture of hard spheres undergoes a phase transition in equilibrium at a density slightly smaller than the glass transition density for an unreplicated system. This result is in agreement with the theories that predict that such a transition is a precursor of the standard ideal glass transition. The critical properties are compatible with those of an Ising system. The relations of this approach to the conventional approach based on configurational entropy are briefly discussed.

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

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

    Matyushov, Dmitry V., E-mail: dmitrym@asu.edu

    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{sup 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 formore » 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.« less

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

    PubMed

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

    2016-06-09

    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.

  6. Johari-Goldstein Relaxation Far Below Tg: Experimental Evidence for the Gardner Transition in Structural Glasses?

    NASA Astrophysics Data System (ADS)

    Geirhos, K.; Lunkenheimer, P.; Loidl, A.

    2018-02-01

    Experimental evidence for the Gardner transition, theoretically predicted to arise deep in the glassy state of matter, is scarce. At this transition, the energy landscape sensed by the particles forming the glass is expected to become more complex. In the present Letter, we report the dielectric response of two typical glass formers with well-pronounced Johari-Goldstein β relaxation, following this response down to unprecedented low temperatures, far below the glass transition. As the Johari-Goldstein process is believed to arise from the local structure of the energy landscape, its investigation seems an ideal tool to seek evidence for the Gardner transition. Indeed, we find an unusual broadening of the β relaxation below about 110 K for sorbitol and 100 K for xylitol, in excess of the expected broadening arising from a distribution of energy barriers. These results are well consistent with the presence of the Gardner transition in canonical structural glass formers.

  7. Testing the paradigms of the glass transition in colloids

    NASA Astrophysics Data System (ADS)

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

    2017-11-01

    Many molecular liquids freeze upon fast enough cooling. This so-called glass state is path dependent and out of equilibrium, as measured by the Kovacs signature experiments, i.e. intrinsic isotherms, asymmetry of approach and memory effect. The reasons for this path- and time-dependence are not fully understood, due to fast molecular relaxations. Colloids provide a natural way to model such behavior, owing to disparity in colloidal versus solvent time scales that can slow dynamics. To shed light on the ambiguity of glass transition, we study via large-scale dynamic simulation of hard-sphere colloidal glass after volume-fraction jumps, where particle size increases at fixed system volume followed by protocols of the McKenna-Kovacs signature experiments. During and following each jump, the positions, velocities, and particle-phase stress are tracked and utilized to characterize relaxation time scales. The impact of both quench depth and quench rate on arrested dynamics and ``state'' variables is explored. In addition, we expand our view to various structural signatures, and rearrangement mechanism is proposed. The results provide insight into not only the existence of an ``ideal'' glass transition, but also the role of structure in such a dense amorphous system.

  8. ``Ideal glassformers'' vs ``ideal glasses'': Studies of crystal-free routes to the glassy state by ``potential tuning'' molecular dynamics, and laboratory calorimetry

    NASA Astrophysics Data System (ADS)

    Kapko, Vitaliy; Zhao, Zuofeng; Matyushov, Dmitry V.; Austen Angell, C.

    2013-03-01

    of "ideal glassformers" - single or multicomponent liquids that vitrify before ever becoming metastable with respect to crystals. We find evidence that "ideal glassformer" systems might also be highly fragile systems, approaching the "ideal glass" condition. We link this to the high "volume fragility" behavior observed in recent hard dumbbell studies at similar length/diameter ratios [R. Zhang and K. S. Schweitzer, J. Chem. Phys. 133, 104902 (2010), 10.1063/1.3483601]. The discussion suggests some unusual systems for laboratory study. Using differential scanning calorimetry detection of fusion points Tm, liquidus temperatures Tl, and glass transition temperatures Tg, we describe a system that would seem incapable of crystallizing before glass transition, i.e., an "ideal glassformer." The existence of crystal-free routes to the glassy state will eliminate precrystalline fluctuations as a source of the dynamic heterogeneities that are generally considered important in the discussion of the "glassy state problem [P. W. Anderson, Science 267, 1615 (1995), 10.1126/science.267.5204.1615-e]."

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

    PubMed

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

    2013-09-28

    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.

  10. 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.

  11. Evidence for a universal localization transition underlying the glass transition

    NASA Astrophysics Data System (ADS)

    Simmons, David; Hung, Jui-Hsiang; Patra, Tarak; Meenakshisundaram, Venkatesh; Mangalara, Jayachandra Hari

    The glass transition is a ubiquitous pathway to the development of solid-like character, occurring in materials ranging from polymers to metals. Despite its technological and fundamental importance across diverse materials, the underlying nature of the glass transition remains a durable open question. Here we describe results from high-throughput simulations of the glass transition in metals, polymers, small organic molecules, and organics, indicating that a universal particle localization transition underlies the dynamic glass transition. We find that a single adjustable parameter is sufficient to describe the nonuniversal growth in relaxation time resulting from this localization event. These results point to an opportunity to advance the modern understanding of the glass transition by refocusing attention on the onset of localization rather than the growth in relaxation time as the key experimental observable. This work was made possible by generous support from the W. M. Keck Foundation. This material is based in part on work sup-ported by the National Science Foundation NSF Career Award Grant Number DMR1554920.

  12. Characteristic length of glass transition

    NASA Astrophysics Data System (ADS)

    Donth, E.

    1996-03-01

    The characteristic length of the glass transition (ξ _α ) is based on the concept of cooperatively rearranging regions (CRR's) by Adam & Gibbs (1965): ξ _α is the diameter of one CRR. In the theoretical part of the talk a formula is derived how this length can be calculated from calorimetric data of the transformation interval. The approach is based on fluctuations in natural functional subsystems. The corresponding thermodynamics is represented e.g. in a book of the author (E. Donth, Relaxation and Thermodynamics in Polymers. Glass Transition, Akademie-Verlag, Berlin 1992). A typical value for this length is 3 nanometers. In the experimental part several examples are reported to enlarge the experimental evidence for such a length: Squeezing the glass transition in the amorphous layers of partially crystallized PET (C. Schick, Rostock), glass transition of small-molecule glass formers in a series of nanoscaled pores of porous glasses (F. Kremer, Leipzig), comparison with a concentration fluctuation model in homogeneous polymer mixtures (E.W. Fischer, Mainz), and, from our laboratory, backscaling to ξ _α across the main transition from the entanglement spacing in several amorphous polymers such as PVAC, PS, NR, and some polymer networks. Rouse backscaling was possible in the α β splitting region of several poly(n alkyl methacrylates) resulting in small characteristic lengths of order 1 nanometer near the onset of α cooperativity. In a speculative outlook a dynamic density pattern is presented, having a cellular structure with higher density and lower mobility of the cell walls. It will be explained, with the aid of different thermal expansion of wall and clusters, how the clusters within the cells maintain a certain mobility far below the glass temperature.

  13. Glass-Glass Transitions by Means of an Acceptor-Donor Percolating Electric-Dipole Network

    NASA Astrophysics Data System (ADS)

    Zhang, Le; Lou, Xiaojie; Wang, Dong; Zhou, Yan; Yang, Yang; Kuball, Martin; Carpenter, Michael A.; Ren, Xiaobing

    2017-11-01

    We report the ferroelectric glass-glass transitions in KN (K+/Nb5 +) -doped BaTiO3 ferroelectric ceramics, which have been proved by x-ray diffraction profile and Raman spectra data. The formation of glass-glass transitions can be attributed to the existence of cubic (C )-tetragonal (T )-orthorhombic (O )-rhombohedral (R ) ferroelectric transitions in short-range order. These abnormal glass-glass transitions can perform very small thermal hysteresis (approximately 1.0 K ) with a large dielectric constant (approximately 3000), small remanent polarization Pr , and relative high maximum polarization Pm remaining over a wide temperature range (220-350 K) under an electrical stimulus, indicating the potential applications in dielectric recoverable energy-storage devices with high thermal reliability. Further phase field simulations suggest that these glass-glass transitions are induced by the formation of a percolating electric defect-dipole network (PEDN). This proper PEDN breaks the long-range ordered ferroelectric domain pattern and results in the local phase transitions at the nanoscale. Our work may further stimulate the fundamental physical theory and accelerate the development of dielectric energy-storing devices.

  14. Paramagnetic and glass transitions in sudoku

    NASA Astrophysics Data System (ADS)

    Williams, A.; Ackland, G. J.

    2012-09-01

    We study the statistical mechanics of a model glassy system based on sudoku, a familiar and popular mathematical puzzle. Sudoku puzzles provide a very rare example of a class of frustrated systems with a unique ground state without symmetry. Here, the puzzle is recast as a thermodynamic system where the number of violated rules defines the energy. We use Monte Carlo simulation to show that the “sudoku Hamiltonian” exhibits two transitions as a function of temperature, a paramagnetic, and a glass transition. Of these, the intermediate condensed phase is the only one that visits the ground state (i.e., it solves the puzzle, though this is not the purpose of the study). Both transitions are associated with an entropy change, paramagnetism measured from the dynamics of the Monte Carlo run, showing a peak in specific heat, while the residual glass entropy is determined by finding multiple instances of the glass by repeated annealing. There are relatively few such simple models for frustrated or glassy systems that exhibit both ordering and glass transitions; sudoku puzzles are unique for the ease with which they can be obtained, with the proof of the existence of a unique ground state via the satisfiability of all constraints. Simulations suggest that in the glass phase there is an increase in information entropy with lowering temperature. In fact, we have shown that sudoku puzzles have the type of rugged energy landscape with multiple minima that typifies glasses in many physical systems. This puzzling result is a manifestation of the paradox of the residual glass entropy. These readily available puzzles can now be used as solvable model Hamiltonian systems for studying the glass transition.

  15. 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

  16. The glass transition in high-density amorphous ice.

    PubMed

    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 T g 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 T g 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.

  17. Polymer brushes: a controllable system with adjustable glass transition temperature of fragile glass formers.

    PubMed

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

    2014-01-28

    We present results of molecular dynamics simulations for coarse-grained polymer brushes in a wide temperature range to investigate the factors that affect the glass transition in these systems. We focus on the influences of free surface, polymer-substrate interaction strength, grafting density, and chain length not only on the change of glass transition temperature Tg, but also the fragility D of the glass former. It is found that the confinement can enhance the dependence of the Tg on the cooling rate as compared to the bulk melt. Our layer-resolved analysis demonstrates that it is possible to control the glass transition temperature Tg of polymer brushes by tuning the polymer-substrate interaction strength, the grafting density, and the chain length. Moreover, we find quantitative differences in the influence range of the substrate and the free surface on the density and dynamics. This stresses the importance of long range cooperative motion in glass formers near the glass transition temperature. Furthermore, the string-like cooperative motion analysis demonstrates that there exists a close relation among glass transition temperature Tg, fragility D, and string length ⟨S⟩. The polymer brushes that possess larger string length ⟨S⟩ tend to have relatively higher Tg and smaller D. Our results suggest that confining a fragile glass former through forming polymer brushes changes not only the glass transition temperature Tg, but also the very nature of relaxation process.

  18. 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.

  19. Glass transition of anhydrous starch by fast scanning calorimetry.

    PubMed

    Monnier, Xavier; Maigret, Jean-Eudes; Lourdin, Denis; Saiter, Allisson

    2017-10-01

    By means of fast scanning calorimetry, the glass transition of anhydrous amorphous starch has been measured. With a scanning rate of 2000Ks -1 , thermal degradation of starch prior to the glass transition has been inhibited. To certify the glass transition measurement, structural relaxation of the glassy state has been investigated through physical aging as well as the concept of limiting fictive temperature. In both cases, characteristic enthalpy recovery peaks related to the structural relaxation of the glass have been observed. Thermal lag corrections based on the comparison of glass transition temperatures measured by means of differential and fast scanning calorimetry have been proposed. The complementary investigations give an anhydrous amorphous starch glass transition temperature of 312±7°C. This estimation correlates with previous extrapolation performed on hydrated starches. Copyright © 2017 Elsevier Ltd. All rights reserved.

  20. Ionic Ckonductivity and Glass Transition of Phosphoric Acids

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

    Wang, Yangyang; Lane, Nathan A; Sun, Che-Nan

    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.

  1. Ionic conductivity and glass transition of phosphoric acids

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

    Wang, Yangyang; Lane, Nathan A; Sun, Che-Nan

    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.

  2. 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

  3. On relaxation nature of glass transition in amorphous materials

    NASA Astrophysics Data System (ADS)

    Sanditov, Damba S.; Ojovan, Michael I.

    2017-10-01

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

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

    PubMed

    Hill, Robert G; Brauer, Delia S

    2011-10-01

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

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

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

    Riley, Brian J.; Vienna, John D.

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

  6. A Second Glass Transition in Pressure Collapsed Type II Clathrate Hydrates.

    PubMed

    Andersson, Ove; Häussermann, Ulrich

    2018-04-19

    Type II clathrate hydrates (CHs) M·17 H 2 O, with M = tetrahydrofuran (THF) or 1,3-dioxolane, are known to collapse, or amorphize, on pressurization to ∼1.3 GPa in the temperature range 77-140 K. On heating at 1 GPa, these pressure-amorphized CH states show a weak, stretched sigmoid-shaped, heat-capacity increase because of a glass transition. Here we use thermal conductivity and heat capacity measurements to show that also type II CH with M = cyclobutanone (CB) collapses on isothermal pressurization and undergoes a similar, weak, glass transition upon heating at 1 GPa. Furthermore, we reveal for both THF CH and CB CH a second, much more pronounced, glass transition at temperatures above the thermally weak glass transition on heating in the 0.2-0.7 GPa range. This result suggests the general occurrence of two glass transitions in water-rich (94 mol %) pressure-collapsed CHs. Because of a large increase in dielectric permittivity concurrently as the weak heat capacity increase, the first glass transition must be due to kinetic unfreezing of water molecules. The thermal features of the second glass transition, measured on isobaric temperature cycling, are typical of a glass-liquid-glass transition, which suggests that pressure-amorphized CHs transform reversibly to liquids.

  7. 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.

  8. Direct observation of molecular cooperativity near the glass transition.

    PubMed

    Russell, E V; Israeloff, N E

    2000-12-07

    The increasingly sluggish response of a supercooled liquid as it nears its glass transition (for example, refrigerated honey) is prototypical of glassy dynamics found in proteins, neural networks and superconductors. The notion that molecules rearrange cooperatively has long been postulated to explain diverging relaxation times and broadened (non-exponential) response functions near the glass transition. Recently, cooperativity was observed and analysed in colloid glasses and in simulations of binary liquids well above the glass transition. But nanometre-scale studies of cooperativity at the molecular glass transition are lacking. Important issues to be resolved include the precise form of the cooperativity and its length scale, and whether the broadened response is intrinsic to individual cooperative regions, or arises only from heterogeneity in an ensemble of such regions. Here we describe direct observations of molecular cooperativity near the glass transition in polyvinylacetate (PVAc), using nanometre-scale probing of dielectric fluctuations. Molecular clusters switched spontaneously among two to four distinct configurations, producing random telegraph noise. Our analysis of these noise signals and their power spectra reveals that individual clusters exhibit transient dynamical heterogeneity and non-exponential kinetics.

  9. Effect of particle size on the glass transition.

    PubMed

    Larsen, Ryan J; Zukoski, Charles F

    2011-05-01

    The glass transition temperature of a broad class of molecules is shown to depend on molecular size. This dependency results from the size dependence of the pair potential. A generalized equation of state is used to estimate how the volume fraction at the glass transition depends on the size of the molecule, for rigid molecule glass-formers. The model shows that at a given pressure and temperature there is a size-induced glass transition: For molecules larger than a critical size, the volume fraction required to support the effective pressure due to particle attractions is above that which characterizes the glassy state. This observation establishes the boundary between nanoparticles, which exist in liquid form only as dispersions in low molecular weight solvents and large molecules which form liquids that have viscosities below those characterized by the glassy state.

  10. A universal reduced glass transition temperature for liquids

    NASA Technical Reports Server (NTRS)

    Fedors, R. F.

    1979-01-01

    Data on the dependence of the glass transition temperature on the molecular structure for low-molecular-weight liquids are analyzed in order to determine whether Boyer's reduced glass transition temperature (1952) is a universal constant as proposed. It is shown that the Boyer ratio varies widely depending on the chemical nature of the molecule. It is pointed out that a characteristic temperature ratio, defined by the ratio of the sum of the melting temperature and the boiling temperature to the sum of the glass transition temperature and the boiling temperature, is a universal constant independent of the molecular structure of the liquid. The average value of the ratio obtained from data for 65 liquids is 1.15.

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

    NASA Astrophysics Data System (ADS)

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

    2017-02-01

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

  12. Electron anions and the glass transition temperature.

    PubMed

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

    2016-09-06

    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.

  13. Electron anions and the glass transition temperature

    DOE PAGES

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

    2016-08-24

    Properties of glasses are typically controlled by judicious selection of the glass-forming and glass-modifying constituents. Through an experimental and computational study of the crystalline, molten, and amorphous [Ca 12Al 14O 32] 2+ ∙ (e –) 2, we demonstrate that electron anions in this system behave as glass-modifiers that strongly affect solidification dynamics, the glass transition temperature, and spectroscopic properties of the resultant amorphous material. Concentration of such electron anions is a consequential control parameter: it invokes materials evolution pathways and properties not available in conventional glasses, which opens a new avenue in rational materials design.

  14. Light-scattering study of the glass transition in lubricants

    NASA Technical Reports Server (NTRS)

    Alsaad, M. A.; Winer, W. O.; Medina, F. D.; Oshea, D. C.

    1977-01-01

    The sound velocity of four lubricants has been measured as a function of temperature and pressure using Brillouin scattering. A change in slope of the velocity as a function of temperature or pressure allowed the determination of the glass transition temperature and pressure. The glass transition data were used to construct a phase diagram for each lubricant. The data indicate that the glass transition temperature increased with pressure at a rate which ranged from 120 to 200 C/GPa. The maximum pressure attained was 0.69 GPa and the temperature range was from 25 to 100 C.

  15. Kinetic Equations for Describing the Liquid-Glass Transition in Polymers

    NASA Astrophysics Data System (ADS)

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

    2018-01-01

    We present a theoretical approach based on nonequilibrium thermodynamics and used to describe the kinetics of the transition from the liquid to the glassy state (glass transition). In the framework of this approach, we construct kinetic equations describing the time and temperature evolution of the structural parameter. We discuss modifications of the equations required for taking the nonexponential, nonlinear character of the relaxation in the vitrification region into account. To describe the formation of polymer glasses, we present modified expressions for the system relaxation time. We compare the obtained results with experimental data, measurements of the polystyrene glass transition for different cooling rates using the method of differential scanning calorimetry. We discuss prospects for developing a method for describing the polymer glass transition.

  16. Transition to exponential relaxation in weakly disordered electron glasses

    NASA Astrophysics Data System (ADS)

    Ovadyahu, Z.

    2018-06-01

    The out-of-equilibrium excess conductance of electron-glasses Δ G (t ) typically relaxes with a logarithmic time dependence. Here it is shown that the log(t ) relaxation of a weakly disordered InxO film crosses over asymptotically to an exponential dependence Δ G (t )∝exp {-[t /τ (∞ )]} . This allows for assigning a well-defined relaxation-time τ (∞ ) for a given system disorder (characterized by the Ioffe-Regel parameter kFℓ ). Near the metal-insulator transition, τ (∞ ) obeys the scaling relation τ (∞ ) ∝[(kFℓ)C-kFℓ ] with the same critical disorder (kFℓ)C where the zero-temperature conductivity of this system vanishes. The latter defines the position of the disorder-driven metal-to-insulator transition which is a quantum-phase transition. In this regard the electron glass differs from classical glasses, such as the structural glass and spin glass. The ability to experimentally assign an unambiguous relaxation time allows us to demonstrate the steep dependence of the electron-glass dynamics on carrier concentration.

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

    PubMed

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

    2016-09-28

    A series of transition and post-transition metal ion (Mn, Cu, Zn, Pb, Bi) binary borate glasses was studied with special consideration of the cations impact on the borate structure, the cations cross-linking capacity, and more generally, structure-property correlations. Infrared (IR) and Raman spectroscopies were used for the structural characterization. These complementary techniques are sensitive to the short-range order as in the differentiation of tetrahedral and trigonal borate units or regarding the number of non-bridging oxygen ions per unit. Moreover, vibrational spectroscopy is also sensitive to the intermediate-range order and to the presence of superstructural units, such as rings and chains, or the combination of rings. In order to clarify band assignments for the various borate entities, examples are given from pure vitreous B 2 O 3 to meta-, pyro-, ortho-, and even overmodified borate glass compositions. For binary metaborate glasses, the impact of the modifier cation on the borate speciation is shown. High field strength cations such as Zn 2+ enhance the disproportionation of metaborate to polyborate and pyroborate units. Pb 2+ and Bi 3+ induce cluster formation, resulting in PbO n - and BiO n -pseudophases. Both lead and bismuth borate glasses show also a tendency to stabilize very large superstructural units in the form of diborate polyanions. Far-IR spectra reflect on the bonding states of modifier cations in glasses. The frequency of the measured cation-site vibration band was used to obtain the average force constant for the metal-oxygen bonding, F M-O . A linear correlation between glass transition temperature (T g ) and F M-O was shown for the metaborate glass series. The mechanical properties of the glasses also correlate with the force constant F M-O , though for cations of similar force constant the fraction of tetrahedral borate units (N 4 ) strongly affects the thermal and mechanical properties. For paramagnetic Cu- and Mn-borate glasses

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

    PubMed

    Djemour, A; Sanctuary, R; Baller, J

    2015-04-07

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

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

    PubMed

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

    2010-05-19

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

  20. A thermally tunable inverse opal photonic crystal for monitoring glass transition.

    PubMed

    Sun, Liguo; Xie, Zhuoying; Xu, Hua; Xu, Ming; Han, Guozhi; Wang, Cheng; Bai, Xuduo; Gu, ZhongZe

    2012-03-01

    An optical method was developed to monitor the glass transition of the polymer by taking advantage of reflection spectrum change of the thermally tunable inverse opal photonic crystal. The thermally tunable photonic bands of the polymer inverse opal photonic crystal were traceable to the segmental motion of macromolecules, and the segmental motion was temperature dependent. By observing the reflection spectrum change of the polystyrene inverse opal photonic crystal during thermal treatment, the glass transition temperature of polystyrene was gotten. Both changes of the position and intensity of the reflection peak were observed during the glass transition process of the polystyrene inverse opal photonic crystal. The optical change of inverse opal photonic crystal was so large that the glass transition temperature could even be estimated by naked eyes. The glass transition temperature derived from this method was consistent with the values measured by differential scanning calorimeter.

  1. Calorimetric study of water's two glass transitions in the presence of LiCl

    PubMed Central

    Ruiz, Guadalupe N.; Amann-Winkel, Katrin; Bove, Livia E.; Corti, Horacio R.

    2018-01-01

    A DSC study of dilute glassy LiCl aqueous solutions in the water-dominated regime provides direct evidence of a glass-to-liquid transition in expanded high density amorphous (eHDA)-type solutions. Similarly, low density amorphous ice (LDA) exhibits a glass transition prior to crystallization to ice Ic. Both glass transition temperatures are independent of the salt concentration, whereas the magnitude of the heat capacity increase differs. By contrast to pure water, the glass transition endpoint for LDA can be accessed in LiCl aqueous solutions above 0.01 mole fraction. Furthermore, we also reveal the endpoint for HDA's glass transition, solving the question on the width of both glass transitions. This suggests that both equilibrated HDL and LDL can be accessed in dilute LiCl solutions, supporting the liquid–liquid transition scenario to understand water's anomalies. PMID:29442107

  2. The study of glass transition temperature in Sb-V2O5-TeO2 glasses at different heating rates

    NASA Astrophysics Data System (ADS)

    Souri, Dariush

    2015-12-01

    The glass transition of xSb-(60 - x)V2O5-40TeO2 glasses with 0 < x <15 (in mol%) at different heating rates ( φ = 3-12 K/min) has been studied using differential scanning calorimetry. The glass transition temperature ( T g) and crystallization temperature ( T cr) of these glasses have been determined. The effects of the heating rate and the Sb content on T g have been discussed. It has been observed that the transition region shifts to higher temperatures when the measuring time is reduced. The compositional dependence of T g has been determined and so an empirical equation has been deduced relating the glass transition temperature with the Sb concentration. Also, the value of glass-forming tendency has been studied for the present glasses.

  3. A new approach for describing glass transition kinetics.

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

    Vasin, N. M.; Shchelkachev, M. G.; Vinokur, V. M.

    2010-04-01

    We use a functional integral technique generalizing the Keldysh diagram technique to describe glass transition kinetics. We show that the Keldysh functional approach takes the dynamical determinant arising in the glass dynamics into account exactly and generalizes the traditional approach based on using the supersymmetric dynamic generating functional method. In contrast to the supersymmetric method, this approach allows avoiding additional Grassmannian fields and tracking the violation of the fluctuation-dissipation theorem explicitly. We use this method to describe the dynamics of an Edwards-Anderson soft spin-glass-type model near the paramagnet-glass transition. We show that a Vogel-Fulcher-type dynamics arises in the fluctuation regionmore » only if the fluctuation-dissipation theorem is violated in the process of dynamical renormalization of the Keldysh action in the replica space.« less

  4. Using Dielectric Relaxation Spectroscopy to Characterize the Glass Transition Time of Polydextrose.

    PubMed

    Buehler, Martin G; Kindle, Michael L; Carter, Brady P

    2015-06-01

    Dielectric relaxation spectroscopy was used to characterize the glass transition time, tg , of polydextrose, where the glass transition temperature, Tg , and water activity, aw (relative humidity), were held constant during polydextrose relaxation. The tg was determined from a shift in the peak frequency of the imaginary capacitance spectrum with time. It was found that when the peak frequency reaches 30 mHz, polydextrose undergoes glass transition. Glass transition time, tg , is the time for polydextrose to undergo glass transition at a specific Tg and aw . Results lead to a modified state diagram, where Tg is depressed with increasing aw . This curve forms a boundary: (a) below the boundary, polydextrose does not undergo glass transition and (b) above the boundary, polydextrose rapidly undergoes glass transition. As the boundary curve is specified by a tg value, it can assist in the selection of storage conditions. An important point on the boundary curve is at aw = 0, where Tg0 = 115 °C. The methodology can also be used to calculate the stress-relaxation viscosity of polydextrose as a function of Tg and aw , which is important when characterizing the flow properties of polydextrose initially in powder form. © 2015 Institute of Food Technologists®

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

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

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

    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 diffractionmore » (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.« less

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

    DOE PAGES

    Xia, Chengjie; Li, Jindong; Cao, Yixin; ...

    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

  7. 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

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

    PubMed

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

    2016-03-04

    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.

  9. 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

  10. Unusual Crystallization Behavior Close to the Glass Transition

    NASA Astrophysics Data System (ADS)

    Desgranges, Caroline; Delhommelle, Jerome

    2018-03-01

    Using molecular simulations, we shed light on the mechanism underlying crystal nucleation in metal alloys and unravel the interplay between crystal nucleation and glass transition, as the conditions of crystallization lie close to this transition. While decreasing the temperature of crystallization usually results in a lower free energy barrier, we find an unexpected reversal of behavior for glass-forming alloys as the temperature of crystallization approaches the glass transition. For this purpose, we simulate the crystallization process in two glass-forming Copper alloys, Ag6 Cu4 , which has a positive heat of mixing, and CuZr, characterized by a large negative heat of mixing. Our results allow us to identify this unusual behavior as directly correlated with a nonmonotonic temperature dependence for the formation energy of connected icosahedral structures, which are incompatible with crystalline order and impede the development of the crystal nucleus, leading to an unexpectedly larger free energy barrier at low temperature. This, in turn, promotes the formation of a predominantly closed-packed critical nucleus, with fewer defects, thereby suggesting a new way to control the structure of the crystal nucleus, which is of key importance in catalysis.

  11. Free energy landscape theory of glass transition

    NASA Astrophysics Data System (ADS)

    Odagaki, Takashi

    2010-03-01

    I first present a free energy landscape (FEL) description of statistical mechanics, which is an exact reformulation of statistical mechanics and can be applied to non-equilibrium systems. Then, I discuss thermodynamic and dynamic properties of the vitrification process on the basis of the FEL formalism. I show that thermodynamic and dynamic anomalies at the glass transition, including the cooling rate dependence, can be understood in a unified manner which has not been achieved by any other theories of the glass transition. Namely, I show that the vitrification is a transition from annealed to quenched averages in the FEL and that the fast beta, the JG and the slow alpha relaxations are attributed to stochastic dynamics within a basin of FEL, jumping motion among locally connected basins and diffusive dynamics over barriers of the FEL.

  12. 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

  13. Structural signal of a dynamic glass transition

    NASA Astrophysics Data System (ADS)

    Chattopadhyay, Sudeshna; Uysal, Ahmet; Stripe, Benjamin; Evmenenko, Guennadi; Dutta, Pulak; Ehrlich, Steven; Karapetrova, Evguenia A.

    2010-03-01

    Conventional wisdom states that there is no significant difference between the static structures of the glass and liquid states of a given material. Using x-ray reflectivity, we have studied pentaphenyl trimethyl trisiloxane, an isotropic liquid at room temperature with a dynamic glass transition at 224K. Surface density oscillations (surface layers) develop below 285K, similar to those seen in other metallic and dielectric liquids and in computer simulations [1]. Upon cooling further, there is a sharp increase in the penetration of the surface layers into the bulk material, i.e. an apparently discontinuous change in the static structure, exactly at the glass transition (224K) [2]. [4pt] [1]. e.g. O. M. Magnussen et al., PRL 74, 4444 (1995); H. Mo et al. PRL 96, 096107 (2006); E. Chac'on et al., PRL 87, 166101 (2001) [0pt] [2] S. Chattopadhyay et al, PRL 103, 175701 (2009)

  14. Glass Transitions in a Monatomic Liquid with Two Glassy States

    NASA Astrophysics Data System (ADS)

    Gordon, Andrew; Giovambattista, Nicolas

    2014-04-01

    We perform out-of-equilibrium molecular dynamics simulations of a monatomic liquid that exhibits liquid and glass polymorphism, with two distinct glasses, low- (LDA) and high-density (HDA) amorphous solids. By performing isobaric heating simulations of LDA and HDA at different pressures, we determine (a) the glass transition temperature of LDA and HDA, TgLDA(P) and TgHDA(P), as well as (b) the corresponding glass-glass transformation temperatures, TLDA-HDA(P) and THDA-LDA(P). It is found that TgLDA(P) is anomalous; i.e., it decreases with increasing pressure, while TgHDA(P) increases with increasing pressure. Interestingly, the TgLDA(P) and TLDA-HDA(P) loci, as well as the TgHDA(P) and THDA-LDA(P) loci, constitute smooth single lines in the P -T plane, suggesting that heating-induced glass-glass and glass transitions are related. We discuss the present results in the context of water experiments and simulations.

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

    PubMed Central

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

    2015-01-01

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

  16. Investigation of the Atypical Glass Transition and Recrystallization Behavior of Amorphous Prazosin Salts

    PubMed Central

    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

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

    PubMed

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

    2011-08-25

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

  18. 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

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

    NASA Astrophysics Data System (ADS)

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

    2012-05-01

    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.

  20. Predictions of glass transition temperature for hydrogen bonding biomaterials.

    PubMed

    van der Sman, R G M

    2013-12-19

    We show that the glass transition of a multitude of mixtures containing hydrogen bonding materials correlates strongly with the effective number of hydroxyl groups per molecule, which are available for intermolecular hydrogen bonding. This correlation is in compliance with the topological constraint theory, wherein the intermolecular hydrogen bonds constrain the mobility of the hydrogen bonded network. The finding that the glass transition relates to hydrogen bonding rather than free volume agrees with our recent finding that there is little difference in free volume among carbohydrates and polysaccharides. For binary and ternary mixtures of sugars, polyols, or biopolymers with water, our correlation states that the glass transition temperature is linear with the inverse of the number of effective hydroxyl groups per molecule. Only for dry biopolymer/sugar or sugar/polyol mixtures do we find deviations due to nonideal mixing, imposed by microheterogeneity.

  1. The effect of polymeric excipients on the physical properties and performance of amorphous dispersions: Part I, free volume and glass transition.

    PubMed

    Li, Jinjiang; Zhao, Junshu; Tao, Li; Wang, Jennifer; Waknis, Vrushali; Pan, Duohai; Hubert, Mario; Raghavan, Krishnaswamy; Patel, Jatin

    2015-02-01

    To investigate the structural effect of polymeric excipients on the behavior of free volume of drug-polymer dispersions in relation to glass transition. Two drugs (indomethacin and ketoconazole) were selected to prepare amorphous dispersions with PVP, PVPVA, HPC, and HPMCAS through spray drying. The physical attributes of the dispersions were characterized using SEM and PXRD. The free volume (hole-size) of the dispersions along with drugs and polymers was measured using positron annihilation lifetime spectroscopy (PALS). Their glass transition temperatures (Tgs) were determined using DSC and DMA. FTIR spectra were recorded to identify hydrogen bonding in the dispersions. The chain structural difference-flexible (PVP and PVPVA) vs. inflexible (HPC and HPMCAS)-significantly impacts the free volume and Tgs of the dispersions as well as their deviation from ideality. Relative to Tg, free volume seems to be a better measure of hydrogen bonding interaction for the dispersions of PVP, HPC, and HPMCAS. The free volume of polymers and their dispersions in general appears to be related to their conformations in solution. Both the backbone chain rigidity of polymers as well as drug-polymer interaction can impact the free volume and glass transition behaviors of the dispersions.

  2. Long-wavelength fluctuations and the glass transition in two dimensions and three dimensions

    PubMed Central

    Vivek, Skanda; Kelleher, Colm P.; Chaikin, Paul M.

    2017-01-01

    Phase transitions significantly differ between 2D and 3D systems, but the influence of dimensionality on the glass transition is unresolved. We use microscopy to study colloidal systems as they approach their glass transitions at high concentrations and find differences between two dimensions and three dimensions. We find that, in two dimensions, particles can undergo large displacements without changing their position relative to their neighbors, in contrast with three dimensions. This is related to Mermin–Wagner long-wavelength fluctuations that influence phase transitions in two dimensions. However, when measuring particle motion only relative to their neighbors, two dimensions and three dimensions have similar behavior as the glass transition is approached, showing that the long-wavelength fluctuations do not cause a fundamental distinction between 2D and 3D glass transitions. PMID:28137847

  3. Long-wavelength fluctuations and the glass transition in two dimensions and three dimensions.

    PubMed

    Vivek, Skanda; Kelleher, Colm P; Chaikin, Paul M; Weeks, Eric R

    2017-02-21

    Phase transitions significantly differ between 2D and 3D systems, but the influence of dimensionality on the glass transition is unresolved. We use microscopy to study colloidal systems as they approach their glass transitions at high concentrations and find differences between two dimensions and three dimensions. We find that, in two dimensions, particles can undergo large displacements without changing their position relative to their neighbors, in contrast with three dimensions. This is related to Mermin-Wagner long-wavelength fluctuations that influence phase transitions in two dimensions. However, when measuring particle motion only relative to their neighbors, two dimensions and three dimensions have similar behavior as the glass transition is approached, showing that the long-wavelength fluctuations do not cause a fundamental distinction between 2D and 3D glass transitions.

  4. Polymeric nanoparticles - Influence of the glass transition temperature on drug release.

    PubMed

    Lappe, Svenja; Mulac, Dennis; Langer, Klaus

    2017-01-30

    The physico-chemical characterisation of nanoparticles is often lacking the determination of the glass transition temperature, a well-known parameter for the pure polymer carrier. In the present study the influence of water on the glass transition temperature of poly (DL-lactic-co-glycolic acid) nanoparticles was assessed. In addition, flurbiprofen and mTHPP as model drugs were incorporated in poly (DL-lactic-co-glycolic acid), poly (DL-lactic acid), and poly (L-lactic acid) nanoparticles. For flurbiprofen-loaded nanoparticles a decrease in the glass transition temperature was observed while mTHPP exerted no influence on this parameter. Based on this observation, the release behaviour of the drug-loaded nanoparticles was investigated at different temperatures. For all preparations an initial burst release was measured that could be attributed to the drug adsorbed to the large nanoparticle surface. At temperatures above the glass transition temperature an instant drug release of the nanoparticles was observed, while at lower temperatures less drug was released. It could be shown that the glass transition temperature of drug loaded nanoparticles in suspension more than the corresponding temperature of the pure polymer is the pivotal parameter when characterising a nanostructured drug delivery system. Copyright © 2016 Elsevier B.V. All rights reserved.

  5. Flory Model of Polymer Crystallization, Kauzmann Paradox and Gibbs-DiMarzio Theory of Glass Transition

    NASA Astrophysics Data System (ADS)

    Corsi, A.; Gujrati, P. D.

    2000-03-01

    The Flory model of crystallization of polymers is well known and forms the cornerstone of the Gibbs-DiMarzio theory of glass transition. The model has no known exact solution and the original calculation [1] was shown to be incorrect [2]. Still it is interesting to know the order of the phase transition, if it has one. We have studied the thermodynamics of the model in the limit of infinite molecular weight. We have solved it exactly on a recursive lattice with coordination number q=4, relevant for a tetrahedral lattice. Our results show that there is a continuous, i.e. a second-order, transition at which the entropy of the system is continuous. It is finite at all temperatures and approaches 0 as T goes to 0 so that the system is never completely ordered except at T=0. As the temperature is raised above T=0 the system begins to disorder with a degree of disorder that depends on T, which is in accordance with the analysis of Gujrati and Goldstein [2]. Since there is no first order transition there is no Kauzmann paradox. Similarly there is no possible metastable extension in the model which is central to the Gibbs-DiMarzio conjecture for an ideal glass transition. Thus, our solution does not justify their conjecture. [1] P.J. Flory, Proc. R. Soc. London Ser., A234, 60 (1956) [2] P.D. Gujrati, J. Phys. A: Math. Gen., 13, L437 (1980), P.D. Gujrati, M. Goldstein, J. Chem. Phys., 74(4), 2596 (1981)

  6. Communication: Glass transition and melting lines of an ionic liquid

    NASA Astrophysics Data System (ADS)

    Lima, Thamires A.; Faria, Luiz F. O.; Paschoal, Vitor H.; Ribeiro, Mauro C. C.

    2018-05-01

    The phase diagram of the ionic liquid 1-butyl-1-methylpyrrolidinium bis(trifluoromethanesufonyl)imide, [Pyrr1,4][NTf2], was explored by synchroton X-ray diffraction and Raman scattering measurements as a function of temperature and pressure. Glass transition Tg(p) and melting Tm(p) temperatures were obtained from atmospheric pressure up to ca. 2.0 GPa. We found that both the Tg(p) and Tm(p) curves follow essentially the same pressure dependence. The similarity of pressure coefficients, dTg/dp ≈ dTm/dp, is explained within the non-equilibrium thermodynamics approach for the glass transition by assuming that one of the Ehrenfest equations is appropriated for Tg(p), whereas Tm(p) follows the Clausius-Clapeyron equation valid for the first-order transitions. The results highlight that ionic liquids are excellent model systems to address fundamental questions related to the glass transition.

  7. 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.

  8. 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.

  9. Stereodynamic insight into the thermal history effects on poly(vinyl chloride) calorimetric sub-glass and glass transitions as a fragile glass model.

    PubMed

    Pin, Jean-Mathieu; Behazin, Ehsan; Misra, Manjusri; Mohanty, Amar

    2018-05-02

    The dynamic thermal history impact of poly(vinyl chloride) (PVC) has been explored for a wide range of pre-cooling rates, from 1 to 30 °C min-1. A first macroscopic insight into the dynamic thermal history influence has been highlighted through a decrease in the apparent activation energy (Eapp) in the first stage of the glass transition. The overall glass transition Eapp surface was successfully modeled in a polynomial fashion regarding the pre-cooling range. Raman scattering was used to associate the Eapp variations along the glass transition conversion with the stereochemistry evolution during the polymeric relaxation. Herein, the selection of atactic PVC as the polymer model permits us to monitor the glassy polymer segment stereodynamics during the heating ramp through the C-Cl stretching. The intermolecular H-Cl dipole interactions, as well as intramolecular conformational reorganizations among syndiotactic, isotactic and heterotactic polymer sequences, have been associated with non-cooperative and cooperative motions, i.e. the β- and α-process, respectively. The fruitful comparison of the two extreme values of the pre-cooling rates permits us to propose a thermokinetic scenario that explains the occurrence, intensity, and inter-dependence of β- and α-processes in the glassy state and during the glass transition. This scenario could potentially be generalized to all the other polymeric glass-formers.

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

    NASA Astrophysics Data System (ADS)

    Sanditov, D. S.

    2016-09-01

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

  11. Predicting glass-to-glass and liquid-to-liquid phase transitions in supercooled water using classical nucleation theory

    NASA Astrophysics Data System (ADS)

    Tournier, Robert F.

    2018-01-01

    Glass-to-glass and liquid-to-liquid phase transitions are observed in bulk and confined water, with or without applied pressure. They result from the competition of two liquid phases separated by an enthalpy difference depending on temperature. The classical nucleation equation of these phases is completed by this quantity existing at all temperatures, a pressure contribution, and an enthalpy excess. This equation leads to two homogeneous nucleation temperatures in each liquid phase; the first one (Tn- below Tm) being the formation temperature of an "ordered" liquid phase and the second one corresponding to the overheating temperature (Tn+ above Tm). Thermodynamic properties, double glass transition temperatures, sharp enthalpy and volume changes are predicted in agreement with experimental results. The first-order transition line at TLL = 0.833 × Tm between fragile and strong liquids joins two critical points. Glass phase above Tg becomes "ordered" liquid phase disappearing at TLL at low pressure and at Tn+ = 1.302 × Tm at high pressure.

  12. Communication: Glass transition and melting lines of an ionic liquid.

    PubMed

    Lima, Thamires A; Faria, Luiz F O; Paschoal, Vitor H; Ribeiro, Mauro C C

    2018-05-07

    The phase diagram of the ionic liquid 1-butyl-1-methylpyrrolidinium bis(trifluoromethanesufonyl)imide, [Pyrr 1,4 ][NTf 2 ], was explored by synchroton X-ray diffraction and Raman scattering measurements as a function of temperature and pressure. Glass transition T g (p) and melting T m (p) temperatures were obtained from atmospheric pressure up to ca. 2.0 GPa. We found that both the T g (p) and T m (p) curves follow essentially the same pressure dependence. The similarity of pressure coefficients, dT g /dp ≈ dT m /dp, is explained within the non-equilibrium thermodynamics approach for the glass transition by assuming that one of the Ehrenfest equations is appropriated for T g (p), whereas T m (p) follows the Clausius-Clapeyron equation valid for the first-order transitions. The results highlight that ionic liquids are excellent model systems to address fundamental questions related to the glass transition.

  13. Glass transition behavior of polystyrene/silica nanocomposites.

    NASA Astrophysics Data System (ADS)

    Xie, Yuping; Sen, Sudeepto; Kumar, Sanat; Bansal, Amitabh

    2006-03-01

    The change in thermomechanical properties of nano-filled polymers is of considerable scientific and technological interest. The interaction between the nanofillers and the matrix polymer controls the nanocomposite properties. We will present the results from recent and ongoing DSC experiments on polystyrene/silica nanocomposites. Polystyrene of different molecular weights (and from different sources) and silica nanoparticles 10-15 nm in diameter (both as received from Nissan and surface modified by grafted or physisorbed polystyrene) are being used to process the nanocomposites. We are studying trends in the glass transition behavior by changing the matrix molecular weights and the silica weight fractions. Recent data indicate that the glass transition temperature can both decrease and increase depending on the polymer-nanofiller combination as well as the thermal treatment of the nanocomposites prior to the DSC runs.

  14. Size-Dependent Brittle-to-Ductile Transition in Silica Glass Nanofibers.

    PubMed

    Luo, Junhang; Wang, Jiangwei; Bitzek, Erik; Huang, Jian Yu; Zheng, He; Tong, Limin; Yang, Qing; Li, Ju; Mao, Scott X

    2016-01-13

    Silica (SiO2) glass, an essential material in human civilization, possesses excellent formability near its glass-transition temperature (Tg > 1100 °C). However, bulk SiO2 glass is very brittle at room temperature. Here we show a surprising brittle-to-ductile transition of SiO2 glass nanofibers at room temperature as its diameter reduces below 18 nm, accompanied by ultrahigh fracture strength. Large tensile plastic elongation up to 18% can be achieved at low strain rate. The unexpected ductility is due to a free surface affected zone in the nanofibers, with enhanced ionic mobility compared to the bulk that improves ductility by producing more bond-switching events per irreversible bond loss under tensile stress. Our discovery is fundamentally important for understanding the damage tolerance of small-scale amorphous structures.

  15. Correlation between average melting temperature and glass transition temperature in metallic glasses

    NASA Astrophysics Data System (ADS)

    Lu, Zhibin; Li, Jiangong

    2009-02-01

    The correlation between average melting temperature (⟨Tm⟩) and glass transition temperature (Tg) in metallic glasses (MGs) is analyzed. A linear relationship, Tg=0.385⟨Tm⟩, is observed. This correlation agrees with Egami's suggestion [Rep. Prog. Phys. 47, 1601 (1984)]. The prediction of Tg from ⟨Tm⟩ through the relationship Tg=0.385⟨Tm⟩ has been tested using experimental data obtained on a large number of MGs. This relationship can be used to predict and design MGs with a desired Tg.

  16. Does a Growing Static Length Scale Control the Glass Transition?

    NASA Astrophysics Data System (ADS)

    Wyart, Matthieu; Cates, Michael E.

    2017-11-01

    Several theories of the glass transition propose that the structural relaxation time τα is controlled by a growing static length scale ξ that is determined by the free energy landscape but not by the local dynamic rules governing its exploration. We argue, based on recent simulations using particle-radius-swap dynamics, that only a modest factor in the increase in τα on approach to the glass transition may stem from the growth of a static length, with a vastly larger contribution attributable, instead, to a slowdown of local dynamics. This reinforces arguments that we base on the observed strong coupling of particle diffusion and density fluctuations in real glasses.

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

    NASA Astrophysics Data System (ADS)

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

    2014-06-01

    Molecular dynamics simulations are used to study the structural and dynamic properties of calcium aluminosilicate, (CaO-Al2O3)1-x(SiO2)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 AlO5 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. 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

    2016-09-05

    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. Copyright © 2016 Elsevier Ltd. All rights reserved.

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

    PubMed

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

    2015-07-01

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

  20. Investigation of low glass transition temperature on COTS PEMs reliability

    NASA Technical Reports Server (NTRS)

    Sandor, M.; Agarwal, S.

    2002-01-01

    Many factors influence PEM component reliability.One of the factors that can affect PEM performance and reliability is the glass transition temperature (Tg) and the coefficient of thermal expansion (CTE) of the encapsulant or underfill. JPL/NASA is investigating how the Tg and CTE for PEMs affect device reliability under different temperature and aging conditions. Other issues with Tg are also being investigated. Some preliminary data will be presented on glass transition temperature test results conducted at JPL.

  1. Glass transition behavior of the vitrification solutions containing propanediol, dimethyl sulfoxide and polyvinyl alcohol.

    PubMed

    Wang, Hai-Yan; Lu, Shu-Shen; Lun, Zhao-Rong

    2009-02-01

    Knowledge of the glass transition behavior of vitrification solutions is important for research and planning of the cryopreservation of biological materials by vitrification. This brief communication shows the analysis for the glass transition and glass stability of the multi-component vitrification solutions containing propanediol (PE), dimethyl sulfoxide (Me2SO) and polyvinyl alcohol (PVA) by using differential scanning calorimetry (DSC) during the cooling and subsequent warming between 25 and -150 degrees C. The glass formation of the solutions was enhanced by introduction of PVA. Partial glass formed during cooling and the fractions of free water in the partial glass matrix increased with the increasing of PVA concentration, which caused slight decline of glass transition temperature, T(g). Exothermic peaks of devitrification were delayed and broadened, which may result from the inhibition of ice nucleation or recrystallization of PVA.

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

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

    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 ofmore » the glass-transition temperature as well as of the fragility as a function of silica content along the three joins.« less

  3. Subcritical transition to turbulence: What we can learn from the physics of glasses.

    PubMed

    Dauchot, Olivier; Bertin, Eric

    2012-09-01

    In this note, we discuss possible analogies between the subcritical transition to turbulence in shear flows and the glass transition in supercooled liquids. We briefly review recent experimental and numerical results, as well as theoretical proposals, and compare the difficulties arising in assessing the divergence of the turbulence lifetime in subcritical shear flow with that encountered for the relaxation time in the study of the glass transition. In order to go beyond the purely methodological similarities, we further elaborate on this analogy and propose a simple model for the transition to turbulence, inspired by the random energy model (a standard model for the glass transition), with the aim to possibly foster yet-unexplored directions of research in subcritical shear flows.

  4. Brittle to ductile transition in densified silica glass.

    PubMed

    Yuan, Fenglin; Huang, Liping

    2014-05-22

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

  5. 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

  6. Investigation of low glass transition temperature on COTS PEM's reliability for space applications

    NASA Technical Reports Server (NTRS)

    Sandor, M.; Agarwal, S.; Peters, D.; Cooper, M. S.

    2003-01-01

    Plastic Encapsulated Microelectronics (PEM) reliability is affected by many factors. Glass transition temperature (Tg) is one such factor. In this presentation issues relating to PEM reliability and the effect of low glass transition temperature epoxy mold compounds are presented.

  7. 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. Copyright © 2013 Elsevier B.V. All rights reserved.

  8. 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.

  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. Instantaneous Normal Modes and the Protein Glass Transition

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

    Schulz, Roland; Krishnan, Marimuthu; Daidone, Isabella

    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 ~ 220more » 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.« less

  11. Instantaneous Normal Modes and the Protein Glass Transition

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

    Schultz, Roland; Krishnan, Marimuthu; Daidone, Isabella

    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.more » 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.« less

  12. 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

  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. Revealing the glass transition in shape memory polymers using Brillouin spectroscopy

    NASA Astrophysics Data System (ADS)

    Steelman, Zachary A.; Weems, Andrew C.; Traverso, Andrew J.; Szafron, Jason M.; Maitland, Duncan J.; Yakovlev, Vladislav V.

    2017-12-01

    Emerging medical devices which employ shape memory polymers (SMPs) require precise measurements of the glass transition temperature (Tg) to ensure highly controlled shape recovery kinetics. Conventional techniques like differential scanning calorimetry (DSC) and dynamic mechanical analysis (DMA) have limitations that prevent utilization for certain devices, including limited accuracy and the need for sacrificial samples. In this report, we employ an approach based on Brillouin spectroscopy to probe the glass transition of SMPs rapidly, remotely, and nondestructively. Further, we compare the Tg obtained from Brillouin scattering with DMA- and DSC-measured Tg to demonstrate the accuracy of Brillouin scattering for this application. We conclude that Brillouin spectroscopy is an accurate technique for obtaining the glass transition temperature of SMPs, aligning closely with the most common laboratory standards while providing a rapid, remote, and nondestructive method for the analysis of unique polymeric medical devices.

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

    NASA Astrophysics Data System (ADS)

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

    2017-06-01

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

  16. Glass transition memorized by the enthalpy-entropy compensation in the shear thinning of supercooled metallic liquids.

    PubMed

    Zhang, Meng; Liu, Lin

    2018-05-03

    To unravel the true nature of glass transition, broader insights into glass forming have been gained by examining the stress-driven glassy systems, where strong shear thinning, i.e., a reduced viscosity under increasing shear rate, is encountered. It is argued that arbitrarily small stress-driven shear rates would "melt" the glass and erase any memory of its thermal history. In this work, we report a glass transition memorized by the enthalpy-entropy compensation in strongly shear-thinned supercooled metallic liquids, which coincides with the thermal glass transition in both the transition temperature and the activation Gibbs free energy. Our findings provide distinctive insights into both glass forming and shear thinning, and enrich current knowledge on the ubiquitous enthalpy-entropy compensation empirical law in condensed matter physics. © 2018 IOP Publishing Ltd.

  17. Glass transition memorized by the enthalpy-entropy compensation in the shear thinning of supercooled metallic liquids

    NASA Astrophysics Data System (ADS)

    Zhang, Meng; Liu, Lin

    2018-06-01

    To unravel the true nature of glass transition, broader insights into glass forming have been gained by examining the stress-driven glassy systems, where strong shear thinning, i.e. a reduced viscosity under increasing shear rate, is encountered. It is argued that arbitrarily small stress-driven shear rates would ‘melt’ the glass and erase any memory of its thermal history. In this work, we report a glass transition memorized by the enthalpy-entropy compensation in strongly shear-thinned supercooled metallic liquids, which coincides with the thermal glass transition in both the transition temperature and the activation Gibbs free energy. Our findings provide distinctive insights into both glass forming and shear thinning, and enrich current knowledge on the ubiquitous enthalpy-entropy compensation empirical law in condensed matter physics.

  18. Effects of steaming treatment on crystallinity and glass transition temperature of Eucalyptuses grandis × E. urophylla

    NASA Astrophysics Data System (ADS)

    Kong, Lulu; Zhao, Zijian; He, Zhengbin; Yi, Songlin

    To investigate the effects of steaming treatment on crystallinity and glass transition temperature, samples of Eucalyptuses grandis × E. urophylla with moisture content of 50%, 70%, and 90% were steamed in saturated steam at 100 °C for 2, 4, 6, and 8 h. The degree of crystallinity (CrI) and glass transition temperature (Tg) were measured via X-ray diffraction and dynamic mechanical analysis, respectively. Results revealed a crystallinity degree of Eucalyptus of 29.9%-34.2%, and a glass transition temperature of 80-94 °C with moisture contents of steamed samples of 20%. Furthermore, steaming was revealed to have an obvious effect on crystallization and glass transition. Values of CrI and Tg showed similar changing characteristics: increasing initially, followed by a decrease with increasing steaming time, reaching a maximum at 2 h. Water within the wood seemed to promote crystallization and glass transition during steaming. All steamed samples tested in this study reached glass transition temperature after 50 min of steaming, and the residual growth stress was released.

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

    NASA Astrophysics Data System (ADS)

    Giovambattista, Nicolas

    2013-03-01

    Most liquids can form a single glass or amorphous state when cooled sufficiently fast (in order to prevent crystallization). However, there are a few substances that are relevant to scientific and technological applications which can exist in at least two different amorphous states, a property known as polyamorphism. Examples include silicon, silica, and in particular, water. In the case of water, experiments show the existence of a low-density (LDA) and high-density (HDA) amorphous ice that are separated by a dramatic, first-order like phase transition. It has been argued that the LDA-HDA transformation evolves into a first-order liquid-liquid phase transition (LLPT) at temperatures above the glass transition temperature Tg. However, obtaining direct experimental evidence of the LLPT has been challenging since the LLPT occurs at conditions where water rapidly crystallizes. In this talk, I will (i) discuss the general phenomenology of polyamorphism in water and its implications, and (ii) explore the effects of a LLPT on the pressure dependence of Tg(P) for LDA and HDA. Our study is based on computer simulations of two water models - one with a LLPT (ST2 model), and one without (SPC/E model). In the absence of a LLPT, Tg(P) for all glasses nearly coincide. Instead, when there is a LLPT, different glasses exhibit dramatically different Tg(P) loci which are directly linked with the LLPT. Available experimental data for Tg(P) are only consistent with the scenario that includes a LLPT (ST2 model) and hence, our results support the view that a LLPT may exist for the case of water.

  20. Thermodynamic, crystallographic, and dielectric study of the nature of glass transitions in cyclo-octanol

    NASA Astrophysics Data System (ADS)

    Puertas, Ricardo; Rute, Maria A.; Salud, Josep; López, David O.; Diez, Sergio; van Miltenburg, J. Kees; Pardo, Luis C.; Tamarit, Josep Ll.; Barrio, Maria; Pérez-Jubindo, Miguel A.; de La Fuente, Maria R.

    2004-06-01

    The stable solid polymorphism of cyclooctanol (C8H16O, for short C8 OH) is revealed to be a complex problem and only two stable solid phases, denoted on cooling from the liquid as phases I and II, are found using static (thermodynamic and x-ray diffraction) as well as dynamic (dielectric spectroscopy) experimental techniques. Both solid phases are known to exhibit glass transitions if they are cooled down fast enough to prevent transition to ordered crystalline states. Although glass transitions corresponding to both phases had been well documented by means of specific heat measurements, x-ray measurements constitute, as far as we know, the first evidence from the structural point of view. In addition, a great amount of dielectric works devoted to phase I and its glass transition, were published in the past but next to nothing relating to the dielectric properties of phase II and its glass transition. The nature of the disorder of phase II will be discussed.

  1. Revealing the glass transition in shape memory polymers using Brillouin spectroscopy.

    PubMed

    Steelman, Zachary A; Weems, Andrew C; Traverso, Andrew J; Szafron, Jason M; Maitland, Duncan J; Yakovlev, Vladislav V

    2017-12-11

    Emerging medical devices which employ shape memory polymers (SMPs) require precise measurements of the glass transition temperature (T g ) to ensure highly controlled shape recovery kinetics. Conventional techniques like differential scanning calorimetry (DSC) and dynamic mechanical analysis (DMA) have limitations that prevent utilization for certain devices, including limited accuracy and the need for sacrificial samples. In this report, we employ an approach based on Brillouin spectroscopy to probe the glass transition of SMPs rapidly, remotely, and nondestructively. Further, we compare the T g obtained from Brillouin scattering with DMA- and DSC-measured T g to demonstrate the accuracy of Brillouin scattering for this application. We conclude that Brillouin spectroscopy is an accurate technique for obtaining the glass transition temperature of SMPs, aligning closely with the most common laboratory standards while providing a rapid, remote, and nondestructive method for the analysis of unique polymeric medical devices.

  2. Glass transition in thin supported polystyrene films probed by temperature-modulated ellipsometry in vacuum.

    PubMed

    Efremov, Mikhail Yu; Kiyanova, Anna V; Last, Julie; Soofi, Shauheen S; Thode, Christopher; Nealey, Paul F

    2012-08-01

    Glass transition in thin (1-200 nm thick) spin-cast polystyrene films on silicon surfaces is probed by ellipsometry in a controlled vacuum environment. A temperature-modulated modification of the method is used alongside a traditional linear temperature scan. A clear glass transition is detected in films with thicknesses as low as 1-2 nm. The glass transition temperature (T(g)) shows no substantial dependence on thickness for coatings greater than 20 nm. Thinner films demonstrate moderate T(g) depression achieving 18 K for thicknesses 4-7 nm. Less than 4 nm thick samples are excluded from the T(g) comparison due to significant thickness nonuniformity (surface roughness). The transition in 10-20 nm thick films demonstrates excessive broadening. For some samples, the broadened transition is clearly resolved into two separate transitions. The thickness dependence of the glass transition can be well described by a simple 2-layer model. It is also shown that T(g) depression in 5 nm thick films is not sensitive to a wide range of experimental factors including molecular weight characteristics of the polymer, specifications of solvent used for spin casting, substrate composition, and pretreatment of the substrate surface.

  3. The glass and jamming transitions in dense granular matter

    NASA Astrophysics Data System (ADS)

    Coulais, Corentin; Candelier, Raphaël; Dauchot, Olivier

    2013-06-01

    Everyday life tells us that matter acquires rigidity either when it cools down, like lava flows which turn into solid rocks, or when it is compacted, like tablets simply formed by powder compression. As suggested by these examples, solidification is not the sole privilege of crystals but also happens for disordered media such as glass formers, granular media, foams, emulsions and colloidal suspensions. Fifteen years ago the "Jamming paradigm" emerged to encompass in a unique framework the glass transition and the emergence of yield stress, two challenging issues in modern condensed matter physics. One must realize how bold this proposal was, given that the glass transition is a finite temperature transition governing the dynamical properties of supercooled liquids, while Jamming is essentially a zero temperature, zero external stress and purely geometric transition which occurs when a given packing of particles reaches the maximum compression state above which particles start to overlap. More recently, the observation of remarkable scaling properties on the approach to jamming led to the conjecture that this zero temperature "critical point" could determine the properties of dense particle systems within a region of the parameter space to be determined, which in principle could include thermal and stressed systems. Fifteen years of intense theoretical and experimental work later, what have we learned about Jamming and glassy dynamics? In this paper, we discuss these issues in the light of the experiments we have been conducting with vibrated grains.

  4. Glass dynamics and anomalous aging in a family of ionic liquids above the glass transition temperature.

    PubMed

    Shamim, Nabila; McKenna, Gregory B

    2010-12-09

    The present paper reports the results of a systematic rheological study of the dynamic moduli of 1-butyl 3-methylimidazolium tetrafluoroborate ([Bmim][BF(4)]), 1-butyl 3-methylimidazolium hexafluorophosphate ([Bmim][PF(6)]), and 1-ethyl 3-methylimidazolium ethylsulfate ([Emim][EtSO(4)]) in the vicinity of their respective glass transition temperatures. The results show an anomalous aging in that the dynamic and the low shear rate viscosities decrease with time at temperatures near to, but above, the glass transition temperature, and this is described. The samples that are aged into equilibrium obey the time-temperature superposition principle, and the shift factors and the viscosities follow classic super-Arrhenius behaviors with intermediate fragility values as the glass transition is approached. Similar experiments using a high-purity [Bmim][BF(4)] show that using a higher purity of the ionic liquid, while changing absolute values of the properties, does not eliminate the anomalous aging response. The data are also analyzed in a fashion similar to that used for polymer melts, and we find that these ionic liquids do not follow, for example, the Cox-Merz relationship between the steady shear viscosity and the dynamic viscosity.

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

    PubMed

    O'Donnell, Matthew D

    2011-05-01

    The glass transition temperature (T(g)) of inorganic glasses is an important parameter than can be used to correlate with other glass properties, such as dissolution rate, which governs in vitro and in vivo bioactivity. Seven bioactive glass compositional series reported in the literature (77 in total) were analysed here with T(g) values obtained by a number of different methods: differential thermal analysis, differential scanning calorimetry and dilatometry. An iterative least-squares fitting method was used to correlate T(g) from thermal analysis of these compositions with the levels of individual oxide and fluoride components in the glasses. When all seven series were fitted a reasonable correlation was found between calculated and experimental values (R(2)=0.89). When the two compositional series that were designed in weight percentages (the remaining five were designed in molar percentage) were removed from the model an improved fit was achieved (R(2)=0.97). This study shows that T(g) for a wide range in compositions (e.g. SiO(2) content of 37.3-68.4 mol.%) can be predicted to reasonable accuracy enabling processing parameters to be predicted such as annealing, fibre-drawing and sintering temperatures. Copyright © 2011 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

  6. The Perfect Glass Paradigm: Disordered Hyperuniform Glasses Down to Absolute Zero.

    PubMed

    Zhang, G; Stillinger, F H; Torquato, S

    2016-11-28

    Rapid cooling of liquids below a certain temperature range can result in a transition to glassy states. The traditional understanding of glasses includes their thermodynamic metastability with respect to crystals. However, here we present specific examples of interactions that eliminate the possibilities of crystalline and quasicrystalline phases, while creating mechanically stable amorphous glasses down to absolute zero temperature. We show that this can be accomplished by introducing a new ideal state of matter called a "perfect glass". A perfect glass represents a soft-interaction analog of the maximally random jammed (MRJ) packings of hard particles. These latter states can be regarded as the epitome of a glass since they are out of equilibrium, maximally disordered, hyperuniform, mechanically rigid with infinite bulk and shear moduli, and can never crystallize due to configuration-space trapping. Our model perfect glass utilizes two-, three-, and four-body soft interactions while simultaneously retaining the salient attributes of the MRJ state. These models constitute a theoretical proof of concept for perfect glasses and broaden our fundamental understanding of glass physics. A novel feature of equilibrium systems of identical particles interacting with the perfect-glass potential at positive temperature is that they have a non-relativistic speed of sound that is infinite.

  7. 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

  8. Determination of the glass-transition temperature of proteins from a viscometric approach.

    PubMed

    Monkos, Karol

    2015-03-01

    All fully hydrated proteins undergo a distinct change in their dynamical properties at glass-transition temperature Tg. To determine indirectly this temperature for dry albumins, the viscosity measurements of aqueous solutions of human, equine, ovine, porcine and rabbit serum albumin have been conducted at a wide range of concentrations and at temperatures ranging from 278 K to 318 K. Viscosity-temperature dependence of the solutions is discussed on the basis of the three parameters equation resulting from Avramov's model. One of the parameter in the Avramov's equation is the glass-transition temperature. For all studied albumins, Tg of a solution monotonically increases with increasing concentration. The glass-transition temperature of a solution depends both on Tg for a dissolved dry protein Tg,p and water Tg,w. To obtain Tg,p for each studied albumin the modified Gordon-Taylor equation was applied. This equation describes the dependence of Tg of a solution on concentration, and Tg,p and a parameter depending on the strength of the protein-solvent interaction are the fitting parameters. Thus determined the glass-transition temperature for the studied dry albumins is in the range (215.4-245.5)K. Copyright © 2014 Elsevier B.V. All rights reserved.

  9. Using 20-million-year-old amber to test the super-Arrhenius behaviour of glass-forming systems.

    PubMed

    Zhao, Jing; Simon, Sindee L; McKenna, Gregory B

    2013-01-01

    Fossil amber offers the opportunity to investigate the dynamics of glass-forming materials far below the nominal glass transition temperature. This is important in the context of classical theory, as well as some new theories that challenge the idea of an 'ideal' glass transition. Here we report results from calorimetric and stress relaxation experiments using a 20-million-year-old Dominican amber. By performing the stress relaxation experiments in a step-wise fashion, we measured the relaxation time at each temperature and, above the fictive temperature of this 20-million-year-old glass, this is an upper bound to the equilibrium relaxation time. The results deviate dramatically from the expectation of classical theory and are consistent with some modern ideas, in which the diverging timescale signature of complex fluids disappears below the glass transition temperature.

  10. 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

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

    PubMed

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

    2003-01-01

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

  12. 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.

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

    PubMed

    Narumi, Takayuki; Tokuyama, Michio

    2017-03-01

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

  14. 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.

  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. The Perfect Glass Paradigm: Disordered Hyperuniform Glasses Down to Absolute Zero

    NASA Astrophysics Data System (ADS)

    Zhang, G.; Stillinger, F. H.; Torquato, S.

    2016-11-01

    Rapid cooling of liquids below a certain temperature range can result in a transition to glassy states. The traditional understanding of glasses includes their thermodynamic metastability with respect to crystals. However, here we present specific examples of interactions that eliminate the possibilities of crystalline and quasicrystalline phases, while creating mechanically stable amorphous glasses down to absolute zero temperature. We show that this can be accomplished by introducing a new ideal state of matter called a “perfect glass”. A perfect glass represents a soft-interaction analog of the maximally random jammed (MRJ) packings of hard particles. These latter states can be regarded as the epitome of a glass since they are out of equilibrium, maximally disordered, hyperuniform, mechanically rigid with infinite bulk and shear moduli, and can never crystallize due to configuration-space trapping. Our model perfect glass utilizes two-, three-, and four-body soft interactions while simultaneously retaining the salient attributes of the MRJ state. These models constitute a theoretical proof of concept for perfect glasses and broaden our fundamental understanding of glass physics. A novel feature of equilibrium systems of identical particles interacting with the perfect-glass potential at positive temperature is that they have a non-relativistic speed of sound that is infinite.

  17. The Perfect Glass Paradigm: Disordered Hyperuniform Glasses Down to Absolute Zero

    PubMed Central

    Zhang, G.; Stillinger, F. H.; Torquato, S.

    2016-01-01

    Rapid cooling of liquids below a certain temperature range can result in a transition to glassy states. The traditional understanding of glasses includes their thermodynamic metastability with respect to crystals. However, here we present specific examples of interactions that eliminate the possibilities of crystalline and quasicrystalline phases, while creating mechanically stable amorphous glasses down to absolute zero temperature. We show that this can be accomplished by introducing a new ideal state of matter called a “perfect glass”. A perfect glass represents a soft-interaction analog of the maximally random jammed (MRJ) packings of hard particles. These latter states can be regarded as the epitome of a glass since they are out of equilibrium, maximally disordered, hyperuniform, mechanically rigid with infinite bulk and shear moduli, and can never crystallize due to configuration-space trapping. Our model perfect glass utilizes two-, three-, and four-body soft interactions while simultaneously retaining the salient attributes of the MRJ state. These models constitute a theoretical proof of concept for perfect glasses and broaden our fundamental understanding of glass physics. A novel feature of equilibrium systems of identical particles interacting with the perfect-glass potential at positive temperature is that they have a non-relativistic speed of sound that is infinite. PMID:27892452

  18. Dynamical heterogeneity in a glass-forming ideal gas.

    PubMed

    Charbonneau, Patrick; Das, Chinmay; Frenkel, Daan

    2008-07-01

    We conduct a numerical study of the dynamical behavior of a system of three-dimensional "crosses," particles that consist of three mutually perpendicular line segments of length sigma rigidly joined at their midpoints. In an earlier study [W. van Ketel, Phys. Rev. Lett. 94, 135703 (2005)] we showed that this model has the structural properties of an ideal gas, yet the dynamical properties of a strong glass former. In the present paper we report an extensive study of the dynamical heterogeneities that appear in this system in the regime where glassy behavior sets in. On the one hand, we find that the propensity of a particle to diffuse is determined by the structure of its local environment. The local density around mobile particles is significantly less than the average density, but there is little clustering of mobile particles, and the clusters observed tend to be small. On the other hand, dynamical susceptibility results indicate that a large dynamical length scale develops even at moderate densities. This suggests that propensity and other mobility measures are an incomplete measure of the dynamical length scales in this system.

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

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

    Andersson, Ove; Johari, G. P., E-mail: joharig@mcmaster.ca

    2016-02-14

    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) κ{sub crystal} is 3.6-times the κ{sub liquid} value at 140 K at 0.1 MPa and 2.2-times at 290 K, and it varies with T according to 138 × T{sup −0.95}; (ii) the ratio κ{sub liquid} (p)/κ{sub liquid} (0.1 MPa) is 1.45 GPa{sup −1} at 280 K, which, unexpectedly, is about themore » same as κ{sub crystal} (p)/κ{sub crystal} (0.1 MPa) of 1.42 GPa{sup −1} at 298 K; (iii) κ{sub glass} is relatively insensitive to T but sensitive to the applied p (1.38 GPa{sup −1} at 150 K); (iv) κ{sub glass}-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, κ{sub crystal} 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.« less

  20. Energy Transfer between Post-Transition Elements & Rare Earths in Oxide & Chalcogenide Glasses.

    DTIC Science & Technology

    1979-08-27

    Caird [13]. A calculation of reduced matrix elements of Pr3 in 20 Na O • 80 TeO2 glass [14] showed that they differ slightly from data of ref. [121... glasses Transition (lass 35 ZnO 65 TeO2 20 Na2 O 80 TeO 2 fX 106 fX 106 l.,eas 3a, a) Ia’l. faI f.me.s f al f+ I fal 3 H4 - 3 H6 1.56 1.65 1.12...Rare-Earth Doped Glasses 20. jIST HAEV CCnFn~m ,i cn,on ra e sideit If c."*Ar’ -- ~ 14-r by t?-h.c .: r Intensity parameters, radiative transition

  1. Ultra-slow dynamics in low density amorphous ice revealed by deuteron NMR: indication of a glass transition.

    PubMed

    Löw, Florian; Amann-Winkel, Katrin; Loerting, Thomas; Fujara, Franz; Geil, Burkhard

    2013-06-21

    The postulated glass-liquid transition of low density amorphous ice (LDA) is investigated with deuteron NMR stimulated echo experiments. Such experiments give access to ultra-slow reorientations of water molecules on time scales expected for structural relaxation of glass formers close to the glass-liquid transition temperature. An involved data analysis is necessary to account for signal contributions originating from a gradual crystallization to cubic ice. Even if some ambiguities remain, our findings support the view that pressure amorphized LDA ices are of glassy nature and undergo a glass-liquid transition before crystallization.

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

    NASA Astrophysics Data System (ADS)

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

    2017-10-01

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

  3. Oxidation feature and diffusion mechanism of Zr-based metallic glasses near the glass transition point

    NASA Astrophysics Data System (ADS)

    Hu, Zheng; Lei, Xianqi; Wang, Yang; Zhang, Kun

    2018-03-01

    The oxidation behaviors of as-cast, pre-deformed, and crystallized Zr47.9Ti0.3Ni3.1Cu39.3Al9.4 metallic glasses (MGs) were studied near the glass transition point. The oxidation kinetics of the crystallized MGs followed a parabolic-rate law, and the as-cast and pre-deformed MGs exerted a typical two-stage behavior above the glass transition temperature (T g). Most interesting, pre-deformed treatment can significantly improve the oxidation rate of MGs, as the initial oxidation appeared earlier than for the as-cast MGs, and was accompanied by much thicker oxide scale. The EDS and XPS results showed that the metal Al acted as the preferred scavenger that absorbed intrinsic oxygen in the near-surface region of as-cast MGs. However, a homogeneous mixed layer without Al was observed in the pre-deformed MGs. We speculated the accelerated diffusion of other elements in the MGs was due to the local increase in the free volume and significant shear-induced dilation of the local structure. The results from this study demonstrate that MGs exhibit controllable atomic diffusion during the oxidation process, which can facilitate use in super-cooled liquid region applications.

  4. Exploration of a new method in determining the glass transition temperature of BMGs by electrical resistivity

    NASA Astrophysics Data System (ADS)

    Guo, Jing; Zu, Fangqiu; Chen, Zhihao; Zheng, Shubin; Yuan, Yuan

    2005-07-01

    Based on a brief retrospect of the method in establishing Tg of the bulk metallic glasses (BMGs), some perplexities concerning this are pointed out. With the experimental results of Zr-Al-Ni-Cu-X (Nb,Ti) BMGs, a electrical resistivity method is proposed to determine the glass transition temperature of BMGs. With the method, we define two kinds of characteristic temperature related to the glass transition, Tg-dep and Tg-int, respectively. By comparing Tg-dep and Tg-int with Tg determined by the DSC method, we have found that, for the same alloy at the same heating rate, Tg-dep is very close to Tg-onset while Tg-int is approximate to Tg-mid. As a method to determine the glass transition temperature, the electrical resistivity method has proved to be more convenient and practical in comparison with the DSC method, especially when the DSC curve cannot show the glass transition character of BMGs. In addition, we would emphasize that when we refer to Tg, it is necessary to expatiate on the way of denoting the glass transition temperature, such as Tg-dep or Tg-int ( Tg-onset or Tg-mid), and on the heating rate, in order to avoid ambiguity.

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

    NASA Astrophysics Data System (ADS)

    Souda, Ryutaro

    2008-09-01

    Interactions of thin water films with surfaces of graphite and vitrified room-temperature ionic liquid [1-butyl-3-methylimidazolium hexafluorophosphate ([bmim][PF6])] were investigated using time-of-flight secondary ion mass spectrometry as a function of temperature and annealing time to elucidate the glass-liquid transition of water at the molecular level. Surface diffusion of water occurs at temperatures higher than 120K, thereby forming three-dimensional clusters (a two-dimensional layer) on the [bmim][PF6] (graphite) surface. The hydrophobic effect of the surface decreases with increasing coverage of water; the bulklike properties evolve up to 40 ML, as evidenced by the occurrence of film dewetting at around the conventional glass transition temperature (140K). Results also showed that aging is necessary for the water monolayer (a 40 ML water film) to dewet the graphite ([bmim][PF6]) surface. The occurrence of aging is explainable by the successive evolution of two distinct liquids during the glass-liquid transition: low density liquid is followed by supercooled liquid water. The water monolayer on graphite is characterized by the preferred orientation of unpaired OH groups toward the surface; this structure is arrested during the aging time despite the occurrence of surface diffusion. However, the water monolayer formed on the [bmim][PF6] surface agglomerates immediately after the commencement of surface diffusion. The structure of low density liquid tends to be arrested by the attractive interaction with the neighbors.

  6. The characterisation of atomic structure and glass-forming ability of the Zr-Cu-Co metallic glasses studied by molecular dynamics simulations

    NASA Astrophysics Data System (ADS)

    Celtek, M.; Sengul, S.

    2018-03-01

    In the present work, the glass formation process and structural properties of Zr50Cu50-xCox (0 ≤ x ≤ 50) bulk metallic glasses were investigated by a molecular dynamics simulation with the many body tight-binding potentials. The evolution of structure and glass formation process with temperature were discussed using the coordination number, the radial distribution functions, the volume-temperature curve, icosahedral short-range order, glass transition temperature, Voronoi analysis, Honeycutt-Andersen pair analysis technique and the distribution of bond-angles. Results indicate that adding Co causes similar responses on the nature of the Zr50Cu50-xCox (0 ≤ x ≤ 50) alloys except for higher glass transition temperature and ideal icosahedral type ordered local atomic environment. Also, the differences of the atomic radii play the key role in influencing the atomic structure of these alloys. Both Cu and Co atoms play a significant role in deciding the chemical and topological short-range orders of the Zr50Cu50-xCox ternary liquids and amorphous alloys. The glass-forming ability of these alloys is supported by the experimental observations reported in the literature up to now.

  7. Effects of adding LiBF4 on the glass-transition kinetics of 1,2-propanediol

    NASA Astrophysics Data System (ADS)

    Terashima, Yukio; Takeda, Kiyoshi

    2017-11-01

    By applying an isoconversional method to differential-scanning calorimetry (DSC) data, we have discovered that the addition of LiBF4 significantly affects the activation energy Eα of the glass transition of 1,2-propanediol. Depending upon its concentration, the dynamics of the glass transition are affected more by adding LiBF4 at an early stage of the glass-to-liquid transition rather than at later stages. As the mole fraction x of LiBF4 increases, the value of Eα initially increases, but it decreases dramatically during the glass transition. The abrupt decline in Eα suggests that the addition of LiBF4 breaks cooperative rearranging motions into smaller parts. The expansion of cooperativity, and its fragmentation with increasing temperature, can be explained in terms of competition between the hydrogen-bond networks of the alcohol solvent and the ionic interactions due to the added salt. The variability of Eα with temperature is found to correlate exponentially with the dynamic fragility.

  8. 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,

  9. Impact of medium-range order on the glass transition in liquid Ni-Si alloys

    NASA Astrophysics Data System (ADS)

    Lü, Y. J.; Entel, P.

    2011-09-01

    We study the thermophysical properties and structure of liquid Ni-Si alloys using molecular dynamics simulations. The liquid Ni-5% and 10%Si alloys crystallize to form the face-centered cubic (Ni) at 900 and 850 K, respectively, and the glass transitions take place in Ni-20% and 25%Si alloys at about 700 K. The temperature-dependent self-diffusion coefficients and viscosities exhibit more pronounced non-Arrhenius behavior with the increase of Si content before phase transitions, indicating the enhanced glass-forming ability. These appearances of thermodynamic properties and phase transitions are found to closely relate to the medium-range order clusters with the defective face-centered cubic structure characterized by both local translational and orientational order. This locally ordered structure tends to be destroyed by the addition of more Si atoms, resulting in a delay of nucleation and even glass transition instead.

  10. Changes in the Microenvironment of Nitroxide Radicals around the Glass Transition Temperature.

    PubMed

    Bordignon, Enrica; Nalepa, Anna I; Savitsky, Anton; Braun, Lukas; Jeschke, Gunnar

    2015-10-29

    For structural characterization by pulsed EPR methods, spin-labeled macromolecules are routinely studied at cryogenic temperatures. The equilibration of the conformational ensemble during shock-freezing occurs to a good approximation at the glass transition temperature (Tg). In this work, we used X-band power saturation continuous wave (cw) EPR to obtain information on the glass transition temperatures in the microenvironment of nitroxide radicals in solvents or bound to different sites in proteins. The temperature dependence of the saturation curve of nitroxide probes in pure glycerol or ortho-terphenyl showed detectable transitions at the respective Tg values, with the latter solvent characterized by a sharper change of the saturation properties, according to its higher fragility. In contrast, nitroxide probes in a glycerol/water mixture showed a discontinuity in the saturation properties close to the expected glass transition temperature, which made the determination of Tg complicated. Low-temperature W-band cw EPR and W-band ELDOR-detected NMR experiments demonstrated that the discontinuity is due to local rearrangements of H-bonds between water molecules and the nitroxide reporter group. The change in the network of H-bonds formed between the nitroxide and water molecules that occurs around Tg was found to be site-dependent in spin-labeled proteins. This effect can therefore be modulated by neighboring residues with different steric hindrances and/or charge distributions and possibly by the glycerol enrichment on protein surfaces. In conclusion, if the thermal history of the sample is carefully reproduced, the nitroxide probe is extremely sensitive in reporting site-specific changes in the H-bonding to water molecules close to Tg and local glass transition temperatures in spin-labeled macromolecules.

  11. Weak correlations between local density and dynamics near the glass transition.

    PubMed

    Conrad, J C; Starr, F W; Weitz, D A

    2005-11-17

    We perform experiments on two different dense colloidal suspensions with confocal microscopy to probe the relationship between local structure and dynamics near the glass transition. We calculate the Voronoi volume for our particles and show that this quantity is not a universal probe of glassy structure for all colloidal suspensions. We correlate the Voronoi volume to displacement and find that these quantities are only weakly correlated. We observe qualitatively similar results in a simulation of a polymer melt. These results suggest that the Voronoi volume does not predict dynamical behavior in experimental colloidal suspensions; a purely structural approach based on local single particle volume likely cannot describe the colloidal glass transition.

  12. 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.

  13. Glassy nature and glass-to-crystal transition in the binary metallic glass CuZr

    NASA Astrophysics Data System (ADS)

    Wei, Zi-Yang; Shang, Cheng; Zhang, Xiao-Jie; Liu, Zhi-Pan

    2017-06-01

    The prediction for the stability of glassy material is a key challenge in physical science. Here, we report a theoretical framework to predict the glass stability based on stochastic surface walking global optimization and reaction pathway sampling. This is demonstrated by revealing for the first time the global potential energy surface (PES) of two systems, CuZr binary metallic glass and nonglassy pure Cu systems, and establishing the lowest energy pathways linking glassy/amorphous structures with crystalline structures. The CuZr system has a significant number of glassy structures on PES that are ˜0.045 eV /atom above the crystal structure. Two clear trends are identified from global PES in the glass-to-crystal transition of the CuZr system: (i) the local Zr-Cu coordination (nearest neighbor) increases, and (ii) the local Zr bonding environment becomes homogeneous. This allows us to introduce quantitative structural and energetics conditions to distinguish the glassy structures from the crystalline structures. Because of the local Zr-Cu exchange in the glass-to-crystal transition, a high reaction barrier (>0.048 eV /atom ) is present to separate the glassy structures and the crystals in CuZr. By contrast, the Cu system, although it does possess amorphous structures that appear at much higher energy (˜0.075 eV /atom ) with respect to the crystal structure, has very low reaction barriers for the crystallization of amorphous structures, i.e. <0.011 eV /atom . The quantitative data on PES now available from global optimization techniques deepens our understanding on the microscopic nature of glassy material and might eventually facilitate the design of stable glassy materials.

  14. Space-time thermodynamics of the glass transition

    NASA Astrophysics Data System (ADS)

    Merolle, Mauro; Garrahan, Juan P.; Chandler, David

    2005-08-01

    We consider the probability distribution for fluctuations in dynamical action and similar quantities related to dynamic heterogeneity. We argue that the so-called “glass transition” is a manifestation of low action tails in these distributions where the entropy of trajectory space is subextensive in time. These low action tails are a consequence of dynamic heterogeneity and an indication of phase coexistence in trajectory space. The glass transition, where the system falls out of equilibrium, is then an order-disorder phenomenon in space-time occurring at a temperature Tg, which is a weak function of measurement time. We illustrate our perspective ideas with facilitated lattice models and note how these ideas apply more generally. Author contributions: M.M., J.P.G., and D.C. performed research and wrote the paper.

  15. Glass transition temperature of hard chairside reline materials after post-polymerisation treatments.

    PubMed

    Urban, Vanessa M; Machado, Ana L; Alves, Marinês O; Maciel, Adeilton P; Vergani, Carlos E; Leite, Edson R

    2010-09-01

    This study evaluated the effect of post-polymerisation treatments on the glass transition temperature (T(g)) of five hard chairside reline materials (Duraliner II-D, Kooliner-K, New Truliner-N, Ufi Gel hard-U and Tokuso Rebase Fast-T). Specimens (10 x 10 x 1 mm) were made following the manufacturers' instructions and divided into three groups (n = 5). Control group specimens were left untreated. Specimens from the microwave group were irradiated with pre-determined power/time combinations, and specimens from the water-bath group were immersed in hot water at 55 degrees C for 10 min. Glass transition ( degrees C) was performed by differential scanning calorimetry. Data were analysed using anova, followed by post hoc Tukey's test (alpha = 0.05). Both post-polymerisation treatments promoted a significant (p < 0.05) increase in the T(g) of reline material K. Materials K, D and N showed the lowest T(g) (p < 0.05). No significant difference between T and U specimens was observed. Post-polymerisation treatments improved the glass transition of material Kooliner, with the effect being more pronounced for microwave irradiation.

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

    NASA Astrophysics Data System (ADS)

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

    2017-08-01

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

  17. 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)

  18. 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.

  19. The glass transition, crystallization and melting in Au-Pb-Sb alloys

    NASA Technical Reports Server (NTRS)

    Lee, M. C.; Allen, J. L.; Fecht, H. J.; Perepezko, J. H.; Ohsaka, K.

    1988-01-01

    The glass transition, crystallization and melting of Au(55)Pb(22.5)Sb(22.5) alloys have been studied by differential scanning calorimetry DSC. Crystallization on heating above the glass transition temperature Tg (45 C) begins at 64 C. Further crystallization events are observed at 172 C and 205 C. These events were found to correspond to the formation of the intermetallic compounds AuSb2, Au2Pb, and possibly AuPb2, respectively. Isothermal DSC scans of the glassy alloy above Tg were used to monitor the kinetics of crystallization. The solidification behavior and heat capacity in the glass-forming composition range were determined with droplet samples. An undercooling level of 0.3T(L) below the liquidus temperature T(L) was achieved, resulting in crystallization of different stable and metastable phases. The heat capacity C(P) of the undercooled liquid was measured over an undercooling range of 145 C.

  20. Composition formulas of Fe-based transition metals-metalloid bulk metallic glasses derived from dual-cluster model of binary eutectics.

    PubMed

    Naz, Gul Jabeen; Dong, Dandan; Geng, Yaoxiang; Wang, Yingmin; Dong, Chuang

    2017-08-22

    It is known that bulk metallic glasses follow simple composition formulas [cluster](glue atom) 1 or 3 with 24 valence electrons within the framework of the cluster-plus-glue-atom model. Though the relevant nearest-neighbor cluster can be readily identified from a devitrification phase, the glue atoms remains poorly defined. The present work is devoted to understanding the composition rule of Fe-(B,P,C) based multi-component bulk metallic glasses, by introducing a cluster-based eutectic liquid model. This model regards a eutectic liquid to be composed of two stable liquids formulated respectively by cluster formulas for ideal metallic glasses from the two eutectic phases. The dual cluster formulas are first established for binary Fe-(B,C,P) eutectics: [Fe-Fe 14 ]B 2 Fe + [B-B 2 Fe 8 ]Fe ≈ Fe 83.3 B 16.7 for eutectic Fe 83 B 17 , [P-Fe 14 ]P + [P-Fe 9 ]P 2 Fe≈Fe 82.8 P 17.2 for Fe 83 P 17 , and [C-Fe 6 ]Fe 3  + [C-Fe 9 ]C 2 Fe ≈ Fe 82.6 C 17.4 for Fe 82.7 C 17.3 . The second formulas in these dual-cluster formulas, being respectively relevant to devitrification phases Fe 2 B, Fe 3 P, and Fe 3 C, well explain the compositions of existing Fe-based transition metals-metalloid bulk metallic glasses. These formulas also satisfy the 24-electron rule. The proposition of the composition formulas for good glass formers, directly from known eutectic points, constitutes a new route towards understanding and eventual designing metallic glasses of high glass forming abilities.

  1. Pushing the glass transition towards random close packing using self-propelled hard spheres

    NASA Astrophysics Data System (ADS)

    Ni, Ran; Stuart, Martien A. Cohen; Dijkstra, Marjolein

    2013-10-01

    Although the concept of random close packing with an almost universal packing fraction of approximately 0.64 for hard spheres was introduced more than half a century ago, there are still ongoing debates. The main difficulty in searching the densest packing is that states with packing fractions beyond the glass transition at approximately 0.58 are inherently non-equilibrium systems, where the dynamics slows down with a structural relaxation time diverging with density; hence, the random close packing is inaccessible. Here we perform simulations of self-propelled hard spheres, and we find that with increasing activity the relaxation dynamics can be sped up by orders of magnitude. The glass transition shifts to higher packing fractions upon increasing the activity, allowing the study of sphere packings with fluid-like dynamics at packing fractions close to RCP. Our study opens new possibilities of investigating dense packings and the glass transition in systems of hard particles.

  2. 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.

  3. Glass transition of soft colloids

    NASA Astrophysics Data System (ADS)

    Philippe, Adrian-Marie; Truzzolillo, Domenico; Galvan-Myoshi, Julian; Dieudonné-George, Philippe; Trappe, Véronique; Berthier, Ludovic; Cipelletti, Luca

    2018-04-01

    We explore the glassy dynamics of soft colloids using microgels and charged particles interacting by steric and screened Coulomb interactions, respectively. In the supercooled regime, the structural relaxation time τα of both systems grows steeply with volume fraction, reminiscent of the behavior of colloidal hard spheres. Computer simulations confirm that the growth of τα on approaching the glass transition is independent of particle softness. By contrast, softness becomes relevant at very large packing fractions when the system falls out of equilibrium. In this nonequilibrium regime, τα depends surprisingly weakly on packing fraction, and time correlation functions exhibit a compressed exponential decay consistent with stress-driven relaxation. The transition to this novel regime coincides with the onset of an anomalous decrease in local order with increasing density typical of ultrasoft systems. We propose that these peculiar dynamics results from the combination of the nonequilibrium aging dynamics expected in the glassy state and the tendency of colloids interacting through soft potentials to refluidize at high packing fractions.

  4. Gibbs free-energy difference between the glass and crystalline phases of a Ni-Zr alloy

    NASA Technical Reports Server (NTRS)

    Ohsaka, K.; Trinh, E. H.; Holzer, J. C.; Johnson, W. L.

    1993-01-01

    The heats of eutectic melting and devitrification, and the specific heats of the crystalline, glass, and liquid phases have been measured for a Ni24Zr76 alloy. The data are used to calculate the Gibbs free-energy difference, Delta G(AC), between the real glass and the crystal on an assumption that the liquid-glass transition is second order. The result shows that Delta G(AC) continuously increases as the temperature decreases in contrast to the ideal glass case where Delta G(AC) is assumed to be independent of temperature.

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

    PubMed

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

    2017-07-26

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

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

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

    Pyda, Marek; Wunderlich, Bernhard

    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 observedmore » 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).« less

  7. 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. © 2015 Wiley Periodicals, Inc. and the American Pharmacists Association.

  8. Glass transition temperature of dried lens tissue pretreated with trehalose, maltose, or cyclic tetrasaccharide.

    PubMed

    Kawata, Tetsuhiro; Matsuo, Toshihiko; Uchida, Tetsuya

    2014-01-01

    Glass transition temperature is a main indicator for amorphous polymers and biological macromolecules as materials, and would be a key for understanding the role of trehalose in protecting proteins and cells against desiccation. In this study, we measured the glass transition temperature by differential scanning calorimetry of dried lens tissues as a model of a whole biological tissue to know the effect of pretreatment by trehalose and other sugars. Isolated porcine lenses were incubated with saline, 100 or 1000 mM concentration of trehalose, maltose, or cyclic tetrasaccharide dissolved in saline at room temperature for 150 minutes. The solutions were removed and all samples were dried at room temperature in a desiccator until no weight change. The dried tissues were ground into powder and placed in a measuring pan for differential scanning calorimetry. The glass transition temperature of the dried lens tissues, as a mean and standard deviation, was 63.0 ± 6.4°C (n = 3) with saline pretreatment; 53.0 ± 0.8°C and 56.3 ± 2.7°C (n = 3), respectively, with 100 and 1000 mM trehalose pretreatment; 56.0 ± 1.6°C and 55.8 ± 1.1°C (n = 3), respectively, with 100 and 1000 mM maltose pretreatment; 60.0 ± 8.8°C and 59.2 ± 6.3°C (n = 3), respectively, with 100 and 1000 mM cyclic tetrasaccharide pretreatment. The glass transition temperature appeared lower, although not significantly, with trehalose and maltose pretreatments than with saline and cyclic tetrasaccharide pretreatments (P > 0.05, Kruskal-Wallis test). The glass transition temperature of the dried lens tissues with trehalose pretreatment appeared more noticeable on the thermogram, compared with other pretreatments. The glass transition temperature was measured for the first time in the dried lens tissues as an example of a whole biological tissue and might provide a basis for tissue preservation in the dried condition.

  9. Investigation of transition States in bulk and freestanding film polymer glasses.

    PubMed

    Jain, Tushar S; de Pablo, Juan J

    2004-04-16

    We have performed transition state searches on the potential energy landscape for bulk and freestanding film polymer glasses and identified connected minima. An analysis of the displacements between minima shows that the sites that undergo the greatest displacement are highly localized in space for both the bulk and the thin-film systems studied. In the case of the thin film, the clusters originate at the surface and penetrate into the center of the film thereby coupling the relaxation in the center of the film to the mobile surface layer. Furthermore, the energy barriers between minima are lower in the thin film than in the bulk system. These findings can rationalize the experimentally observed depression of the glass transition temperature in freestanding polymer films.

  10. 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.

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

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

    Dmowski, W.; Gierlotka, S.; Wang, Z.

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

  12. 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+.

  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.

  14. 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.

  15. Glass Former Effects on Photoluminescence and Optical Properties of Some Heavy Metal Oxide Glasses Doped with Transition Metal Ions

    NASA Astrophysics Data System (ADS)

    Marzouk, M. A.; Abo-Naf, S. M.; Zayed, H. A.; Hassan, N. S.

    2017-03-01

    Heavy metal oxide (PbO and Bi2O3) glasses doped with transition metal (TM) ions (TiO2, V2O5, Cr2O3, and MnO2) and having low content of common glass formers (B2O3, SiO2, or P2O5) were prepared by the conventional melt annealing method. Ultraviolet, visible absorption, and photoluminescence properties of these glasses were measured, and the data were employed to investigate the prepared glassy samples. The optical absorption spectra of TiO2 and V2O5 exhibited three bands centered at about 240, 305, and 380 nm, followed by a broad asymmetrical near-visible band centered at 425-432 nm, while Cr2O3 and MnO2 exhibited an extended visible peak at 517-548 nm. Results showed that the luminescence intensity changed with different transition metal oxides. From the absorption edge data, the values of the optical band gap Eopt and Urbach energy (ΔE) were calculated. The calculated values of the optical energy gap were found to be dependent on the glass composition. The changing values of optical band gap and band tail can be related to the structural changes that are taking place in the glass samples. The variations of the luminescence intensity, values of optical band gap, band tail, and refractive index gave an indication of the potential use of the prepared glasses to design novel optical functional materials with higher optical performance.

  16. Calorimetric and Neutron Scattering Studies on Glass Transitions and Ionic Diffusions in Imidazolium-based Ionic Liquids

    NASA Astrophysics Data System (ADS)

    Yamamuro, O.; Kofu, M.

    2017-05-01

    Glass transition is one of the central research issues of ionic liquids (ILs). In particular, the most typical ILs, imidazolium-basedones (ImILs) are readily supercooled and exhibit glass transitions below room temperature. We have measured the heat capacities of several ImILs, encoded as CnmimX (n: alkyl carbon number, n = 2-8, X: anion, X = Cl, I, FeCl4, TFSI) using an adiabatic calorimeter. We found that most of ImILs exhibit glass transitions with large Cp jumps in a temperature range between 170 K and 230 K. The large Cp jumps reflect that these ILs are fragile liquids that exhibit large structural change depending on temperature near the glass transition temperature T g. It is also revealed that T g does not depend much on n but on the anion radius. We have investigated the dynamics of CnmimX (n = 2-8, X = Cl, NO3, PF6, TF, FSI, TFSI) by means of a quasielastic neutron scattering (QENS) technique. It was clarified that the ionic diffusion is directly associated with the viscosity and glass transition. The activation energy ΔE a of the ionic diffusion increases with decreasing anion size but remains almost unchanged with n as found for T g. These systematic change of T g and ΔE a can be explained well by taking account the nano-domain structure which is the most characteristic feature of ImILs.

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

    PubMed

    Feng, Li; Wu, Yinsu

    2015-05-05

    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. Copyright © 2015 Elsevier B.V. All rights reserved.

  18. Correlating Free-Volume Hole Distribution to the Glass Transition Temperature of Epoxy Polymers.

    PubMed

    Aramoon, Amin; Breitzman, Timothy D; Woodward, Christopher; El-Awady, Jaafar A

    2017-09-07

    A new algorithm is developed to quantify the free-volume hole distribution and its evolution in coarse-grained molecular dynamics simulations of polymeric networks. This is achieved by analyzing the geometry of the network rather than a voxelized image of the structure to accurately and efficiently find and quantify free-volume hole distributions within large scale simulations of polymer networks. The free-volume holes are quantified by fitting the largest ellipsoids and spheres in the free-volumes between polymer chains. The free-volume hole distributions calculated from this algorithm are shown to be in excellent agreement with those measured from positron annihilation lifetime spectroscopy (PALS) experiments at different temperature and pressures. Based on the results predicted using this algorithm, an evolution model is proposed for the thermal behavior of an individual free-volume hole. This model is calibrated such that the average radius of free-volumes holes mimics the one predicted from the simulations. The model is then employed to predict the glass-transition temperature of epoxy polymers with different degrees of cross-linking and lengths of prepolymers. Comparison between the predicted glass-transition temperatures and those measured from simulations or experiments implies that this model is capable of successfully predicting the glass-transition temperature of the material using only a PDF of the initial free-volume holes radii of each microstructure. This provides an effective approach for the optimized design of polymeric systems on the basis of the glass-transition temperature, degree of cross-linking, and average length of prepolymers.

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

    PubMed

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

    2012-07-05

    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.

  20. Effect of the glass transition temperature on alpha-amylase activity in a starch matrix.

    PubMed

    Chaudhary, Vinita; Panyoyai, Naksit; Small, Darryl M; Shanks, Robert A; Kasapis, Stefan

    2017-02-10

    This study optimises a protocol for the estimation of α-amylase activity in a condensed starch matrix in the vicinity of the glass transition region. Enzymatic activity on the vitrified starch system was compared with that of a reference substrate, maltodextrin. The activity was assayed as the rate of release of reducing sugar using a dinitrosalicylic acid procedure. The condensed carbohydrate matrices served the dual purpose of acting as a substrate as well as producing a pronounced effect on the ability to enzymatic hydrolysis. Activation energies were estimated throughout the glass transition region of condensed carbohydrate preparations based on the concept of the spectroscopic shift factor. Results were used to demonstrate a considerable moderation by the mechanical glass transition temperature, beyond the expected linear effect of the temperature dependence, on the reaction rate of starch hydrolysis by α-amylase in comparison with the low-molecular weight chain of maltodextrin. Copyright © 2016. Published by Elsevier Ltd.

  1. 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.

  2. SU-F-T-17: A Feasibility Study for the Transit Dosimetry with a Glass Dosimeter in Brachytherapy

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

    Moon, S; Yoon, M; Chung, W

    Purpose: Confirming the dose delivered to a patient is important to make sure the treatment quality and safety of the radiotherapy. Measuring a transit dose of the patient during the radiotherapy could be an interesting way to confirm the patient dose. In this study, we evaluated the feasibility of the transit dosimetry with a glass dosimeter in brachytherapy. Methods: We made a phantom that inserted the glass dosimeters and placed under patient lying on a couch for cervix cancer brachytherapy. The 18 glass dosimeters were placed in the phantom arranged 6 per row. A point putting 1cm vertically from themore » source was prescribed as 500.00 cGy. Solid phantoms of 0, 2, 4, 6, 8, 10 cm were placed between the source and the glass dosimeter. The transit dose was measured each thickness using the glass dosimeters and compared with a treatment planning system (TPS). Results: When the transit dose was smaller than 10 cGy, the average of the differences between measured values and calculated values by TPS was 0.50 cGy and the standard deviation was 0.69 cGy. If the transit dose was smaller than 100 cGy, the average of the error was 1.67 ± 4.01 cGy. The error to a point near the prescription point was −14.02 cGy per 500.00 cGy of the prescription dose. Conclusion: The distances from the sources to skin of the patient generally are within 10 cm for cervix cancer cases in brachytherapy. The results of this preliminary study showed the probability of the glass dosimeter as the transit dosimeter in brachytherapy.« less

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

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

    Komatsu, Marina, E-mail: mkomatsu@toki.waseda.jp; Mizuno, Maya; Fukunaga, Kaori

    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 thatmore » a specific feature appears in the THz absorption spectrum of PCL associated with its glass transition.« less

  4. Glass Transition Temperature Measurement for Undercured Cyanate Ester Networks: Challenges, Tips, and Tricks (Briefing Charts)

    DTIC Science & Technology

    2014-01-29

    DISTRIBUTION A: Approved for public release; distribution is unlimited. Thermosetting Polymers Have a TG Envelope – Not Just a TG 4 • The glass transition...glass transition temperature of a thermosetting polymer can vary over a wide range of temperatures depending on how the polymer is processed • A... thermosetting polymer with only one kind of network formation and negligible side reactions, the conversion may be determined at every point in the scan. • By

  5. Fabrication of single crystal architecture in Sb-S-I glass: Transition from dot to line

    DOE PAGES

    Savytskii, Dmytro; Dierolf, Volkmar; Tamura, Nobumichi; ...

    2017-12-08

    We have investigated the occurrence of the sometimes observed grain boundaries, as initial seed is extended to form line in laser-fabricated single-crystal architecture in glass (SCAG). In particular, for Sb 2S 3 SCAG in Sb-S-I glass as a model system, grain boundaries are formed during the transition from laser-written initial seed dot to crystal line. Such grain boundaries during the growth of Sb 2S 3 crystals occur in 16SbI 3-84Sb 2S 3glass, whereas they are absent in Sb 2S 3 glass. We correlate this difference in tendency to form multiple grains with the relative glass forming ability i.e. the dynamicsmore » of nucleation and crystal growth as determined by differential scanning calorimetry (DSC). On the basis of this understanding, methods to minimize the appearance of grain boundaries in the transition region are suggested.« less

  6. Fabrication of single crystal architecture in Sb-S-I glass: Transition from dot to line

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

    Savytskii, Dmytro; Dierolf, Volkmar; Tamura, Nobumichi

    We have investigated the occurrence of the sometimes observed grain boundaries, as initial seed is extended to form line in laser-fabricated single-crystal architecture in glass (SCAG). In particular, for Sb 2S 3 SCAG in Sb-S-I glass as a model system, grain boundaries are formed during the transition from laser-written initial seed dot to crystal line. Such grain boundaries during the growth of Sb 2S 3 crystals occur in 16SbI 3-84Sb 2S 3glass, whereas they are absent in Sb 2S 3 glass. We correlate this difference in tendency to form multiple grains with the relative glass forming ability i.e. the dynamicsmore » of nucleation and crystal growth as determined by differential scanning calorimetry (DSC). On the basis of this understanding, methods to minimize the appearance of grain boundaries in the transition region are suggested.« less

  7. Effects of fragility and reduced glass transition temperature on the glass formation ability of amorphous alloys

    NASA Astrophysics Data System (ADS)

    Xu, Xiao-Jin; Long, Zhi-Lin; Liu, Wei; Liao, Guang-Kai

    2017-11-01

    In this paper, based on the reduced glass transition temperature ({{T}rg} ) proposed by Turnbull and the relation between the glass-forming ability (GFA) and the short-range bond ordering of liquids demonstrated by Tanaka, a detailed analysis on the specific roles of {{T}rg} and fragility of the glass forming liquid (m) in characterizing the GFA has been conducted, and then a novel GFA parameter α [=2/3× (100{{T}rg}{)}-(16/100)× m=67{{T}rg}-0.16m] was put forward. This new GFA parameter α , which increases with a decrease in the critical cooling rate (R c) for glass formation, is a complex function of {{T}rg} and m. The relationship between R c and the parameter α was identified and verified using available literature data for broad range of amorphous alloys with widely varying GFA. The correlation coefficient (R 2) of 0.9 clearly shows an excellent correlation between GFA and the parameter α and that α is a more superior indicator compared to currently reported similar GFA parameters.

  8. The glass transition temperature of thin films: A molecular dynamics study for a bead-spring model.

    PubMed

    Stevenson, Craig S; Curro, John G; McCoy, John D

    2017-05-28

    Molecular dynamics simulations were carried out on free-standing liquid films of different thicknesses h using a bead-spring model of 10 beads per chain. The glass transition temperatures, T g , of the various films were determined from plots of the internal energy versus temperature. We used these simulations to test the validity of our earlier conjecture that the glass transition of a confined liquid could be approximated by pre-averaging over the non-uniform density profile of the film. Using the density profiles from our simulations, we computed the average density of the free-standing films as a function of temperature. In all our film simulations we found, within the error of the simulation, that T g of the film occurred at the same density (or packing fraction) as the bulk system at the bulk glass transition temperature T g B . By equating these densities at their respective glass transition temperatures, as suggested by the simulations, we deduced that T g /T g B is proportional to h 0 /h. This is consistent with previous simulations and experimental data. Moreover, the parameter h 0 is determinable in our model from the density profile of the films.

  9. Dimensional transitions in thermodynamic properties of ideal Maxwell-Boltzmann gases

    NASA Astrophysics Data System (ADS)

    Aydin, Alhun; Sisman, Altug

    2015-04-01

    An ideal Maxwell-Boltzmann gas confined in various rectangular nanodomains is considered under quantum size effects. Thermodynamic quantities are calculated from their relations with the partition function, which consists of triple infinite summations over momentum states in each direction. To obtain analytical expressions, summations are converted to integrals for macrosystems by a continuum approximation, which fails at the nanoscale. To avoid both the numerical calculation of summations and the failure of their integral approximations at the nanoscale, a method which gives an analytical expression for a single particle partition function (SPPF) is proposed. It is shown that a dimensional transition in momentum space occurs at a certain magnitude of confinement. Therefore, to represent the SPPF by lower-dimensional analytical expressions becomes possible, rather than numerical calculation of summations. Considering rectangular domains with different aspect ratios, a comparison of the results of derived expressions with those of summation forms of the SPPF is made. It is shown that analytical expressions for the SPPF give very precise results with maximum relative errors of around 1%, 2% and 3% at exactly the transition point for single, double and triple transitions, respectively. Based on dimensional transitions, expressions for free energy, entropy, internal energy, chemical potential, heat capacity and pressure are given analytically valid for any scale.

  10. Effect of In-situ Cure on Measurement of Glass Transition Temperatures in High-temperature Thermosetting Polymers

    DTIC Science & Technology

    2015-01-01

    TEMPERATURES IN HIGH-TEMPERATURE THERMOSETTING POLYMERS 5a. CONTRACT NUMBER In-House 5b. GRANT NUMBER 5c. PROGRAM ELEMENT NUMBER 6. AUTHOR(S...illustrated the difficulties inherent in measurement of the glass transition temperature of this high-temperature thermosetting polymer via dynamic...copyright protection in the United States. EFFECT OF IN-SITU CURE ON MEASUREMENT OF GLASS TRANSITION TEMPERATURES IN HIGH-TEMPERATURE THERMOSETTING

  11. Simulated glass transition of poly(ethylene oxide) bulk and film: a comparative study.

    PubMed

    Wu, Chaofu

    2011-09-29

    Stepwise cooling molecular dynamics (MD) simulations have been carried out on the bulk and film models for poly(ethylene oxide) (PEO) to understand glass transition of amorphous polymer films. Three types of properties--density, energy, and dynamics--are computed and plotted against the temperature for the two systems. It has been confirmed that all these properties can reveal glass transition in both PEO bulk and film systems. All the determined glass transition temperatures (T(g)'s) drop in the same order of magnitude to the experimental data available. Among various methods, the T(g)'s obtained from the density and energy data are close to each other if the same space regions are defined, which can suggest the same free volume theory, and dynamic T(g)'s obtained from mean-squared displacements (MSDs) are highest, which can suggest the kinetic theory for structural relaxation. Consistently, all these T(g)'s obtained using different methods show that the T(g)'s of PEO film are lower than those of PEO bulk. The free surface layers of polymer films dictate this offset. © 2011 American Chemical Society

  12. Quantum percolation phase transition and magnetoelectric dipole glass in hexagonal ferrites

    NASA Astrophysics Data System (ADS)

    Rowley, S. E.; Vojta, T.; Jones, A. T.; Guo, W.; Oliveira, J.; Morrison, F. D.; Lindfield, N.; Baggio Saitovitch, E.; Watts, B. E.; Scott, J. F.

    2017-07-01

    Hexagonal ferrites not only have enormous commercial impact (£2 billion/year in sales) due to applications that include ultrahigh-density memories, credit-card stripes, magnetic bar codes, small motors, and low-loss microwave devices, they also have fascinating magnetic and ferroelectric quantum properties at low temperatures. Here we report the results of tuning the magnetic ordering temperature in PbF e12 -xG axO19 to zero by chemical substitution x . The phase transition boundary is found to vary as TN˜(1-x /xc ) 2 /3 with xc very close to the calculated spin percolation threshold, which we determine by Monte Carlo simulations, indicating that the zero-temperature phase transition is geometrically driven. We find that this produces a form of compositionally tuned, insulating, ferrimagnetic quantum criticality. Close to the zero-temperature phase transition, we observe the emergence of an electric dipole glass induced by magnetoelectric coupling. The strong frequency behavior of the glass freezing temperature Tm has a Vogel-Fulcher dependence with Tm finite, or suppressed below zero in the zero-frequency limit, depending on composition x . These quantum-mechanical properties, along with the multiplicity of low-lying modes near the zero-temperature phase transition, are likely to greatly extend applications of hexaferrites into the realm of quantum and cryogenic technologies.

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

    PubMed

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

    2012-04-01

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

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

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

    Koperwas, K., E-mail: kkoperwas@us.edu.pl; Grzybowski, A.; Grzybowska, K.

    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 thismore » 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.« less

  15. NMR signature of evolution of ductile-to-brittle transition in bulk metallic glasses.

    PubMed

    Yuan, C C; Xiang, J F; Xi, X K; Wang, W H

    2011-12-02

    The mechanical properties of monolithic metallic glasses depend on the structures at atomic or subnanometer scales, while a clear correlation between mechanical behavior and structures has not been well established in such amorphous materials. In this work, we find a clear correlation of (27)Al NMR isotropic shifts with a microalloying induced ductile-to-brittle transition at ambient temperature in bulk metallic glasses, which indicates that the (27)Al NMR isotropic shift can be regarded as a structural signature to characterize plasticity for this metallic glass system. The study provides a compelling approach for investigating and understanding the mechanical properties of metallic glasses from the point of view of electronic structure. © 2011 American Physical Society

  16. Nature of the transition between a ferromagnetic metal and a spin-glass insulator in pyrochlore molybdates.

    PubMed

    Hanasaki, N; Watanabe, K; Ohtsuka, T; Kézsmárki, I; Iguchi, S; Miyasaka, S; Tokura, Y

    2007-08-24

    The metal-insulator transition has been investigated for pyrochlore molybdates R(2)Mo(2)O(7) with nonmagnetic rare-earth ions R. The dynamical scaling analysis of ac susceptibility reveals that the geometrical frustration causes the atomic spin-glass state. The reentrant spin-glass phase exists below the ferromagnetic transition. The electronic specific heat is enhanced as compared to the band calculation result, perhaps due to the orbital fluctuation in the half-metallic ferromagnetic state. The large specific heat is rather reduced upon the transition, likely because the short-range antiferromagnetic fluctuation shrinks the Fermi surface.

  17. Fragility, network adaptation, rigidity- and stress- transitions in homogenized binary GexS100-x glasses

    NASA Astrophysics Data System (ADS)

    Chakraborty, Shibalik; Boolchand, Punit

    2014-03-01

    Binary GexS100-x glasses reveal elastic and chemical phase transitions driven by network topology. With increasing Ge content x, well defined rigidity (xc(1) =19.3%) and stress(xc(2) =24.85%) transitions and associated optical elasticity power-laws are observed in Raman scattering. Calorimetric measurements reveal a square-well like minimum with window walls that coincide with the two elastic phase transitions. Molar volumes show a trapezoidal-like minimum with edges that nearly coincide with the reversibility window. These results are signatures of the isostatically rigid nature of the elastic phase formed between the rigidity and stress transitions. Complex Cp measurements show melt fragility index, m(x) to also show a global minimum in the reversibility window, underscoring that melt dynamics encode the elastic behavior of the glass formed at Tg. The strong nature of melts formed in the IP has an important practical consequence; they lead to slow homogenization of non-stoichiometric batch compositions reacted at high temperatures. Homogenization of chalcogenides melts/glasses over a scale of a few microns is a pre-requisite to observe the intrinsic physical properties of these materials. Supported by NSF Grant DMR 0853957.

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

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

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

    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 themore » 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.« less

  19. The electrical properties and glass transition of some dental materials after temperature exposure.

    PubMed

    Marcinkowska, Agnieszka; Gauza-Wlodarczyk, Marlena; Kubisz, Leszek; Hedzelek, Wieslaw

    2017-10-17

    The physicochemical properties of dental materials will remain stable only when these materials in question are resistant to the changes in the oral cavity. The oral environment is subject to large temperature variations. The aim of the study was the assessment of electrical properties and glass transition of some dental materials after temperature exposure. Composite materials, compomers, materials for temporary prosthetic replacement and resin-based pit and fissure sealants were used in the study. The method used was electric conductivity of materials under changing temperature. The order of materials presenting the best characteristics for insulators was as follows: materials for temporary prosthetic replacement, resin-based pit and fissure sealants, composites, and compomers. Thanks to comparisons made between graphs during I and II heating run, the method could be used to observe changes in the heated material and determine whether the changes observed are reversible or permanent. The graphs also provided temperature values which contain information on glass transition during heating. In the oral cavity the effect of the constant temperature stimulus influences maturity of dental materials and improves their properties. But high temperatures over glass transition temperature can cause irreversible deformation and changes of the materials properties, even in a short time.

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

    PubMed

    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 20-200 nm thick poly(methyl methacrylate) and polystyrene films coated on silicon substrates at 10(-6)-10(-8) torr 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.

  1. Glass Transition Temperature and Density Scaling in Cumene at Very High Pressure.

    PubMed

    Ransom, T C; Oliver, W F

    2017-07-14

    We present a new method that allows direct measurements of the glass transition temperature T_{g} at pressures up to 4.55 GPa in the glass-forming liquid cumene (isopropylbenzene). This new method uses a diamond anvil cell and can measure T_{g} at pressures of 10 GPa or greater. Measuring T_{g} at the glass→liquid transition involves monitoring the disappearance of pressure gradients initially present in the glass, but also takes advantage of the large increase in the volume expansion coefficient α_{p} at T_{g} as the supercooled or superpressed liquid is entered. Accurate T_{g}(P) values in cumene allow us to show that density scaling holds along this isochronous line up to pressures much higher than any previous study, corresponding to a density increase of 29%. Our results for cumene over this huge compression range yield ρ^{γ}/T=C, where C is a constant and where γ=4.77±0.02 for this nonassociated glass-forming system. Finally, high-pressure cumene viscosity data from the literature taken at much lower pressures and at several different temperatures, corresponding to a large dynamic range of nearly 13 orders of magnitude, are shown to superimpose on a plot of η vs ρ^{γ}/T for the same value of γ.

  2. 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.

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

    PubMed

    Limmer, David T

    2014-06-07

    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.

  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. Molecular dynamics in stiff ionene below glass transition.

    PubMed

    Makrocka-Rydzyk, M; Glowinkowski, S; Jurga, S; Meyer, W H

    1995-08-01

    Temperature dependences of proton and fluorine second moments and spin-lattice relaxation time T1 below glass transition were measured in glassy "I-Do,Pip-Me-BF4" ionene. The existence of motions of methyl groups and segments linking the cationic centers, namely piperidinium rings and trimethylene groups, for the polymeric part of ionene were established. Isotropic rotation of the counter-ion was evidenced and its limited diffusion suggested. To interpret the proton and fluorine relaxation data, a Davidson-Cole distribution of correlation times was assumed.

  6. Cooling rate dependence of the glass transition at free surfaces

    NASA Astrophysics Data System (ADS)

    Streit-Nierobisch, S.; Gutt, C.; Paulus, M.; Tolan, M.

    2008-01-01

    In situ x-ray reflectivity measurements are used to determine the cooling rate dependent freezing of capillary waves on the oligomer poly(propylene glycol). Only above the glass transition temperature TG can the surface roughness σ be described by the capillary wave model for simple liquids, whereas the surface fluctuations are frozen-in at temperatures below TG . As the state of a glass forming liquid strongly depends on its thermal history, this effect occurs for fast cooling rates already at a higher temperature than for slow cooling. For the fastest cooling rates a very large shift of TG up to 240K compared to the bulk value of 196K was observed.

  7. Glass transition temperature and thermodynamic scaling under extreme compression

    NASA Astrophysics Data System (ADS)

    Oliver, William; Ransom, Timothy

    Direct measurements of the glass transition temperature Tg between pressures 1 atm and 4.55 GPa in the glass-forming liquid isopropylbenzene (IPB) will be presented. These data were obtained using a diamond anvil cell enabling measurement of Tg to pressures of 10 GPa or greater. A new method was employed that takes advantage of the large increase in the volume expansion coefficient αp at Tg as the supercooled or superpressed liquid is entered by heating from the glass. Accurate Tg (P) values in IPB allow us to show that thermodynamic scaling holds along this isochronous line up to pressures nearly an order of magnitude greater than any previous study on viscoelastic systems concomitant with an unprecedented density change of 29.4%. Our results for IPB over this huge compression range yield ργ / T = C , where C is a constant and where γ = 4 . 77 +/- 0 . 02 for this non-associated liquid glass-forming system. Finally, high pressure IPB viscosity data from the literature taken at much lower pressures and several different temperatures, corresponding to a dynamic range of nearly 13 orders of magnitude, are shown to superimpose on a plot of η vs. ργ / T using the same value of the scaling exponent γ. Support from the National Science Foundation-DMR, Ray Hughes Fellowship, and the University of Arkansas Honors College are gratefully acknowledged.

  8. The twin cell model and its excellence in determining the glass transition temperature of thin film metallic glass

    NASA Astrophysics Data System (ADS)

    Kanjilal, Baishali; Iram, Samreen; Das, Atreyee; Chakrabarti, Haimanti

    2018-05-01

    This work reports a novel two dimensional approach to the theoretical computation of the glass transition temperature in simple hypothetical icosahedral packed structures based on Thin Film metallic glasses using liquid state theories in the realm of transport properties. The model starts from Navier-Stokes equation and evaluates the statistical average velocity of each different species of atom under the condition of ensemble equality to compute diffusion lengths and the diffusion coefficients as a function of temperature. The additional correction brought in is that of the limited states due to tethering of one nodule vis -a-vis the others. The movement of the molecules use our Twin Cell Model a typical model pertinent for modeling chain motions. A temperature viscosity correction by Cohen and Grest is included through the temperature dependence of the relaxation times for glass formers.

  9. 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

  10. Developmental Idealism, Body Weight and Shape, and Marriage Entry in Transitional China.

    PubMed

    Xu, Hongwei

    2016-04-01

    New trends toward later and less marriage are emerging in post-reform China. Previous research has examined the changing individual-level socioeconomic and demographic characteristics shaping marriage entry in Chinese adults. Employing a cultural model known as developmental idealism (DI), this study argues that a new worldview specifying an ideal body type has become popular in the West and that this new worldview has been exported to China. This new part of the DI package is likely stratified by gender, has a stronger impact on women than on men, and has likely penetrated urban areas more than rural areas. Drawing on the 1991-2009 longitudinal data from the China Health and Nutrition Survey, this study employs discrete-time logit models to estimate the relationships between various body types and transition to first marriage in Chinese young adults 18-30 years old. Body weight status and body shape are measured by body mass index (BMI) and waist-to-hip ratio (WHR), respectively, and further divided into categories of underweight, normal, and obese. Regression results indicate that larger values of BMI and WHR were associated with delayed entry into first marriage in urban women, whereas being overweight or obese was associated with accelerated transition to first marriage in rural men. Not only were these associations statistically significant, but their strengths were substantively remarkable. Findings from this study suggest that both body weight and body shape have important implications for marital success, independent of individual-level socioeconomic and demographic characteristics, and contribute to evolving gender and rural-urban disparities, as China is undergoing a rapid nutrition transition.

  11. Developmental Idealism, Body Weight and Shape, and Marriage Entry in Transitional China

    PubMed Central

    Xu, Hongwei

    2016-01-01

    New trends toward later and less marriage are emerging in post-reform China. Previous research has examined the changing individual-level socioeconomic and demographic characteristics shaping marriage entry in Chinese adults. Employing a cultural model known as developmental idealism (DI), this study argues that a new worldview specifying an ideal body type has become popular in the West and that this new worldview has been exported to China. This new part of the DI package is likely stratified by gender, has a stronger impact on women than on men, and has likely penetrated urban areas more than rural areas. Drawing on the 1991-2009 longitudinal data from the China Health and Nutrition Survey, this study employs discrete-time logit models to estimate the relationships between various body types and transition to first marriage in Chinese young adults 18-30 years old. Body weight status and body shape are measured by body mass index (BMI) and waist-to-hip ratio (WHR), respectively, and further divided into categories of underweight, normal, and obese. Regression results indicate that larger values of BMI and WHR were associated with delayed entry into first marriage in urban women, whereas being overweight or obese was associated with accelerated transition to first marriage in rural men. Not only were these associations statistically significant, but their strengths were substantively remarkable. Findings from this study suggest that both body weight and body shape have important implications for marital success, independent of individual-level socioeconomic and demographic characteristics, and contribute to evolving gender and rural-urban disparities, as China is undergoing a rapid nutrition transition. PMID:27909585

  12. Prediction of the glass transition in aqueous solutions of simple amides by molecular dynamics simulations

    NASA Astrophysics Data System (ADS)

    Kreck, Cara A.; Mandumpal, Jestin B.; Mancera, Ricardo L.

    2011-01-01

    Some simple amides in aqueous solution are used in the cryopreservation of biological tissues as they are believed to promote the vitrification of water, inhibiting its crystallisation and the ensuing damage from ice formation. Molecular dynamics annealing simulations reveal a broadening in the glass transition of aqueous acetamide and N-methylacetamide solutions, suggesting a thermodynamic stabilisation of the glassy state, which may be responsible for their increased tendency of vitrification and their cryoprotective ability. By contrast, aqueous formamide solutions do not exhibit broadening of the glass transition; instead, it is shifted to lower temperatures, which explains their lack of vitrification properties.

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

    PubMed

    Prevosto, Daniele; Capaccioli, Simone; Ngai, K L

    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(u)(g)(h) is higher than the lower transition temperature T(l)(g)(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(u)(g)(h) and T(l)(g)(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(α)(g)associated with the segmental relaxation in the ultrathin film is determined. It turns out that T(α)(g) is nearly the same as T(l)(g)(h) of the lower transition, and hence definitely segmental α-relaxation is the mechanism for the lower transition. Since it is unlikely that the

  14. Local variation of fragility and glass transition temperature of ultra-thin supported polymer films.

    PubMed

    Hanakata, Paul Z; Douglas, Jack F; Starr, Francis W

    2012-12-28

    Despite extensive efforts, a definitive picture of the glass transition of ultra-thin polymer films has yet to emerge. The effect of film thickness h on the glass transition temperature T(g) has been widely examined, but this characterization does not account for the fragility of glass-formation, which quantifies how rapidly relaxation times vary with temperature T. Accordingly, we simulate supported polymer films of a bead-spring model and determine both T(g) and fragility, both as a function of h and film depth. We contrast changes in the relaxation dynamics with density ρ and demonstrate the limitations of the commonly invoked free-volume layer model. As opposed to bulk polymer materials, we find that the fragility and T(g) do not generally vary proportionately. Consequently, the determination of the fragility profile--both locally and for the film as a whole--is essential for the characterization of changes in film dynamics with confinement.

  15. Kinetics and thermal stability of the Ni62Nb38- x Ta x ( x=5, 10, 15, 20 and 25) bulk metallic glasses

    NASA Astrophysics Data System (ADS)

    He, MengKe; Zhang, Yi; Xia, Lei; Yu, Peng

    2017-07-01

    We studied thermal stability and its relationship to the glass-forming ability (GFA) of the Ni62Nb38- x Ta x ( x=5, 10, 15, 20, 25) bulk metallic glasses (BMG) from a kinetic point of view. By fitting the heating-rate dependence of glass transition temperature ( T g onset) and crystallization temperatures ( T x onset and T x peak) of the Ni62Nb38- x Ta x BMG using the Vogel-Fulcher-Tammann (VFT) equation, we obtained the ideal glass transition and crystallization temperatures ( T g 0 and T x 0) and the fragility parameter ( m), and also constructed continuous heating transition (CHT) diagrams for crystallization of the BMG. The CHT diagrams of the BMG indicate enhanced thermal stability by Ta addition; the T g 0 as well as the T x 0 also illustrates this improved stability limit. The compositional dependence of m, which agrees well with that of the reduced glass-transition temperature, indicates a strong correlation between liquid fragility and glass-forming ability in the present alloy system. These results provide new evidence for understanding thermal stability, liquid fragility, and GFA in BMG.

  16. Thermodynamic evidence for the Bose glass transition in twinned YBa 2 Cu 3 O 7 - δ crystals

    DOE PAGES

    Pérez-Morelo, D. J.; Osquiguil, E.; Kolton, A. B.; ...

    2015-07-21

    We used a micromechanical torsional o scillator 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.

  17. Local-structure change rendered by electronic localization-delocalization transition in cerium-based metallic glasses

    NASA Astrophysics Data System (ADS)

    Luo, Qiang; Schwarz, Björn; Swarbrick, Janine C.; Bednarčik, Jozef; Zhu, Yingcai; Tang, Meibo; Zheng, Lirong; Li, Ran; Shen, Jun; Eckert, Jürgen

    2018-02-01

    With increasing temperature, metallic glasses (MGs) undergo first glass transition without pronounced structural change and then crystallization with distinct variation in structure and properties. The present study shows a structural change of short-range order induced by an electron-delocalization transition, along with an unusual large-volume shrinkage in Ce-based MGs. An f -electron localization-delocalization transition with thermal hysteresis is observed from the temperature dependence of x-ray absorption spectroscopy and resonant inelastic x-ray scattering spectra, indicating an inheritance of the 4 f configuration of pure Ce. However, the delocalization transition becomes broadened due to the local structural heterogeneity and related fluctuation of 4 f levels in the Ce-based MGs. The amorphous structure regulated 4 f delocalization of Ce leads to bond shortening and abnormal structure change of the topological and chemical short-range orders. Due to the hierarchical bonding nature, the structure should change in a similar manner on different length scales (but not isostructurally like the Ce metal) in Ce-based MGs.

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

    NASA Astrophysics Data System (ADS)

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

    2017-03-01

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

  20. Melting and glass transition for Ni clusters.

    PubMed

    Teng, Yuyong; Zeng, Xianghua; Zhang, Haiyan; Sun, Deyan

    2007-03-08

    The melting of NiN clusters (N = 29, 50-150) has been investigated by using molecular dynamics (MD) simulations with a quantum corrected Sutton-Chen (Q-SC) many-body potential. Surface melting for Ni147, direct melting for Ni79, and the glass transition for Ni29 have been found, and those melting points are equal to 540, 680, and 940 K, respectively. It shows that the melting temperatures are not only size-dependent but also a symmetrical structure effect; in the neighborhood of the clusters, the cluster with higher symmetry has a higher melting point. From the reciprocal slopes of the caloric curves, the specific heats are obtained as 4.1 kB per atom for the liquid and 3.1 kB per atom for the solid; these values are not influenced by the cluster size apart in the transition region. The calculated results also show that latent heat of fusion is the dominant effect on the melting temperatures (Tm), and the relationship between S and L is given.

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

    NASA Astrophysics Data System (ADS)

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

    2014-04-01

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

  2. Effect of sodium chloride on the glass transition of condensed starch systems.

    PubMed

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

    2015-10-01

    The present investigation deals with the structural properties of condensed potato starch-sodium chloride systems undergoing a thermally induced glass transition. Sample preparation included hot pressing at 120°C for 7 min to produce extensive starch gelatinisation. Materials covered a range of moisture contents from 3.6% to 18.8%, which corresponded to relative humidity values of 11% and 75%. Salt addition was up to 6.0% in formulations. Instrumental work was carried out with dynamic mechanical analysis in tension, modulated differential scanning calorimetry, Fourier transform infrared spectroscopy, scanning electron microscopy and wide angle X-ray diffraction. Experimental conditions ensured the development of amorphous matrices that exhibited thermally reversible glassy consistency. Both moisture content and addition of sodium chloride affected the mechanical strength and glass transition temperature of polymeric systems. Sodium ions interact with chemical moieties of the polysaccharide chain to alter considerably structural properties, as compared to the starch-water matrix. Copyright © 2015. Published by Elsevier Ltd.

  3. 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.

  4. Glass transition and viscosity of P/sub 2/O/sub 5/

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

    Martin, S.W.; Angell, C.A.

    1986-12-04

    The calorimetric glass transition temperature T/sub g/ for pure anhydrous P/sub 2/O/sub 5/ melted in sealed SiO/sub 2/ ampules at 1000 /sup 0/C has been obtained directly for the first time with differential scanning calorimetry, and the increase in heat capacity at T/sub g/ has been determined. T/sub g/ measured in this way is 57 K higher than the value quoted in the literature, which is probably based on an Arrhenius law extrapolation of viscosity data to eta = 10/sup 13/ P. Combining the high-temperature viscosity data with the common observation that, for oxide glasses, eta = 10/sup 12/ Pmore » at the DSC T/sub g/, the authors find that the P/sub 2/O/sub 5/ viscosity obeys an Arrhenius law over at least 6 decades of eta. Furthermore, the intercept at 1/T = 0 coincides with the common point of T/sub g/ - reduced viscosity plots for a wide variety of liquids recently used in establishing the strong vs. fragile classification of glass-forming liquids. On this basis, P/sub 2/O/sub 5/ behaves as the archetypal strong liquid. However, the value of C/sub p/(liquid)/C/sub p/(glass) at T/sub g/, 1.27, is larger than expected on this basis since other strong liquids show smaller values, e.g., GeO/sub 2/ (1.09) and BeF/sub 2/ (no ..delta..C/sub p/ detected). The dependence of T/sub g/ on heating rate has been determined and shows that enthalpy relaxation in the transition region has, within error, the same activation energy (43.9 kcal/mol) as for viscous flow.« less

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

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

    Prevosto, Daniele, E-mail: ngai@df.unipi.it, E-mail: Prevosto@df.unipi.it; Capaccioli, Simone; Dipartimento di Fisica, Università di Pisa, Largo B. Pontecorvo 3, I-56127 Pisa

    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{submore » 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

  6. Shedding Synchrotron Light on a Puzzle of Glasses

    ScienceCinema

    Chumakov, Aleksandr [European Synchrotron Radiation Facility, Grenoble, France

    2017-12-09

    Vibrational dynamics of glasses remains a point of controversial discussions. In particular, the density of vibrational states (DOS) reveals an excess of states above the Debye model called "boson peak." Despite the fact that this universal feature for all glasses has been known for more than 35 years, the nature of the boson peak is still not understood. The application of nuclear inelastic scattering via synchrotron radiation perhaps provides a clearer, more consistent picture of the subject. The distinguishing features of nuclear inelastic scattering relative to, e.g., neutron inelastic scattering, are ideal momentum integration and exact scaling of the DOS in absolute units. This allows for reliable comparison to data from other techniques such as Brillouin light scattering. Another strong point is ideal isotope selectivity: the DOS is measured for a single isotope with a specific low-energy nuclear transition. This allows for special "design" of an experiment to study, for instance, the dynamics of only center-of-mass motions. Recently, we have investigated the transformation of the DOS as a function of several key parameters such as temperature, cooling rate, and density. In all cases the transformation of the DOS is sufficiently well described by a transformation of the continuous medium, in particular, by changes of the macroscopic density and the sound velocity. These results suggest a collective sound-like nature of vibrational dynamics in glasses and cast doubts on microscopic models of glass dynamics. Further insight can be obtained in combined studies of glass with nuclear inelastic and inelastic neutron scattering. Applying two techniques, we have measured the energy dependence of the characteristic correlation length of atomic motions. The data do not reveal localization of atomic vibrations at the energy of the boson peak. Once again, the results suggest that special features of glass dynamics are related to extended motions and not to local models.

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

    NASA Astrophysics Data System (ADS)

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

    2017-02-01

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

  8. Elastic Anomaly and Polyamorphic Transition in (La, Ce)-based Bulk Metallic Glass under Pressure

    DOE PAGES

    Qi, Xintong; Zou, Yongtao; Wang, Xuebing; ...

    2017-04-07

    In this paper, we discovered that in association with the polyamorphism of La 32Ce 32Al 16Ni 5Cu 15 bulk metallic glass, the acoustic velocities, measured up to 12.3 GPa using ultrasonic interferometry, exhibit velocity minima at 1.8 GPa for P wave and 3.2 GPa for S wave. The low and high density amorphous states are distinguished by their distinct pressure derivatives of the bulk and shear moduli. The elasticity, permanent densification, and polyamorphic transition are interpreted by the topological rearrangement of solute-centered clusters in medium-range order (MRO) mediated by the 4f electron delocalization of Ce under pressure. The precisely measuredmore » acoustic wave travel times which were used to derive the velocities and densities provided unprecedented data to document the evolution of the bulk and shear elastic moduli associated with a polyamorphic transition in La 32Ce 32Al 16Ni 5Cu 15 bulk metallic glass and can shed new light on the mechanisms of polyamorphism and structural evolution in metallic glasses under pressure.« less

  9. Photoswitching of glass transition temperatures of azobenzene-containing polymers induces reversible solid-to-liquid transitions.

    PubMed

    Zhou, Hongwei; Xue, Changguo; Weis, Philipp; Suzuki, Yasuhito; Huang, Shilin; Koynov, Kaloian; Auernhammer, Günter K; Berger, Rüdiger; Butt, Hans-Jürgen; Wu, Si

    2017-02-01

    The development of polymers with switchable glass transition temperatures (T g ) can address scientific challenges such as the healing of cracks in high-T g polymers and the processing of hard polymers at room temperature without using plasticizing solvents. Here, we demonstrate that light can switch the T g of azobenzene-containing polymers (azopolymers) and induce reversible solid-to-liquid transitions of the polymers. The azobenzene groups in the polymers exhibit reversible cis-trans photoisomerization abilities. Trans azopolymers are solids with T g above room temperature, whereas cis azopolymers are liquids with T g below room temperature. Because of the photoinduced solid-to-liquid transitions of these polymers, light can reduce the surface roughness of azopolymer films by almost 600%, repeatedly heal cracks in azopolymers, and control the adhesion of azopolymers for transfer printing. The photoswitching of T g provides a new strategy for designing healable polymers with high T g and allows for control over the mechanical properties of polymers with high spatiotemporal resolution.

  10. 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.

  11. 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. Copyright © 2014 Elsevier Ltd. All rights reserved.

  12. 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. Copyright © 2013 Elsevier B.V. All rights reserved.

  13. Stress as an order parameter for the glass transition

    NASA Astrophysics Data System (ADS)

    Visscher, P. B.; Logan, W. T.

    1990-09-01

    The stress tensor has been considered as a possible order parameter for the liquid-glass transition, and its autocorrelation matrix (elements of which are the integrands in the Green-Kubo formulas for bulk and shear viscosity) have been measured in simulations. However, only the k=0 spatial Fourier component has apparently been previously measured. We have measured four Fourier components of all matrix elements of the stress-stress correlation function, and we find that some of those with nonzero wave vector are significantly more persistent (slower decaying) than the k=0 component.

  14. A simple model of entropy relaxation for explaining effective activation energy behavior below the glass transition temperature.

    PubMed

    Bisquert, Juan; Henn, François; Giuntini, Jean-Charles

    2005-03-01

    Strong changes in relaxation rates observed at the glass transition region are frequently explained in terms of a physical singularity of the molecular motions. We show that the unexpected trends and values for activation energy and preexponential factor of the relaxation time tau, obtained at the glass transition from the analysis of the thermally stimulated current signal, result from the use of the Arrhenius law for treating the experimental data obtained in nonstationary experimental conditions. We then demonstrate that a simple model of structural relaxation based on a time dependent configurational entropy and Adam-Gibbs relaxation time is sufficient to explain the experimental behavior, without invoking a kinetic singularity at the glass transition region. The pronounced variation of the effective activation energy appears as a dynamic signature of entropy relaxation that governs the change of relaxation time in nonstationary conditions. A connection is demonstrated between the peak of apparent activation energy measured in nonequilibrium dielectric techniques, with the overshoot of the dynamic specific heat that is obtained in calorimetry techniques.

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

    NASA Astrophysics Data System (ADS)

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

    2015-06-01

    The DC conductivities of glasses having composition x(2NiO.V2O5).(30-x)Li2O.20Bi2O3.50B2O3 (with x=0, 2, 5, 7 and 10, i.e. NVLBB glasses) and glass samples having composition 7NiO.23 Li2O.20Bi2O3.50B2O3 and 7V2O5.23Li2O.20Bi2O3.50B2O3 (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.

  16. Transitioning glass-ceramic scintillators for diagnostic x-ray imaging from the laboratory to commercial scale

    NASA Astrophysics Data System (ADS)

    Beckert, M. Brooke; Gallego, Sabrina; Elder, Eric; Nadler, Jason

    2016-10-01

    This study sought to mitigate risk in transitioning newly developed glass-ceramic scintillator technology from a laboratory concept to commercial product by identifying the most significant hurdles to increased scale. These included selection of cost effective raw material sources, investigation of process parameters with the most significant impact on performance, and synthesis steps that could see the greatest benefit from participation of an industry partner that specializes in glass or optical component manufacturing. Efforts focused on enhancing the performance of glass-ceramic nanocomposite scintillators developed specifically for medical imaging via composition and process modifications that ensured efficient capture of incident X-ray energy and emission of scintillation light. The use of cost effective raw materials and existing manufacturing methods demonstrated proof-of-concept for economical viable alternatives to existing benchmark materials, as well as possible disruptive applications afforded by novel geometries and comparatively lower cost per volume. The authors now seek the expertise of industry to effectively navigate the transition from laboratory demonstrations to pilot scale production and testing to evince the industry of the viability and usefulness of composite-based scintillators.

  17. Heating-induced glass-glass and glass-liquid transformations in computer simulations of water.

    PubMed

    Chiu, Janet; Starr, Francis W; Giovambattista, Nicolas

    2014-03-21

    Water exists in at least two families of glassy states, broadly categorized as the low-density (LDA) and high-density amorphous ice (HDA). Remarkably, LDA and HDA can be reversibly interconverted via appropriate thermodynamic paths, such as isothermal compression and isobaric heating, exhibiting first-order-like phase transitions. We perform out-of-equilibrium molecular dynamics simulations of glassy water using the ST2 model to study the evolution of LDA and HDA upon isobaric heating. Depending on pressure, glass-to-glass, glass-to-crystal, glass-to-vapor, as well as glass-to-liquid transformations are found. Specifically, heating LDA results in the following transformations, with increasing heating pressures: (i) LDA-to-vapor (sublimation), (ii) LDA-to-liquid (glass transition), (iii) LDA-to-HDA-to-liquid, (iv) LDA-to-HDA-to-liquid-to-crystal, and (v) LDA-to-HDA-to-crystal. Similarly, heating HDA results in the following transformations, with decreasing heating pressures: (a) HDA-to-crystal, (b) HDA-to-liquid-to-crystal, (c) HDA-to-liquid (glass transition), (d) HDA-to-LDA-to-liquid, and (e) HDA-to-LDA-to-vapor. A more complex sequence may be possible using lower heating rates. For each of these transformations, we determine the corresponding transformation temperature as function of pressure, and provide a P-T "phase diagram" for glassy water based on isobaric heating. Our results for isobaric heating dovetail with the LDA-HDA transformations reported for ST2 glassy water based on isothermal compression/decompression processes [Chiu et al., J. Chem. Phys. 139, 184504 (2013)]. The resulting phase diagram is consistent with the liquid-liquid phase transition hypothesis. At the same time, the glass phase diagram is sensitive to sample preparation, such as heating or compression rates. Interestingly, at least for the rates explored, our results suggest that the LDA-to-liquid (HDA-to-liquid) and LDA-to-HDA (HDA-to-LDA) transformation lines on heating are related

  18. Heating-induced glass-glass and glass-liquid transformations in computer simulations of water

    NASA Astrophysics Data System (ADS)

    Chiu, Janet; Starr, Francis W.; Giovambattista, Nicolas

    2014-03-01

    Water exists in at least two families of glassy states, broadly categorized as the low-density (LDA) and high-density amorphous ice (HDA). Remarkably, LDA and HDA can be reversibly interconverted via appropriate thermodynamic paths, such as isothermal compression and isobaric heating, exhibiting first-order-like phase transitions. We perform out-of-equilibrium molecular dynamics simulations of glassy water using the ST2 model to study the evolution of LDA and HDA upon isobaric heating. Depending on pressure, glass-to-glass, glass-to-crystal, glass-to-vapor, as well as glass-to-liquid transformations are found. Specifically, heating LDA results in the following transformations, with increasing heating pressures: (i) LDA-to-vapor (sublimation), (ii) LDA-to-liquid (glass transition), (iii) LDA-to-HDA-to-liquid, (iv) LDA-to-HDA-to-liquid-to-crystal, and (v) LDA-to-HDA-to-crystal. Similarly, heating HDA results in the following transformations, with decreasing heating pressures: (a) HDA-to-crystal, (b) HDA-to-liquid-to-crystal, (c) HDA-to-liquid (glass transition), (d) HDA-to-LDA-to-liquid, and (e) HDA-to-LDA-to-vapor. A more complex sequence may be possible using lower heating rates. For each of these transformations, we determine the corresponding transformation temperature as function of pressure, and provide a P-T "phase diagram" for glassy water based on isobaric heating. Our results for isobaric heating dovetail with the LDA-HDA transformations reported for ST2 glassy water based on isothermal compression/decompression processes [Chiu et al., J. Chem. Phys. 139, 184504 (2013)]. The resulting phase diagram is consistent with the liquid-liquid phase transition hypothesis. At the same time, the glass phase diagram is sensitive to sample preparation, such as heating or compression rates. Interestingly, at least for the rates explored, our results suggest that the LDA-to-liquid (HDA-to-liquid) and LDA-to-HDA (HDA-to-LDA) transformation lines on heating are related

  19. 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. Copyright © 2016 Elsevier Ltd. All rights reserved.

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

    DOE PAGES

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

    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 longer waitingmore » 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

  1. The ferromagnetic-spin glass transition in PdMn alloys: symmetry breaking of ferromagnetism and spin glass studied by a multicanonical method.

    PubMed

    Kato, Tomohiko; Saita, Takahiro

    2011-03-16

    The magnetism of Pd(1-x)Mn(x) is investigated theoretically. A localized spin model for Mn spins that interact with short-range antiferromagnetic interactions and long-range ferromagnetic interactions via itinerant d electrons is set up, with no adjustable parameters. A multicanonical Monte Carlo simulation, combined with a procedure of symmetry breaking, is employed to discriminate between the ferromagnetic and spin glass orders. The transition temperature and the low-temperature phase are determined from the temperature variation of the specific heat and the probability distributions of the ferromagnetic order parameter and the spin glass order parameter at different concentrations. The calculation results reveal that only the ferromagnetic phase exists at x < 0.02, that only the spin glass phase exists at x > 0.04, and that the two phases coexist at intermediate concentrations. This result agrees semi-quantitatively with experimental results.

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

    PubMed

    Khabaz, Fardin; Khare, Rajesh

    2015-11-05

    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.

  3. Characterization of the glass transition of water predicted by molecular dynamics simulations using nonpolarizable intermolecular potentials.

    PubMed

    Kreck, Cara A; Mancera, Ricardo L

    2014-02-20

    Molecular dynamics simulations allow detailed study of the experimentally inaccessible liquid state of supercooled water below its homogeneous nucleation temperature and the characterization of the glass transition. Simple, nonpolarizable intermolecular potentials are commonly used in classical molecular dynamics simulations of water and aqueous systems due to their lower computational cost and their ability to reproduce a wide range of properties. Because the quality of these predictions varies between the potentials, the predicted glass transition of water is likely to be influenced by the choice of potential. We have thus conducted an extensive comparative investigation of various three-, four-, five-, and six-point water potentials in both the NPT and NVT ensembles. The T(g) predicted from NPT simulations is strongly correlated with the temperature of minimum density, whereas the maximum in the heat capacity plot corresponds to the minimum in the thermal expansion coefficient. In the NVT ensemble, these points are instead related to the maximum in the internal pressure and the minimum of its derivative, respectively. A detailed analysis of the hydrogen-bonding properties at the glass transition reveals that the extent of hydrogen-bonds lost upon the melting of the glassy state is related to the height of the heat capacity peak and varies between water potentials.

  4. Dielectric spectroscopy for the determination of the glass transition temperature of pharmaceutical solid dispersions.

    PubMed

    O'Donnell, Kevin P; Woodward, W H Hunter

    2015-06-01

    The purpose of this study was to evaluate analytical techniques for the measurement of the glass transition temperature of HPMC and formulated solid dispersions thereof. Unmodified samples of various grades of HPMC and solid dispersions of HPMC and itraconazole produced by hot melt extrusion were analyzed by thermomechanical analysis, differential scanning calorimetry, thermally stimulated depolarization current and dielectric spectroscopy. It was found that dielectric spectroscopy offers the best accuracy and reproducibility for analysis of the base HPMC powders regardless of the substitution type or viscosity grade and that the obtained results were not frequency dependent. The results of dielectric measurements of solid dispersions prepared by hot melt extrusion were compared with predicted values of the Gordon-Taylor equation. It was found that time-temperature superposition effects and small molecule frequency dependence makes broadly applying determination of the glass transition temperature in drug dispersions by dielectric spectroscopy prohibitively difficult.

  5. Disruption of Hydrogen-Bonding Network Eliminates Water Anomalies Normally Observed on Cooling to Its Calorimetric Glass Transition

    DOE PAGES

    Borreguero, Jose M.; Mamontov, Eugene

    2017-04-11

    Here, the calorimetric glass-transition temperature of water is 136 K, but extrapolation of thermodynamic and relaxation properties of water from ambient temperature to below its homogeneous nucleation temperature T H = 235 K predicts divergence at T S = 228 K. The “no-man’s land” between the T H and glassy water crystallization temperature of 150 K, which is encountered on warming up from the vitrified state, precludes a straightforward reconciliation of the two incompatible temperature dependences of water properties, above 235 K and below 150 K. The addition of lithium chloride to water allows bypassing both T H and Tmore » S on cooling, resulting in the dynamics with no features except the calorimetric glass transition, still at 136 K. We show that lithium chloride prevents hydrogen-bonding network completion in water on cooling, as manifested, in particular, in changing microscopic diffusion mechanism of the water molecules. Thus thermodynamic and relaxation peculiarities exhibited by pure water on cooling to its glass transition, such as the existence of the T H and T S, must be associated specifically with the hydrogen-bonding network.« less

  6. Activity statistics in a colloidal glass former: Experimental evidence for a dynamical transition

    NASA Astrophysics Data System (ADS)

    Abou, Bérengère; Colin, Rémy; Lecomte, Vivien; Pitard, Estelle; van Wijland, Frédéric

    2018-04-01

    In a dense colloidal suspension at a volume fraction below the glass transition, we follow the trajectories of an assembly of tracers over a large time window. We define a local activity, which quantifies the local tendency of the system to rearrange. We determine the statistics of the time integrated activity, and we argue that it develops a low activity tail that comes together with the onset of glassy-like behavior and heterogeneous dynamics. These rare events may be interpreted as the reflection of an underlying dynamic phase transition.

  7. 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...

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

    DOE PAGES

    Alderman, O. L. G.; Benmore, C. J.; Tamalonis, A.; ...

    2016-12-01

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

  9. GlassForm

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

    2011-09-16

    GlassForm is a software tool for generating preliminary waste glass formulas for a given waste stream. The software is useful because it reduces the number of verification melts required to develop a suitable additive composition. The software includes property models that calculate glass properties of interest from the chemical composition of the waste glass. The software includes property models for glass viscosity, electrical conductivity, glass transition temperature, and leach resistance as measured by the 7-day product consistency test (PCT).

  10. Evidence for reentrant spin glass behavior in transition metal substituted Co-Ga alloys near critical concentration

    NASA Astrophysics Data System (ADS)

    Yasin, Sk. Mohammad; Srinivas, V.; Kasiviswanathan, S.; Vagadia, Megha; Nigam, A. K.

    2018-04-01

    In the present study magnetic and electrical transport properties of transition metal substituted Co-Ga alloys (near critical cobalt concentration) have been investigated. Analysis of temperature and field dependence of dc magnetization and ac susceptibility (ACS) data suggests an evidence of reentrant spin glass (RSG) phase in Co55.5TM3Ga41.5 (TM = Co, Cr, Fe, Cu). The magnetic transition temperatures (TC and Tf) are found to depend on the nature of TM element substitution with the exchange coupling strength Co-Fe > Co-Co > Co-Cu > Co-Cr. From magnetization dynamics precise transition temperatures for the glassy phases are estimated. It is found that characteristic relaxation times are higher than that of spin glasses with minimal spin-cluster formation. The RSG behavior has been further supported by the temperature dependence of magnetotransport studies. From the magnetic field and substitution effects it has been established that the magnetic and electrical transport properties are correlated in this system.

  11. Weak- versus strong-disorder superfluid—Bose glass transition in one dimension

    NASA Astrophysics Data System (ADS)

    Doggen, Elmer V. H.; Lemarié, Gabriel; Capponi, Sylvain; Laflorencie, Nicolas

    2017-11-01

    Using large-scale simulations based on matrix product state and quantum Monte Carlo techniques, we study the superfluid to Bose glass transition for one-dimensional attractive hard-core bosons at zero temperature, across the full regime from weak to strong disorder. As a function of interaction and disorder strength, we identify a Berezinskii-Kosterlitz-Thouless critical line with two different regimes. At small attraction where critical disorder is weak compared to the bandwidth, the critical Luttinger parameter Kc takes its universal Giamarchi-Schulz value Kc=3 /2 . Conversely, a nonuniversal Kc>3 /2 emerges for stronger attraction where weak-link physics is relevant. In this strong-disorder regime, the transition is characterized by self-similar power-law-distributed weak links with a continuously varying characteristic exponent α .

  12. Using neutrons, X-rays and nuclear magnetism to determine the role of transition metal oxide inclusions on both glass structure and stability in automotive glass enamels.

    PubMed

    Bowron, Daniel T; Booth, Jonathan; Barrow, Nathan S; Sutton, Patricia; Johnson, Simon R

    2018-05-23

    Low levels of transition metal oxides in alkali borosilicate glass systems can drastically influence crystallisation and phase separation properties. We investigated the non-monotonic effect of manganese doping on suppressing crystallisation, and the influence on optical properties by iron oxide doping, in terms of local atomic structure. Structural models based on empirical potential structure refinement were generated from neutron and X-ray scattering data, and compared against multinuclear solid-state NMR. This revealed that a 2.5% manganese doping had a disruptive effect on the entire glass network, supressing crystallisation of an undesired bismuth silicate phase, and that iron species preferentially locate near borate tetrahedra. Preventing phase separation and controlling crystallisation behaviour of glass are critical to the ultimate properties of automotive glass enamels.

  13. Nonequilibrium viscosity of glass

    NASA Astrophysics Data System (ADS)

    Mauro, John C.; Allan, Douglas C.; Potuzak, Marcel

    2009-09-01

    Since glass is a nonequilibrium material, its properties depend on both composition and thermal history. While most prior studies have focused on equilibrium liquid viscosity, an accurate description of nonequilibrium viscosity is essential for understanding the low temperature dynamics of glass. Departure from equilibrium occurs as a glass-forming system is cooled through the glass transition range. The glass transition involves a continuous breakdown of ergodicity as the system gradually becomes trapped in a subset of the available configurational phase space. At very low temperatures a glass is perfectly nonergodic (or “isostructural”), and the viscosity is described well by an Arrhenius form. However, the behavior of viscosity during the glass transition range itself is not yet understood. In this paper, we address the problem of glass viscosity using the enthalpy landscape model of Mauro and Loucks [Phys. Rev. B 76, 174202 (2007)] for selenium, an elemental glass former. To study a wide range of thermal histories, we compute nonequilibrium viscosity with cooling rates from 10-12 to 1012K/s . Based on these detailed landscape calculations, we propose a simplified phenomenological model capturing the essential physics of glass viscosity. The phenomenological model incorporates an ergodicity parameter that accounts for the continuous breakdown of ergodicity at the glass transition. We show a direct relationship between the nonequilibrium viscosity parameters and the fragility of the supercooled liquid. The nonequilibrium viscosity model is validated against experimental measurements of Corning EAGLE XG™ glass. The measurements are performed using a specially designed beam-bending apparatus capable of accurate nonequilibrium viscosity measurements up to 1016Pas . Using a common set of parameters, the phenomenological model provides an accurate description of EAGLE XG™ viscosity over the full range of measured temperatures and fictive temperatures.

  14. 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. © 2011 Wiley Periodicals, Inc.

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

    PubMed

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

    2008-04-01

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

  16. New High Index Optical Glasses

    NASA Astrophysics Data System (ADS)

    Blair, Gerald E.; Greco, Edgar J.; DeJager, Donald; Wylot, James M.

    1982-02-01

    The pioneering work of Charles W. Frederick and George W. Morey on the design by Frederick of an "ideal photographic lens" using hypothetical glasses, and the subsequent discovery and development of rare-element borate glasses by Morey, has been resumed at Eastman Kodak. New ultra-high index, low dispersion crown glasses and companion flint glasses have been developed, based on the needs dictated by lens design studies for novel fast cine' and still camera lenses. These new glasses reduce the number of elements required in a lens while maintaining or improving lens performance. Composition studies leading to these new glasses will be discussed.

  17. Correlation between physical properties and ultrasonic relaxation parameters in transition metal tellurite glasses

    NASA Astrophysics Data System (ADS)

    Abd El-Moneim, A.

    2003-07-01

    The correlation between activation energy of ultrasonic relaxation process through the temperature range from 140 to 300 K and some physical properties has been investigated in pure TeO 2 and transition metal TeO 2-V 2O 5 and TeO 2-MoO 3 glasses according to Bridge and Patel's theory. The oxygen density (loss centers), number of two-well systems, hopping distance and mechanical relaxation time have been calculated in these glasses from the data of density, bulk modulus and stretching force constant of the glass. It has been found that the acoustic activation energy increased linearly with both the oxygen density and the number of two-well systems. The correlation between the acoustic activation energy and bulk modulus was achieved through the stretching force constant of the network and other structural parameters. Moreover, the experimental values of activation energy (V) agree well with those calculated from an empirical equation presented in this study in the form V=2.9×10 -7 F( F/ K) 3.37, where F is the stretching force constant of the glass and K is the experimental bulk modulus.

  18. A new glass option for parenteral packaging.

    PubMed

    Schaut, Robert A; Peanasky, John S; DeMartino, Steven E; Schiefelbein, Susan L

    2014-01-01

    Glass is the ideal material for parenteral packaging because of its chemical durability, hermeticity, strength, cleanliness, and transparency. Alkali borosilicate glasses have been used successfully for a long time, but they do have some issues relating to breakage, delamination, and variation in hydrolytic performance. In this paper, alkali aluminosilicate glasses are introduced as a possible alternative to alkali borosilicate glasses. An example alkali aluminosilicate glass is shown to meet the compendial requirements, and to have similar thermal, optical, and mechanical attributes as the current alkali borosilicate glasses. In addition, the alkali aluminosilicate performed as well or better than the current alkali borosilicates in extractables tests and stability studies, which suggests that it would be suitable for use with the studied liquid product formulation. The physical, mechanical, and optical properties of glass make it an ideal material for packaging injectable drugs and biologics. Alkali borosilicate glasses have been used successfully for a long time for these applications, but there are some issues. In this paper, alkali aluminosilicate glasses are introduced as a possible alternative to alkali borosilicate glasses. An example alkali aluminosilicate glass is shown to meet the requirements for packaging injectable drugs and biologics, and to be suitable for use with a particular liquid drug. © PDA, Inc. 2014.

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

    PubMed

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

    2010-12-28

    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(×) ≈ 10(3) Poise, for all 84 liquids. The crossover temperature, T(×), located well above the calorimetric glass transition temperature T(g), 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.

  20. 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

  1. Diopside-Fluorapatite-Wollastonite Based Bioactive Glasses and Glass-ceramics =

    NASA Astrophysics Data System (ADS)

    Kansal, Ishu

    Bioactive glasses and glass-ceramics are a class of biomaterials which elicit special response on their surface when in contact with biological fluids, leading to strong bonding to living tissue. This particular trait along with good sintering ability and high mechanical strength make them ideal materials for scaffold fabrication. The work presented in this thesis is directed towards understanding the composition-structure-property relationships in potentially bioactive glasses designed in CaO-MgO-P2O5-SiO2-F system, in some cases with added Na2O. The main emphasis has been on unearthing the influence of glass composition on molecular structure, sintering ability and bioactivity of phosphosilicate glasses. The parent glass compositions have been designed in the primary crystallization field of the pseudo-ternary system of diopside (CaO•MgO•2SiO2) - fluorapatite (9CaO•3P2O5•CaF2) - wollastonite (CaO•SiO2), followed by studying the impact of compositional variations on the structure-property relationships and sintering ability of these glasses. All the glasses investigated in this work have been synthesized via melt-quenching route and have been characterized for their molecular structure, sintering ability, chemical degradation and bioactivity using wide array of experimental tools and techniques. It has been shown that in all investigated glass compositions the silicate network was mainly dominated by Q2 units while phosphate in all the glasses was found to be coordinated in orthophosphate environment. The glass compositions designed in alkali-free region of diopside - fluorapatite system demonstrated excellent sintering ability and good bioactivity in order to qualify them as potential materials for scaffold fabrication while alkali-rich bioactive glasses not only hinder the densification during sintering but also induce cytotoxicity in vitro, thus, are not ideal candidates for in vitro tissue engineering. One of our bioglass compositions with low sodium

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

    ERIC Educational Resources Information Center

    Sperling, L. H.

    1982-01-01

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

  3. 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.

  4. Beating Homogeneous Nucleation and Tuning Atomic Ordering in Glass-Forming Metals by Nanocalorimetry.

    PubMed

    Zhao, Bingge; Yang, Bin; Abyzov, Alexander S; Schmelzer, Jürn W P; Rodríguez-Viejo, Javier; Zhai, Qijie; Schick, Christoph; Gao, Yulai

    2017-12-13

    In this paper, the amorphous Ce 68 Al 10 Cu 20 Co 2 (atom %) alloy was in situ prepared by nanocalorimetry. The high cooling and heating rates accessible with this technique facilitate the suppression of crystallization on cooling and the identification of homogeneous nucleation. Different from the generally accepted notion that metallic glasses form just by avoiding crystallization, the role of nucleation and growth in the crystallization behavior of amorphous alloys is specified, allowing an access to the ideal metallic glass free of nuclei. Local atomic configurations are fundamentally significant to unravel the glass forming ability (GFA) and phase transitions in metallic glasses. For this reason, isothermal annealing near T g from 0.001 s to 25,000 s following quenching becomes the strategy to tune local atomic configurations and facilitate an amorphous alloy, a mixed glassy-nanocrystalline state, and a crystalline sample successively. On the basis of the evolution of crystallization enthalpy and overall latent heat on reheating, we quantify the underlying mechanism for the isothermal nucleation and crystallization of amorphous alloys. With Johnson-Mehl-Avrami method, it is demonstrated that the coexistence of homogeneous and heterogeneous nucleation contributes to the isothermal crystallization of glass. Heterogeneous rather than homogeneous nucleation dominates the isothermal crystallization of the undercooled liquid. For the mixed glassy-nanocrystalline structure, an extraordinary kinetic stability of the residual glass is validated, which is ascribed to the denser packed interface between amorphous phase and ordered nanocrystals. Tailoring the amorphous structure by nanocalorimetry permits new insights into unraveling GFA and the mechanism that correlates local atomic configurations and phase transitions in metallic glasses.

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

    NASA Astrophysics Data System (ADS)

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

    2017-05-01

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

  6. High temperature spin-glass-like transition in La0.67Sr0.33MnO3 nanofibers near the Curie point.

    PubMed

    Lu, Ruie; Yang, Sen; Li, Yitong; Chen, Kaiyun; Jiang, Yun; Fu, Bi; Zhang, Yin; Zhou, Chao; Xu, Minwei; Zhou, Xuan

    2017-06-28

    The glassy transition of superparamagnetic (SPM) (r < r 0 ) nanoparticle systems usually occurs at a very low temperature that greatly limits its application to high temperatures. In this work, we report a spin-glass-like (SGL) behavior near the Curie point (T C ), i.e., T 0 = 330 K, in La 0.67 Sr 0.33 MnO 3 (LSMO) nanofibers (NFs) composed of nanoparticles beyond the SPM size (r ≫ r 0 ), resulting in a significant increase of the glass transition temperature. This SGL transition near the T C of bulk LSMO can be explained to be the scenario of locally ordered clusters embedded in a disordered host, in which the assembly of nanoparticles has a magnetic core-shell model driven by surface spin glass. The presence of a surface spin glass of nanoparticles was proved by the Almeida-Thouless line δT f ∝ H 2/3 , exchange bias, and reduced saturation magnetization of the NF system. Composite dynamics were found - that is, both the SPM and the super-spin-glass (SSG) behavior are found in such an NF system. The bifurcation of the zero-field-cooled (ZFC) and field-cooled (FC) magnetization vs. temperature curves at the ZFC peak, and the flatness of FC magnetization involve SSG, while the frequency-dependent ac susceptibility anomaly follows the Vogel-Fulcher law that implies weak dipole interactions of the SPM model. This finding can help us to find a way to search for high temperature spin glass materials.

  7. Evidence for two spin-glass transitions with magnetoelastic and magnetoelectric couplings in the multiferroic (B i1 -xB ax) (F e1 -xT ix ) O3 system

    NASA Astrophysics Data System (ADS)

    Kumar, Arun; Kaushik, S. D.; Siruguri, V.; Pandey, Dhananjai

    2018-03-01

    For disordered Heisenberg systems with small single ion anisotropy (D ), two spin-glass (SG) transitions below the long-range ordered (LRO) phase transition temperature (Tc) have been predicted theoretically for compositions close to the percolation threshold. Experimental verification of these predictions is still controversial for conventional spin glasses. We show that multiferroic spin-glass systems can provide a unique platform for verifying these theoretical predictions via a study of change in magnetoelastic and magnetoelectric couplings, obtained from an analysis of diffraction data, at the spin-glass transition temperatures (TSG). Results of macroscopic (dc M (H , T ), M(t ), ac susceptibility [χ (ω, T )], and specific heat (Cp)) and microscopic (x-ray and neutron scattering) measurements are presented on disordered BiFe O3 , a canonical Heisenberg system with small single ion anisotropy, which reveal appearance of two spin-glass phases, SG1 and SG2, in coexistence with the LRO phase below the Almeida-Thouless (A-T) and Gabey-Toulouse (G-T) lines. It is shown that the temperature dependence of the integrated intensity of the antiferromagnetic (AFM) peak shows dips with respect to the Brillouin function behavior around the SG1 and SG2 transition temperatures. The temperature dependence of the unit cell volume departs from the Debye-Grüneisen behavior below the SG1 transition and the magnitude of departure increases significantly with decreasing temperature up to the electromagnon driven transition temperature below which a small change of slope occurs followed by another similar change of slope at the SG2 transition temperature. The ferroelectric polarization also changes significantly at the two spin-glass transition temperatures. These results, obtained using microscopic techniques, clearly demonstrate that the SG1 and SG2 transitions occur on the same magnetic sublattice and are intrinsic to the system. We also construct a phase diagram showing all

  8. Unusual inhomogeneous microstructures in charge glass state of PbCrO3

    NASA Astrophysics Data System (ADS)

    Kurushima, Kosuke; Tsukasaki, Hirofumi; Ogata, Takahiro; Sakai, Yuki; Azuma, Masaki; Ishii, Yui; Mori, Shigeo

    2018-05-01

    We investigated the microstructures and local structures of perovskite PbCrO3, which shows a metal-to-insulator transition and a 9.8% volume collapse, by electron diffraction, high-resolution transmission electron microscopy (TEM), and high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM). It is revealed that the charge glass state is characterized by the unique coexistence of the crystalline state with a cubic symmetry on average and the noncrystalline state. HAADF-STEM observation at atomic resolution revealed that Pb ions were displaced from the ideal A site position of the cubic perovskite structure, which gives rise to characteristic diffuse scatterings around the fundamental Bragg reflections. These structural inhomogeneities are crucial to the understanding of the unique physical properties in the charge glass state of PbCrO3.

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

    PubMed

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

    2015-11-10

    Amorphous materials are inherently unstable and tend to crystallize upon storage. In this study, we investigated the extent to which the physical stability and inherent crystallization tendency of drugs are related to their glass-forming ability (GFA), the glass transition temperature (Tg) and thermodynamic factors. Differential scanning calorimetry was used to produce the amorphous state of 52 drugs [18 compounds crystallized upon heating (Class II) and 34 remained in the amorphous state (Class III)] and to perform in situ storage for the amorphous material for 12h at temperatures 20°C above or below the Tg. A computational model based on the support vector machine (SVM) algorithm was developed to predict the structure-property relationships. All drugs maintained their Class when stored at 20°C below the Tg. Fourteen of the Class II compounds crystallized when stored above the Tg whereas all except one of the Class III compounds remained amorphous. These results were only related to the glass-forming ability and no relationship to e.g. thermodynamic factors was found. The experimental data were used for computational modeling and a classification model was developed that correctly predicted the physical stability above the Tg. The use of a large dataset revealed that molecular features related to aromaticity and π-π interactions reduce the inherent physical stability of amorphous drugs. Copyright © 2015 Elsevier B.V. All rights reserved.

  10. Impulsive Stimulated Light Scattering Studies of the Liquid-Glass Transition: on the Experimental Verification of Mode-Coupling Theory Predictions.

    NASA Astrophysics Data System (ADS)

    Halalay, Ion C.

    A study of the structural glass transition trough impulsive stimulated light scattering experiments has been carried out in concentrated aqueous lithium chloride solutions, at temperatures ranging from ambient to cryogenic. A specially designed sample cell made it possible to cover the whole temperature interval from simple liquid, to viscoelastic supercooled liquid, to glass. It is shown that a phenomenological description of the results of these experiments in terms of a spectrum of relaxation times through the use of a Kohlrausch-Williams-Watts relaxation function is inadequate. Based on predictions of mode-coupling theory of the liquid-glass transition, an alternative approach to data interpretation is proposed. It is shown that for an aqueous lithium chloride solution, the prediction of simple scaling and identical scaling for mechanical and electrical susceptibilities seems to be valid. However, another prediction of theory is called into question: instead of a power-law behavior on temperature difference, it is found experimentally that the behavior of the susceptibility spectrum minimum is exponential. Similar disagreements are found for other two materials, triphenyl phosphite and polypropylene oxide. The causes for these discrepancies are discussed and it is concluded that additional experimentation is necessary to verify theoretical claims. Experiments are proposed which can test these predictions and serve as guide for the construction of theoretical models for the glass transition in real systems. (Copies available exclusively from MIT Libraries, Rm. 14-0551, Cambridge, MA 02139-4307. Ph. 617 -253-5668; Fax 617-253-1690.).

  11. Slow dynamics approaching the glass transition in repulsive magnetic fluids

    NASA Astrophysics Data System (ADS)

    Mériguet, G.; Dubois, E.; Dupuis, V.; Perzynski, R.

    2004-04-01

    We study the dynamics of concentrated ionic magnetic colloidal dispersions, which are constituted of γ - Fe2O3 nanoparticles dispersed in water, and stabilized with electrostatic interparticle repulsion, using magneto-optical birefringence measurements. By gradually increasing the volume fraction Φ of the particles at constant ionic strength in the repulsive region of the phase diagram, we observe a dramatic increase of the characteristic time associated with the rotation of the particles that we induce by applying a field pulse. This increase is reminiscent of the divergence of the relaxation time observed at the approach of a glass transition and confirms the existence of a glassy phase in these magnetic colloids.

  12. 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.

  13. 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.

  14. Theory of dynamic barriers, activated hopping, and the glass transition in polymer melts

    NASA Astrophysics Data System (ADS)

    Schweizer, Kenneth S.; Saltzman, Erica J.

    2004-07-01

    A statistical mechanical theory of collective dynamic barriers, slow segmental relaxation, and the glass transition of polymer melts is developed by combining, and in some aspects extending, methods of mode coupling, density functional, and activated hopping transport theories. A coarse-grained description of polymer chains is adopted and the melt is treated as a liquid of segments. The theory is built on the idea that collective density fluctuations on length scales considerably longer than the local cage scale are of primary importance in the deeply supercooled regime. The barrier hopping or segmental relaxation time is predicted to be a function primarily of a single parameter that is chemical structure, temperature, and pressure dependent. This parameter depends on the material-specific dimensionless amplitude of thermal density fluctuations (compressibility) and a reduced segmental density determined by the packing length and backbone characteristic ratio. Analytic results are derived for a crossover temperature Tc, collective barrier, and glass transition temperature Tg. The relation of these quantities to structural and thermodynamic properties of the polymer melt is established. A universal power-law scaling behavior of the relaxation time below Tc is predicted based on identification of a reduced temperature variable that quantifies the breadth of the supercooled regime. Connections between the ratio Tc/Tg, two measures of dynamic fragility, and the magnitude of the local relaxation time at Tg logically follow. Excellent agreement with experiment is found for these generic aspects, and the crucial importance of the experimentally observed near universality of the dynamic crossover time is established. Extensions of the theory to treat the full chain dynamics, heterogeneity, barrier fluctuations, and nonpolymeric thermal glass forming liquids are briefly discussed.

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

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

    Li, Yiming; Fu, Yuting; Shi, Yahui

    2016-02-15

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

  16. Evolution of short range order in Ar: Liquid to glass and solid transitions-A computational study

    NASA Astrophysics Data System (ADS)

    Shor, Stanislav; Yahel, Eyal; Makov, Guy

    2018-04-01

    The evolution of the short range order (SRO) as a function of temperature in a Lennard-Jones model liquid with Ar parameters was determined and juxtaposed with thermodynamic and kinetic properties obtained as the liquid was cooled (heated) and transformed between crystalline solid or glassy states and an undercooled liquid. The Lennard-Jones system was studied by non-equilibrium molecular dynamics simulations of large supercells (approximately 20000 atoms) rapidly cooled or heated at selected quenching rates and at constant pressure. The liquid to solid transition was identified by discontinuities in the atomic volume and molar enthalpy; the glass transition temperature range was identified from the temperature dependence of the self-diffusion. The SRO was studied within the quasi-crystalline model (QCM) framework and compared with the Steinhardt bond order parameters. Within the QCM it was found that the SRO evolves from a bcc-like order in the liquid through a bct-like short range order (c/a=1.2) in the supercooled liquid which persists into the glass and finally to a fcc-like ordering in the crystalline solid. The variation of the SRO that results from the QCM compares well with that obtained with Steinhardt's bond order parameters. The hypothesis of icosahedral order in liquids and glasses is not supported by our results.

  17. Location-Specific Measurements of The Glass Transition Temperature in Fluorescently Labeled Diblock Copolymers

    NASA Astrophysics Data System (ADS)

    Christie, Dane; Register, Richard; Priestley, Rodney

    Block copolymers can self-assemble into periodic structures containing a high internal surface area, nanoscale domain periods, and periodically varying composition profiles. Depending on their components, block copolymers may also exhibit variations in their dynamic properties e.g., glass transition temperature (Tg) across the domain period. Measuring the variation of Tg across the domain period of block copolymers has remained a significant challenge due to the nanometer length scale of the domain period. Here we use fluorescence spectroscopy and the selective incorporation of a pyrene-containing methacrylate monomer at various positions along the chain to characterize the distribution of glass transition temperatures across the domain period of an amorphous block copolymer. The pyrene-containing monomer location is determined from the monomer segment distribution calculated using self-consistent field theory. Our model system is a lamella-forming diblock copolymer of poly(butyl methacrylate - b- methyl methacrylate). We show that Tg is asymmetrically distributed across the interface; as the interface is approached, larger gradients in Tg exist in the hard PMMA-rich domain than in the soft PBMA-rich domain. By characterizing Tg of PBMA or PMMA interfacial segments, we show that polymer dynamics at the interface are heterogeneous; there is a 15 K difference in Tg measured between PBMA interfacial segments and PMMA interfacial segments.

  18. 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.

  19. Systematic study of vortex pinning and liquid-glass phase transition in BaFe2-x Ni x As2 single crystals

    NASA Astrophysics Data System (ADS)

    Vlasenko, V. A.; Sobolevskiy, O. A.; Sadakov, A. V.; Pervakov, K. S.; Gavrilkin, S. Yu.; Dik, A. V.; Eltsev, Yu. F.

    2018-01-01

    The vortex pinning and liquid-glass transition have been studied in BaFe2-x Ni x As2 single crystals with different doping levels (x = 0.065; 0.093; 0.1; 0.14; 0.18). We found that Ni-doped Ba-122 has rather narrow vortex-liquid state region. Our results show that the temperature dependence of the resistivity as well as I-V characteristics of Ni-doped Ba-122 is consistent with 3D vortex-glass model. It was found that δl-pinning gives the main contribution to overall pinning in 122 Ni-doped system. The vortex phase diagrams for different doping levels were built based on the obtained data of temperature of the vortex-glass transition T g and the upper critical magnetic field H c2.

  20. Effects of cross-links, pressure and temperature on the thermal properties and glass transition behaviour of polybutadiene.

    PubMed

    Tonpheng, Bounphanh; Yu, Junchun; Andersson, Ove

    2011-09-07

    The thermal conductivity κ, heat capacity per unit volume ρc(p) and glass transition behaviour under pressure have been established for medium and high vinyl content polybutadiene PB with molecular weights 2600 and 100,000 and their highly cross-linked (ebonite) states obtained purely by high-pressure high-temperature treatments. Cross-linking eliminates the glass transitions and increases κ by as much as 50% at 295 K and 1 atm, and decreases ρc(p) to a limiting level close to that of the glassy state of PB, which is reached before the ultimate cross-link density is achieved. The pressure and temperature behaviours of κ are strongly changed by cross-links, which increases the effect of temperature but decreases the effect of pressure. We attribute these changes to a cross-linked induced permanent densification and consequential increase of phonon velocity simultaneously as conduction along polymer chains is disrupted. The glass transition temperatures for a time scale of 1 s are described to within 0.5 K by: T(g)(p) = 202.5 (1 + 2.94 p)(0.286) and T(g)(p) = 272.3 (1 + 2.57 p)(0.233) (p in GPa and T in K) up to 1 GPa, for PB2600 and PB100000, respectively, and can be estimated for medium and high vinyl content PBs with molecular weights in between by a constant, pressure independent, shift in temperature. This journal is © the Owner Societies 2011

  1. Perspective: Highly stable vapor-deposited glasses

    NASA Astrophysics Data System (ADS)

    Ediger, M. D.

    2017-12-01

    This article describes recent progress in understanding highly stable glasses prepared by physical vapor deposition and provides perspective on further research directions for the field. For a given molecule, vapor-deposited glasses can have higher density and lower enthalpy than any glass that can be prepared by the more traditional route of cooling a liquid, and such glasses also exhibit greatly enhanced kinetic stability. Because vapor-deposited glasses can approach the bottom of the amorphous part of the potential energy landscape, they provide insights into the properties expected for the "ideal glass." Connections between vapor-deposited glasses, liquid-cooled glasses, and deeply supercooled liquids are explored. The generality of stable glass formation for organic molecules is discussed along with the prospects for stable glasses of other types of materials.

  2. Molecular dynamics simulations of melting and the glass transition of nitromethane.

    PubMed

    Zheng, Lianqing; Luo, Sheng-Nian; Thompson, Donald L

    2006-04-21

    Molecular dynamics simulations have been used to investigate the thermodynamic melting point of the crystalline nitromethane, the melting mechanism of superheated crystalline nitromethane, and the physical properties of crystalline and glassy nitromethane. The maximum superheating and glass transition temperatures of nitromethane are calculated to be 316 and 160 K, respectively, for heating and cooling rates of 8.9 x 10(9) Ks. Using the hysteresis method [Luo et al., J. Chem. Phys. 120, 11640 (2004)] and by taking the glass transition temperature as the supercooling temperature, we calculate a value of 251.1 K for the thermodynamic melting point, which is in excellent agreement with the two-phase result [Agrawal et al., J. Chem. Phys. 119, 9617 (2003)] of 255.5 K and measured value of 244.73 K. In the melting process, the nitromethane molecules begin to rotate about their lattice positions in the crystal, followed by translational freedom of the molecules. A nucleation mechanism for the melting is illustrated by the distribution of the local translational order parameter. The critical values of the Lindemann index for the C and N atoms immediately prior to melting (the Lindemann criterion) are found to be around 0.155 at 1 atm. The intramolecular motions and molecular structure of nitromethane undergo no abrupt changes upon melting, indicating that the intramolecular degrees of freedom have little effect on the melting. The thermal expansion coefficient and bulk modulus are predicted to be about two or three times larger in crystalline nitromethane than in glassy nitromethane. The vibrational density of states is almost identical in both phases.

  3. Composition-dependent damping and relaxation dynamics in miscible polymer blends above glass transition temperature by anelastic spectroscopy

    NASA Astrophysics Data System (ADS)

    Wu, Xuebang; Shang, Shuying; Xu, Qiaoling; Liu, Changsong; Zhu, Zhengang; Zhang, Guangzhao

    2008-07-01

    Anelastic spectroscopy is used to study the composition dependence of the damping and molecular relaxation dynamics in miscible poly(ethylene oxide) (PEO)/poly(methyl methacrylate) (PMMA) blends above the glass transition temperature. The ultrahigh damping peak of the relaxation type is shown to be associated with the liquid-liquid transition of PMMA. A higher PEO concentration leads to a higher damping performance and a lower transition temperature. The decreasing activation energy with increasing PEO concentration indicates a drastic increase in molecular mobility. Moreover, the relaxation time reveals a transition from the Vogel-Fulcher-Tamman behavior to the Arrhenius behavior due to the intermolecular guest-host interactions.

  4. Effect of water content on the glass transition temperature of mixtures of sugars, polymers, and penetrating cryoprotectants in physiological buffer.

    PubMed

    Drake, Andrew C; Lee, Youngjoo; Burgess, Emma M; Karlsson, Jens O M; Eroglu, Ali; Higgins, Adam Z

    2018-01-01

    Long-term storage of viable mammalian cells is important for applications ranging from in vitro fertilization to cell therapy. Cryopreservation is currently the most common approach, but storage in liquid nitrogen is relatively costly and the requirement for low temperatures during shipping is inconvenient. Desiccation is an alternative strategy with the potential to enable viable cell preservation at more convenient storage temperatures without the need for liquid nitrogen. To achieve stability during storage in the dried state it is necessary to remove enough water that the remaining matrix forms a non-crystalline glassy solid. Thus, the glass transition temperature is a key parameter for design of cell desiccation procedures. In this study, we have investigated the effects of moisture content on the glass transition temperature (Tg) of mixtures of sugars (trehalose or raffinose), polymers (polyvinylpyrrolidone or Ficoll), penetrating cryoprotectants (ethylene glycol, propylene glycol, or dimethyl sulfoxide), and phosphate buffered saline (PBS) solutes. Aqueous solutions were dried to different moisture contents by equilibration with saturated salt solutions, or by baking at 95°C. The glass transition temperatures of the dehydrated samples were then measured by differential scanning calorimetry. As expected, Tg increased with decreasing moisture content. For example, in a desiccation medium containing 0.1 M trehalose in PBS, Tg ranged from about 360 K for a completely dry sample to about 220 K at a water mass fraction of 0.4. Addition of polymers to the solutions increased Tg, while addition of penetrating cryoprotectants decreased Tg. Our results provide insight into the relationship between relative humidity, moisture content and glass transition temperature for cell desiccation solutions containing sugars, polymers and penetrating cryoprotectants.

  5. Effect of water content on the glass transition temperature of mixtures of sugars, polymers, and penetrating cryoprotectants in physiological buffer

    PubMed Central

    Burgess, Emma M.; Karlsson, Jens O. M.; Eroglu, Ali

    2018-01-01

    Long-term storage of viable mammalian cells is important for applications ranging from in vitro fertilization to cell therapy. Cryopreservation is currently the most common approach, but storage in liquid nitrogen is relatively costly and the requirement for low temperatures during shipping is inconvenient. Desiccation is an alternative strategy with the potential to enable viable cell preservation at more convenient storage temperatures without the need for liquid nitrogen. To achieve stability during storage in the dried state it is necessary to remove enough water that the remaining matrix forms a non-crystalline glassy solid. Thus, the glass transition temperature is a key parameter for design of cell desiccation procedures. In this study, we have investigated the effects of moisture content on the glass transition temperature (Tg) of mixtures of sugars (trehalose or raffinose), polymers (polyvinylpyrrolidone or Ficoll), penetrating cryoprotectants (ethylene glycol, propylene glycol, or dimethyl sulfoxide), and phosphate buffered saline (PBS) solutes. Aqueous solutions were dried to different moisture contents by equilibration with saturated salt solutions, or by baking at 95°C. The glass transition temperatures of the dehydrated samples were then measured by differential scanning calorimetry. As expected, Tg increased with decreasing moisture content. For example, in a desiccation medium containing 0.1 M trehalose in PBS, Tg ranged from about 360 K for a completely dry sample to about 220 K at a water mass fraction of 0.4. Addition of polymers to the solutions increased Tg, while addition of penetrating cryoprotectants decreased Tg. Our results provide insight into the relationship between relative humidity, moisture content and glass transition temperature for cell desiccation solutions containing sugars, polymers and penetrating cryoprotectants. PMID:29304068

  6. In-Situ Phase Transition Control in the Supercooled State for Robust Active Glass Fiber.

    PubMed

    Lv, Shichao; Cao, Maoqing; Li, Chaoyu; Li, Jiang; Qiu, Jianrong; Zhou, Shifeng

    2017-06-21

    The construction of a dopant-activated photonic composite is of great technological importance for various applications, including smart lighting, optical amplification, laser, and optical detection. The bonding arrangement around the introduced dopants largely determines the properties, yet it remains a daunting challenge to manipulate the local state of the matrix (i.e., phase) inside the transparent composite in a controllable manner. Here we demonstrate that the relaxation of the supercooled state enables in-situ phase transition control in glass. Benefiting from the unique local atom arrangement manner, the strategy offers the possibility for simultaneously tuning the chemical environment of the incorporated dopant and engineering the dopant-host interaction. This allows us to effectively activate the dopant with high efficiency (calculated as ∼100%) and profoundly enhance the dopant-host energy-exchange interaction. Our results highlight that the in-situ phase transition control in glass may provide new opportunities for fabrication of unusual photonic materials with intense broadband emission at ∼1100 nm and development of the robust optical detection unit with high compactness and broadband photon-harvesting capability (from X-ray to ultraviolet light).

  7. SEM Analysis of the Interfacial Transition Zone between Cement-Glass Powder Paste and Aggregate of Mortar under Microwave Curing

    PubMed Central

    Kong, Yaning; Wang, Peiming; Liu, Shuhua; Zhao, Guorong; Peng, Yu

    2016-01-01

    In order to investigate the effects of microwave curing on the microstructure of the interfacial transition zone of mortar prepared with a composite binder containing glass powder and to explain the mechanism of microwave curing on the improvement of compressive strength, in this study, the compressive strength of mortar under microwave curing was compared against mortar cured using (a) normal curing at 20 ± 1 °C with relative humidity (RH) > 90%; (b) steam curing at 40 °C for 10 h; and (c) steam curing at 80 °C for 4 h. The microstructure of the interfacial transition zone of mortar under the four curing regimes was analyzed by Scanning electron microscopy (SEM). The results showed that the improvement of the compressive strength of mortar under microwave curing can be attributed to the amelioration of the microstructure of the interfacial transition zone. The hydration degree of cement is accelerated by the thermal effect of microwave curing and Na+ partially dissolved from the fine glass powder to form more reticular calcium silicate hydrate, which connects the aggregate, calcium hydroxide, and non-hydrated cement and glass powder into a denser integral structure. In addition, a more stable triangular structure of calcium hydroxide contributes to the improvement of compressive strength. PMID:28773854

  8. SEM Analysis of the Interfacial Transition Zone between Cement-Glass Powder Paste and Aggregate of Mortar under Microwave Curing.

    PubMed

    Kong, Yaning; Wang, Peiming; Liu, Shuhua; Zhao, Guorong; Peng, Yu

    2016-08-27

    In order to investigate the effects of microwave curing on the microstructure of the interfacial transition zone of mortar prepared with a composite binder containing glass powder and to explain the mechanism of microwave curing on the improvement of compressive strength, in this study, the compressive strength of mortar under microwave curing was compared against mortar cured using (a) normal curing at 20 ± 1 °C with relative humidity (RH) > 90%; (b) steam curing at 40 °C for 10 h; and (c) steam curing at 80 °C for 4 h. The microstructure of the interfacial transition zone of mortar under the four curing regimes was analyzed by Scanning electron microscopy (SEM). The results showed that the improvement of the compressive strength of mortar under microwave curing can be attributed to the amelioration of the microstructure of the interfacial transition zone. The hydration degree of cement is accelerated by the thermal effect of microwave curing and Na⁺ partially dissolved from the fine glass powder to form more reticular calcium silicate hydrate, which connects the aggregate, calcium hydroxide, and non-hydrated cement and glass powder into a denser integral structure. In addition, a more stable triangular structure of calcium hydroxide contributes to the improvement of compressive strength.

  9. Influence of Network Structure on Glass Transition Temperature of Elastomers

    PubMed Central

    Bandzierz, Katarzyna; Reuvekamp, Louis; Dryzek, Jerzy; Dierkes, Wilma; Blume, Anke; Bielinski, Dariusz

    2016-01-01

    It is generally believed that only intermolecular, elastically-effective crosslinks influence elastomer properties. The role of the intramolecular modifications of the polymer chains is marginalized. The aim of our study was the characterization of the structural parameters of cured elastomers, and determination of their influence on the behavior of the polymer network. For this purpose, styrene-butadiene rubbers (SBR), cured with various curatives, such as DCP, TMTD, TBzTD, Vulcuren®, DPG/S8, CBS/S8, MBTS/S8 and ZDT/S8, were investigated. In every series of samples a broad range of crosslink density was obtained, in addition to diverse crosslink structures, as determined by equilibrium swelling and thiol-amine analysis. Differential scanning calorimetry (DSC) and dynamic mechanical analysis (DMA) were used to study the glass transition process, and positron annihilation lifetime spectroscopy (PALS) to investigate the size of the free volumes. For all samples, the values of the glass transition temperature (Tg) increased with a rise in crosslink density. At the same time, the free volume size proportionally decreased. The changes in Tg and free volume size show significant differences between the series crosslinked with various curatives. These variations are explained on the basis of the curatives’ structure effect. Furthermore, basic structure-property relationships are provided. They enable the prediction of the effect of curatives on the structural parameters of the network, and some of the resulting properties. It is proved that the applied techniques—DSC, DMA, and PALS—can serve to provide information about the modifications to the polymer chains. Moreover, on the basis of the obtained results and considering the diversified curatives available nowadays, the usability of “part per hundred rubber” (phr) unit is questioned. PMID:28773731

  10. Aging of a Binary Colloidal Glass

    NASA Astrophysics Data System (ADS)

    Lynch, Jennifer M.; Cianci, Gianguido C.; Weeks, Eric R.

    2008-03-01

    After having undergone a glass transition, a glass is in a non-equilibrium state, and its properties depend on the time elapsed since vitrification. We study this phenomenon, known as aging. In particular, we study a colloidal suspension consisting of micron-sized particles in a liquid --- a good model system for studying the glass transition. In this system, the glass transition is approached by increasing the particle concentration, instead of decreasing the temperature. We observe samples composed of particles of two sizes (d1= 1.0μm and d2= 2.0μm) using fast laser scanning confocal microscopy, which yields real-time, three-dimensional movies deep inside the colloidal glass. We then analyze the trajectories of several thousand particles as the glassy suspension ages. Specifically, we look at how the size, motion and structural organization of the particles relate to the overall aging of the glass. We find that areas richer in small particles are more mobile and therefore contribute more to the structural changes found in aging glasses.

  11. 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

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

    PubMed

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

    2014-09-07

    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 f(cp) during tensile extension; (b) the limiting value of f(cp), extrapolated to far below the glass transition temperature T(g), 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

  13. Glass transition dynamics and boiling temperatures of molecular liquids and their isomers.

    PubMed

    Wang, Li-Min; Richert, Ranko

    2007-03-29

    The relation between a dynamic and a thermodynamic temperature, glass transition Tg and boiling point Tb, is investigated for various glass-forming liquids, with emphasis on monohydroxy alcohols. As is well known, Tb and Tg are positively correlated across a large variety of liquids. However, we found that the same quantities show a negative correlation within an isomeric series, i.e., Tb decreases with increasing Tg for different isomers of the same chemical formula. For the alcohol series, CnH2n+1OH with 3 < or = n < or = 10, a master curve of the negative Tg - Tb correlation is obtained if the temperatures are normalized to the respective values of the n-alkanols. This Tg - Tb dependence of isomeric liquids is linked to entropic effects and responsible for much of the scatter of the correlation observed for a large number of molecular organic glass-formers with 45 < Tg < 250 K. Dielectric relaxation is measured for three groups of isomers: (a) 3-methoxyl-1-butanol and 2-iso-propoxyethanol, (b) 1,4-, 1,2-, and 2,4-pentanediol, and (c) di-n- and di-iso-butyl phthalate. Two key parameters of the dynamics, fragility m and stretching exponent beta, are found to be indistinguishable within isomers of moderately different Tgs. Larger fragility differences are readily expected with pronounced structural change, but no systematic trend is observed within an isomer series. The results provide a useful tool for assessing Tg, m, and beta for marginal glass formers on the basis of their isomers.

  14. Perspective: Highly stable vapor-deposited glasses

    DOE PAGES

    Ediger, M. D.

    2017-12-07

    This paper describes recent progress in understanding highly stable glasses prepared by physical vapor deposition and provides perspective on further research directions for the field. For a given molecule, vapor-deposited glasses can have higher density and lower enthalpy than any glass that can be prepared by the more traditional route of cooling a liquid, and such glasses also exhibit greatly enhanced kinetic stability. Because vapor-deposited glasses can approach the bottom of the amorphous part of the potential energy landscape, they provide insights into the properties expected for the “ideal glass”. Connections between vapor-deposited glasses, liquid-cooled glasses, and deeply supercooled liquidsmore » are explored. The generality of stable glass formation for organic molecules is discussed along with the prospects for stable glasses of other types of materials.« less

  15. Perspective: Highly stable vapor-deposited glasses

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

    Ediger, M. D.

    This paper describes recent progress in understanding highly stable glasses prepared by physical vapor deposition and provides perspective on further research directions for the field. For a given molecule, vapor-deposited glasses can have higher density and lower enthalpy than any glass that can be prepared by the more traditional route of cooling a liquid, and such glasses also exhibit greatly enhanced kinetic stability. Because vapor-deposited glasses can approach the bottom of the amorphous part of the potential energy landscape, they provide insights into the properties expected for the “ideal glass”. Connections between vapor-deposited glasses, liquid-cooled glasses, and deeply supercooled liquidsmore » are explored. The generality of stable glass formation for organic molecules is discussed along with the prospects for stable glasses of other types of materials.« less

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

    PubMed

    Sathish, K; Thirumaran, S

    2015-08-05

    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

  17. 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

  18. 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

  19. 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

  20. Crystallization of copper metaphosphate glass

    NASA Technical Reports Server (NTRS)

    Bae, Byeong-Soo; Weinberg, Michael C.

    1993-01-01

    The effect of the valence state of copper in copper metaphosphate glass on the crystallization behavior and glass transition temperature has been investigated. The crystallization of copper metaphosphate is initiated from the surface and its main crystalline phase is copper metaphosphate (Cu(PO)3),independent of the (Cu sup 2+)/(Cu(total)). However, the crystal morphology, the relative crystallization rates, and their temperature dependences are affected by the (Cu sup 2+)/(Cu (total)) ratio in the glass. On the other hand, the totally oxidized glass crystallizes from all over the surface. The relative crystallization rate of the reduced glass to the totally oxidized glass is large at low temperature, but small at high temperature. The glass transition temperature of the glass increases as the (Cu sup 2+)/(Cu(total)) ratio is raised. It is also found that the atmosphere used during heat treatment does not influence the crystallization of the reduced glass, except for the formation of a very thin CuO surface layer when heated in air.

  1. Local structural mechanism for frozen-in dynamics in metallic glasses

    NASA Astrophysics Data System (ADS)

    Liu, X. J.; Wang, S. D.; Wang, H.; Wu, Y.; Liu, C. T.; Li, M.; Lu, Z. P.

    2018-04-01

    The nature of the glass transition is a fundamental and long-standing intriguing issue in the condensed-matter physics and materials science community. In particular, the structural response by which a liquid is arrested dynamically to form a glass or amorphous solid upon approaching its freezing temperature [the glass transition temperature (Tg)] remains unclear. Various structural scenarios in terms of the percolation theory have been proposed recently to understand such a phenomenon; however, there is still no consensus on what the general percolation entity is and how the entity responds to the sudden slowdown dynamics during the glass transition. In this paper, we demonstrate that one-dimensional local linear ordering (LLO) is a universal structural motif associated with the glass transition for various metallic glasses. The quantitative evolution of LLO with temperature indicates that a percolating LLO network forms to serve as the backbone of the rigid glass solid when the temperature approaches the freezing point, resulting in the frozen-in dynamics accompanying the glass transition. The percolation transition occurs by pinning different LLO networks together, which only needs the introduction of a small number of "joint" atoms between them, and therefore the energy expenditure is very low.

  2. Antiferromagnetic inclusions in lunar glass

    USGS Publications Warehouse

    Thorpe, A.N.; Senftle, F.E.; Briggs, Charles; Alexander, Corrine

    1974-01-01

    The magnetic susceptibility of 11 glass spherules from the Apollo 15, 16, and 17 fines and two specimens of a relatively large glass spherical shell were studied as a function of temperature from room temperature to liquid helium temperatures. All but one specimen showed the presence of antiferromagnetic inclusions. Closely spaced temperature measurements of the magnetic susceptibility below 77 K on five of the specimens showed antiferromagnetic temperature transitions (Ne??el transitions). With the exception of ilmenite in one specimen, these transitions did not correspond to any transitions in known antiferromagnetic compounds. ?? 1974.

  3. Modeling the glass transition of amorphous networks for shape-memory behavior

    NASA Astrophysics Data System (ADS)

    Xiao, Rui; Choi, Jinwoo; Lakhera, Nishant; Yakacki, Christopher M.; Frick, Carl P.; Nguyen, Thao D.

    2013-07-01

    In this paper, a thermomechanical constitutive model was developed for the time-dependent behaviors of the glass transition of amorphous networks. The model used multiple discrete relaxation processes to describe the distribution of relaxation times for stress relaxation, structural relaxation, and stress-activated viscous flow. A non-equilibrium thermodynamic framework based on the fictive temperature was introduced to demonstrate the thermodynamic consistency of the constitutive theory. Experimental and theoretical methods were developed to determine the parameters describing the distribution of stress and structural relaxation times and the dependence of the relaxation times on temperature, structure, and driving stress. The model was applied to study the effects of deformation temperatures and physical aging on the shape-memory behavior of amorphous networks. The model was able to reproduce important features of the partially constrained recovery response observed in experiments. Specifically, the model demonstrated a strain-recovery overshoot for cases programmed below Tg and subjected to a constant mechanical load. This phenomenon was not observed for materials programmed above Tg. Physical aging, in which the material was annealed for an extended period of time below Tg, shifted the activation of strain recovery to higher temperatures and increased significantly the initial recovery rate. For fixed-strain recovery, the model showed a larger overshoot in the stress response for cases programmed below Tg, which was consistent with previous experimental observations. Altogether, this work demonstrates how an understanding of the time-dependent behaviors of the glass transition can be used to tailor the temperature and deformation history of the shape-memory programming process to achieve more complex shape recovery pathways, faster recovery responses, and larger activation stresses.

  4. Protein substitution affects glass transition temperature and thermal stability.

    PubMed

    Budhavaram, Naresh K; Miller, Jonathan A; Shen, Ying; Barone, Justin R

    2010-09-08

    When proteins are removed from their native state they suffer from two deficiencies: (1) glassy behavior with glass transition temperatures (Tg) well above room temperature and (2) thermal instability. The glassy behavior originates in multiple hydrogen bonds between amino acids on adjacent protein molecules. Proteins, like most biopolymers, are thermally unstable. Substituting ovalbumin with linear and cyclic substituents using a facile nucleophilic addition reaction can affect Tg and thermal stability. More hydrophobic linear substituents lowered Tg by interrupting intermolecular interactions and increasing free volume. More hydrophilic and cyclic substituents increased thermal stability by increasing intermolecular interactions. In some cases, substituents instituted cross-linking between protein chains that enhanced thermal stability. Internal plasticization using covalent substitution and external plasticization using low molecular weight polar liquids show the same protein structural changes and a signature of plasticization is identified.

  5. Molecular modeling of polycarbonate materials: Glass transition and mechanical properties

    NASA Astrophysics Data System (ADS)

    Palczynski, Karol; Wilke, Andreas; Paeschke, Manfred; Dzubiella, Joachim

    2017-09-01

    Linking the experimentally accessible macroscopic properties of thermoplastic polymers to their microscopic static and dynamic properties is a key requirement for targeted material design. Classical molecular dynamics simulations enable us to study the structural and dynamic behavior of molecules on microscopic scales, and statistical physics provides a framework for relating these properties to the macroscopic properties. We take a first step toward creating an automated workflow for the theoretical prediction of thermoplastic material properties by developing an expeditious method for parameterizing a simple yet surprisingly powerful coarse-grained bisphenol-A polycarbonate model which goes beyond previous coarse-grained models and successfully reproduces the thermal expansion behavior, the glass transition temperature as a function of the molecular weight, and several elastic properties.

  6. Ion-wake field inside a glass box.

    PubMed

    Chen, Mudi; Dropmann, Michael; Zhang, Bo; Matthews, Lorin S; Hyde, Truell W

    2016-09-01

    The confinement provided by a glass box is proving ideal for the formation of vertically aligned structures and a convenient method for controlling the number of dust particles comprising these dust structures as well as their sizes and shapes. In this paper, the electronic confinement of the glass box is mapped, and the particle interactions between the particle pairs inside the glass box are measured. The ion-wake field is shown to exist within the glass box, and its vertical and horizontal extents are measured.

  7. 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.

  8. 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

    2011-11-09

    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.

  9. 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.

  10. Predictive Validity and Adjustment of Ideal Partner Preferences Across the Transition Into Romantic Relationships.

    PubMed

    Gerlach, Tanja M; Arslan, Ruben C; Schultze, Thomas; Reinhard, Selina K; Penke, Lars

    2017-09-18

    Although empirical research has investigated what we ideally seek in a romantic partner for decades, the crucial question of whether ideal partner preferences actually guide our mating decisions in real life has remained largely unanswered. One reason for this is the lack of designs that assess individuals' ideal partner preferences before entering a relationship and then follow up on them over an extended period. In the Göttingen Mate Choice Study (GMCS), a preregistered, large-scale online study, we used such a naturalistic prospective design. We investigated partner preferences across 4 preference domains in a large sample of predominantly heterosexual singles (N = 763, aged 18-40 years) and tracked these individuals across a period of 5 months upon a possible transition into romantic relationships. Attesting to their predictive validity, partner preferences prospectively predicted the characteristics of later partners. This was equally true for both sexes, except for vitality-attractiveness where men's preferences were more predictive of their later partners' standing on this dimension than women's. Self-perceived mate value did not moderate the preference-partner characteristics relations. Preferences proved to be relatively stable across the 5 months interval, yet were less stable for those who entered a relationship. Subgroup analyses using a newly developed indicator of preference adjustment toward (vs. away from) partner characteristics revealed that participants adjusted their preferences downward when partners fell short of initial preferences, but showed no consistent adjustment when partners exceeded them. Results and implications are discussed against the background of ongoing controversies in mate choice and romantic relationship research. (PsycINFO Database Record (c) 2017 APA, all rights reserved).

  11. 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.

  12. Ferromagnetism and spin glass ordering in transition metal alloys (invited)

    NASA Astrophysics Data System (ADS)

    Crane, S.; Carnegie, D. W., Jr.; Claus, H.

    1982-03-01

    Magnetic properties of transition metal alloys near the percolation threshold are often complicated by metallurgical effects. Alloys like AuFe, VFe, CuNi, RhNi, and PdNi are in general not random solid solutions but have various degrees of atomic clustering or short-range order (SRO), depending on the heat treatment. First, it is shown how the magnetic ordering temperature of these alloys varies with the degree of clustering or SRO. Second, by systematically changing this degree of clustering or SRO, important information can be obtained about the magnetic phase diagram. In all these alloys below the percolation limit, the onset of ferromagnetic order is probably preceded by a spin glass-type ordering. However, details of the magnetic phase diagram near the critical point can be quite different alloy systems.

  13. Heat capacities and volumetric changes in the glass transition range: a constitutive approach based on the standard linear solid

    NASA Astrophysics Data System (ADS)

    Lion, Alexander; Mittermeier, Christoph; Johlitz, Michael

    2017-09-01

    A novel approach to represent the glass transition is proposed. It is based on a physically motivated extension of the linear viscoelastic Poynting-Thomson model. In addition to a temperature-dependent damping element and two linear springs, two thermal strain elements are introduced. In order to take the process dependence of the specific heat into account and to model its characteristic behaviour below and above the glass transition, the Helmholtz free energy contains an additional contribution which depends on the temperature history and on the current temperature. The model describes the process-dependent volumetric and caloric behaviour of glass-forming materials, and defines a functional relationship between pressure, volumetric strain, and temperature. If a model for the isochoric part of the material behaviour is already available, for example a model of finite viscoelasticity, the caloric and volumetric behaviour can be represented with the current approach. The proposed model allows computing the isobaric and isochoric heat capacities in closed form. The difference c_p -c_v is process-dependent and tends towards the classical expression in the glassy and equilibrium ranges. Simulations and theoretical studies demonstrate the physical significance of the model.

  14. A review of visible, near-IR, and mid-IR transitions in rare-earth doped glass waveguides for remote sensing and LIDAR

    NASA Astrophysics Data System (ADS)

    Jha, Animesh

    2006-12-01

    In the review article we explain the recent investigations on rare-earth doped glass and optical fibres for designing lasers which may be suitable for remote sensing and LIDAR applications. The paper explains the importance of engineering efficient lasing transitions in visible (480-650 nm) for generating UV lasers via one-stage harmonic generation. Besides visible transitions, we also demonstrate the transitions in near- and mid-IR via near-IR pumping scheme.

  15. Photoluminescence from trivalent-cerium-doped silica glass prepared by sol-gel method with aluminum co-dopant

    NASA Astrophysics Data System (ADS)

    Tokumitsu, Seika; Murakami, Yukon; Oda, Hisaya; Kawabe, Yutaka

    2018-01-01

    Trivalent cerium is an important luminescent center giving light emission in short wavelength region depending on host materials. Sol-gel formed silica glass is an ideal matrix due to its high transparency, robustness, and low-temperature processability, but the emission from cerium in silica matrix is often mixed up with that from defects in the matrix, making it difficult to obtain well-determined characteristics. Bright emission from Ce ions peaking at about 400 nm was observed in sol-gel silica glasses synthesized with aluminum co-dopant. From luminescence decay time, the origin was confirmed to be d-f transition in trivalent Ce. From dependence of emission characteristics and UV absorbance on aluminum concentration, it was found that the co-dopant plays an important role to convert the optically inactive tetravalent ions to emissive trivalent state.

  16. Structural features of single crystals of LuB{sub 12} upon a transition to the cage-glass phase

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

    Bolotina, N. B., E-mail: nb-bolotina@mail.ru; Verin, I. A.; Shitsevalova, N. Yu.

    2016-03-15

    The unit-cell parameters of dodecaboride LuB{sub 12}, 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 structuremore » model, in which a small part (~15%) of Lu atoms are displaced from the 2a sites at the centers of the B{sub 24} cuboctahedra to the 16n sites of sp. gr. I4/mmm, seems preferable.« less

  17. Molecular simulation and mathematical modelling of glass transition temperature depression induced by CO2 plasticization in Polysulfone membranes

    NASA Astrophysics Data System (ADS)

    Lock, S. S. M.; Lau, K. K.; Lock Sow Mei, Irene; Shariff, A. M.; Yeong, Y. F.; Bustam, A. M.

    2017-08-01

    A sequence of molecular modelling procedure has been proposed to simulate experimentally validated membrane structure characterizing the effect of CO2 plasticization, whereby it can be subsequently employed to elucidate the depression in glass transition temperature (Tg ). Based on the above motivation, unswollen and swollen Polysulfone membrane structures with different CO2 loadings have been constructed, whereby the accuracy has been validated through good compliance with experimentally measured physical properties. It is found that the presence of CO2 constitutes to enhancement in polymeric chain relaxation, which consequently promotes the enlargement of molecular spacing and causes dilation in the membrane matrix. A series of glass transition temperature treatment has been conducted on the verified molecular structure to elucidate the effect of CO2 loadings to the depression in Tg induced by plasticization. Subsequently, a modified Michealis-Menten (M-M) function has been implemented to quantify the effect of CO2 loading attributed to plasticization towards Tg .

  18. Fluorescence properties of Nd3+-doped tellurite glasses.

    PubMed

    Kumar, K Upendra; Prathyusha, V A; Babu, P; Jayasankar, C K; Joshi, A S; Speghini, A; Bettinelli, M

    2007-07-01

    The compositional and concentration dependence of luminescence of the (4)F(3/2)-->(4)I(J) (J=13/2, 11/2 and 9/2) transitions in four Nd(3+)-doped tellurite based glasses has been studied. The free-ion energy levels obtained for 60TeO(2)+39ZnO(2)+1.0Nd(2)O(3) (TZN10) glass have been analysed using the free-ion Hamiltonian model and compared with similar results obtained for Nd(3+):glass systems. The absorption spectrum of TZN10 glass has been analysed using the Judd-Ofelt theory. Relatively longer decay rates have been obtained for Nd(3+)-doped phosphotellurite glasses. The emission characteristics of the (4)F(3/2)-->(4)I(11/2) transition, of the Nd(3+):TZN10 glass, are found to be comparable to those obtained for Nd(3+):phosphate laser glasses. The non-exponential shape of the emission decay curves for the (4)F(3/2)-->(4)I(11/2) transition is attributed to the presence of energy transfer processes between the Nd(3+) ions.

  19. Kinetics of Glass Transition and Crystallization of a Zr40Hf10Ti4Y1Al10Cu25Ni7Co2Fe1 Bulk Metallic Glass with High Mixing Entropy

    NASA Astrophysics Data System (ADS)

    Gong, Pan; Wang, Sibo; Li, Fangwei; Wang, Xinyun

    2018-04-01

    The kinetics of glass transition and crystallization of a novel Zr40Hf10Ti4Y1Al10Cu25Ni7Co2Fe1 bulk metallic glass (BMG) with high mixing entropy have been studied by differential scanning calorimetry (DSC) and X-ray diffraction (XRD). The continuous DSC curves show five stages of crystallization at lower heating rates (≤ 20 K/min). The activation energies of glass transition were determined by Moynihan and Kissinger methods, while the activation energies of crystallization were calculated utilizing Kissinger, Ozawa, and Boswell models. The crystalline phases corresponding to each crystallization step have been found out. The kinetic fragility of Zr40Hf10Ti4Y1Al10Cu25Ni7Co2Fe1 BMG has also been evaluated. Based on the isothermal DSC curves, the Avrami exponent, evaluated from the Johnson-Mehl-Avrami equation, has been analyzed in detail. The current study reveals that the crystallization behavior of Zr40Hf10Ti4Y1Al10Cu25Ni7Co2Fe1 BMG exhibits characteristics of both the high entropy BMGs and traditional BMGs with a single principal element, leading to its high glass-forming ability.

  20. Determination of the Glass-Transition Temperature of GRPS and CFRPS Using a Torsion Pendulum in Regimes of Freely Damped Vibrations and Quasi-Stastic Torsion of Specimens

    NASA Astrophysics Data System (ADS)

    Startsev, V. O.; Lebedev, M. P.; Molokov, M. V.

    2018-03-01

    A method to measure the glass-transition temperature of polymers and polymeric matrices of composite materials with the help of an inverse torsion pendulum over a wide range of temperatures is considered combining the method of free torsional vibrations and a quasi-static torsion of specimens. The glass-transition temperature Tg of a KMKS-1-80. T10 fiberglass, on increasing the frequency of freely damped torsional vibrations from 0.7 to 9.6 Hz, was found to increase from 132 to 140°C. The value of Tg of these specimens, determined by measuring the work of their torsion through a small fixed angle was 128.6°C ± 0.8°C. It is shown that the use of a torsion pendulum allows one to determine the glass-transition temperature of polymeric or polymer matrices of PCMs in dynamic and quasi-static deformation regimes of specimens.

  1. Thermal properties and optical transition probabilities of Tm3 + doped TeO2-WO3 glass.

    PubMed

    Cenk, S; Demirata, B; Oveçoglu, M L; Ozen, G

    2001-10-01

    Glasses with the composition of (1 - x)TeO2 + (x)WO3, where x = 0.15, 0.25 and 0.3 were prepared and, their thermal and absorption measurements were carried out. Differential thermal analysis (DTA) curves taken in the 23-600 degrees C temperature range with a heating rate of 10 degrees C/min reveal a change in the value of the glass transition temperature, Tg, while crystallization was not observed for the glasses containing a WO3 content of more than 15 mol%. All the glasses were found to be moisture-resistant. The absorption bands corresponding to the absorption of the 1G4, 3F2, 3F3 and 3F4, 3H5 and 3H4 levels from the 3H6 ground level of the Tm3+ ion were observed in the optical absorption spectra. Integrated absorption cross-sections of each band except that of 3H5 level was found to vary with the glass composition. Judd-Ofelt analysis was carried out for the samples doped with 1.0 mol% Tm2O3. The omega2 parameter shows the strongest dependence on the host composition and it increases with the increasing WO3 amount. The value of omega4 increases rather slowly while the value of omega6 is practically independent of the composition. The strong dependence of the parameter omega2 indicates that this parameter is related to the structural change and the symmetry of the local environment of the Tm3+ ions in this glass.

  2. Optical stability of 3d transition metal ions doped-cadmium borate glasses towards γ-rays interaction

    NASA Astrophysics Data System (ADS)

    Marzouk, M.; ElBatal, H.; Eisa, W.

    2016-07-01

    This work reports the preparation of glasses of binary cadmium borate with the basic composition (mol% 45 CdO 55 B2O3) and samples of the same composition containing 0.2 wt% dopants of 3d transition metal (TM) oxides (TiO2 → CuO). The glasses have been investigated by combined optical and Fourier Transform infrared spectroscopic measurements before and after being subjected to gamma irradiation with a dose of 8 Mrad (8 × 104 Gy). Optical absorption of the undoped glass before irradiation reveals strong charge transfer UV absorption which is related to the presence of unavoidable contaminated trace iron impurities (mainly Fe3+) within the raw materials used for the preparation of the base cadmium borate glass. The optical spectra of the 3d TM ions exhibit characteristic bands which are related the stable oxidation state of the 3d TM ions within the host glass. Gamma irradiation produces some limited variations in the optical spectra due to the stability of the host glass containing high percent 45 mol% of heavy metal oxide (CdO) which causes some shielding effects towards irradiation. From the absorption edge data, the values of the optical band gap Eopt and Urbach energy (ΔE) have been calculated. The values of the optical energy gap are found to be dependent on the glass composition. Infrared absorption spectral measurements reveal characteristic absorption bands due to both triangular and tetrahedral borate groups with the BO3 units vibrations more intense than BO4 units due to the known limit value for the change of BO3 to BO4 groups. The introduction of 3d TM ions with the doping level (0.2 wt%) causes no changes in the number or position of the IR bands because of the presence of TM ions in modifying sites in the glass network. It is observed that gamma irradiation causes some limited changes in the FT-IR spectral bands due to the stability of the host heavy cadmium borate glass.

  3. Simultaneous Determination of Glass Transition Temperatures of Several Polymers.

    PubMed

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

    2016-01-01

    A simple and easy optical method is proposed for the determination of glass transition temperature (Tg) of polymers. 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. 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.

  4. 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

  5. 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.

  6. Study of L-ascorbic acid (vitamin C)/H 2O mixture across glass transition

    NASA Astrophysics Data System (ADS)

    Migliardo, F.; Branca, C.; Faraone, A.; Magazù, S.; Migliardo, P.

    2001-07-01

    In this paper, we report quasi elastic neutron scattering (QENS) spectra of vitamin C aqueous solutions, obtained using MIBEMOL spectrometer (LLB). The main purpose of this work is to characterize the relaxational and vibrational properties of the Vitamin C/H 2O system below and above the glass transition temperature by analysing the low-frequency neutron scattering spectra. The determination of the relative weight of vibrational over relaxational contributions allows to get information on the fragility degree of this peculiar hydrogen-bond system.

  7. Elasticity of MgSiO3 glass to pressures of the transition zone

    NASA Astrophysics Data System (ADS)

    Speziale, S.; Reichmann, H. J.; Marquardt, H.; Shim, S.-H.

    2009-04-01

    Geophysical observations suggest the presence of liquid silicates in regions at the top of the transition zone and at the core-mantle boundary. In addition, a mainly silicate magma ocean probably played a crucial role in the evolution of the early Earth. For these reasons understanding the physical behavior of silicates melts at high pressures is important. In situ experimental investigation of the physical properties of silicate melts at high pressures poses substantial technical difficulties, and computer simulations are nowadays the most effective method to explore the elasticity and the density of such material at relevant conditions of the deep Earth. Due to these difficulties, glasses are often used as "frozen" proxies of melts for experimental studies of their physical properties. Here we present the pressure dependence of sound velocity of MgSiO3 glass measured by Brillouin spectroscopy in the diamond-anvil cell across the whole pressure range of the upper mantle and transition zone. We measured both compressional and shear velocity at 36 different pressures both on compression and decompression. Fixing the starting density to 2.742 ± 0.003 g/cm3, we determined both bulk modulus KS0 and shear modulus G0, and their pressure derivatives at ambient conditions to be KS0 = 76.2 ± 1.0 GPa, G0 = 40.11 ± 0.32 GPa, (‚KS/‚P)0 = 3.04 ± 0.23, and (‚G/‚P )0 = 0.46 ± 0.06. We observe two discontinuities of the pressure dependence of both compressional and shear velocity at 7 ± 2 GPa and at 21 ± 1 GPa. These two discontinuities take place at pressures at which: (a) changes in the pressure dependence of both Si-O-Si bending and Si-O stretching vibrations of the polymerized SiO4 network were observed in the same glass by laser Raman scattering [1], and (b) new spectral features were observed by X-ray Raman scattering [2].The velocities measured upon decompression are significantly different from those measured during compression. The whole of our velocity

  8. Water diffusion in silicate glasses: the effect of glass structure

    NASA Astrophysics Data System (ADS)

    Kuroda, M.; Tachibana, S.

    2016-12-01

    Water diffusion in silicate melts (glasses) is one of the main controlling factors of magmatism in a volcanic system. Water diffusivity in silicate glasses depends on its own concentration. However, the mechanism causing those dependences has not been fully understood yet. In order to construct a general model for water diffusion in various silicate glasses, we performed water diffusion experiments in silica glass and proposed a new water diffusion model [Kuroda et al., 2015]. In the model, water diffusivity is controlled by the concentration of both main diffusion species (i.e. molecular water) and diffusion pathways, which are determined by the concentrations of hydroxyl groups and network modifier cations. The model well explains the water diffusivity in various silicate glasses from silica glass to basalt glass. However, pre-exponential factors of water diffusivity in various glasses show five orders of magnitude variations although the pre-exponential factor should ideally represent the jump frequency and the jump distance of molecular water and show a much smaller variation. Here, we attribute the large variation of pre-exponential factors to a glass structure dependence of activation energy for molecular water diffusion. It has been known that the activation energy depends on the water concentration [Nowak and Behrens, 1997]. The concentration of hydroxyls, which cut Si-O-Si network in the glass structure, increases with water concentration, resulting in lowering the activation energy for water diffusion probably due to more fragmented structure. Network modifier cations are likely to play the same role as water. With taking the effect of glass structure into account, we found that the variation of pre-exponential factors of water diffusivity in silicate glasses can be much smaller than the five orders of magnitude, implying that the diffusion of molecular water in silicate glasses is controlled by the same atomic process.

  9. Dielectric relaxation of 2-ethyl-1-hexanol around the glass transition by thermally stimulated depolarization currents.

    PubMed

    Arrese-Igor, S; Alegría, A; Colmenero, J

    2015-06-07

    We explore new routes for characterizing the Debye-like and α relaxation in 2-ethyl-1-hexanol (2E1H) monoalcohol by using low frequency dielectric techniques including thermally stimulated depolarization current (TSDC) techniques and isothermal depolarization current methods. In this way, we have improved the resolution of the overlapped processes making it possible the analysis of the data in terms of a mode composition as expected for a chain-like response. Furthermore the explored ultralow frequencies enabled to study dynamics at relatively low temperatures close to the glass transition (Tg). Results show, on the one hand, that Debye-like and α relaxation timescales dramatically approach to each other upon decreasing temperature to Tg. On the other hand, the analysis of partial polarization TSDC data confirms the single exponential character of the Debye-like relaxation in 2E1H and rules out the presence of Rouse type modes in the scenario of a chain-like response. Finally, on crossing the glass transition, the Debye-like relaxation shows non-equilibrium effects which are further emphasized by aging treatment and would presumably emerge as a result of the arrest of the structural relaxation below Tg.

  10. Shear-driven dynamic clusters in a colloidal glass

    NASA Astrophysics Data System (ADS)

    Eisenmann, Christoph; Kim, Chanjoong; Mattsson, Johan; Weitz, David

    2007-03-01

    We investigate the effect of shear applied to a colloidal glass on a microscopic level using a shear device that can be mounted on top of a confocal microscope. We find that the glass yields at a critical strain of about 10%, independently of the shear rate. Surprisingly, the yielding is accompanied by an increase of cooperative particle movements and a formation of dynamic clusters which is in contrast to the normal glass transition where one typically finds heterogeneity increasing whilst moving towards the glass transition.

  11. NMR Hole-Burning Experiments on Superionic Conductor Glasses

    NASA Astrophysics Data System (ADS)

    Kawamura, J.; Kuwata, N.; Hattori, T.

    2004-04-01

    Inhomogeneity is an inherent nature of glass, which is the density and concentration fluctuation frozen at glass transition temperature. The inhomogeneity of the glass plays significant role in so called superionic conductor glasses (SIG), since the mobile ions seek to move through energetically favorable paths. The localization of mobile ions in SIG near the 2nd glass transition is a remaining issue, where the trapping, percolation and many-body interactions are playing the roles. In order to investigate the trapping process in SIG, the authors have applied 109Ag NMR Hole-Burning technique to AgI containing SIG glasses. By using this technique, the slowing down process of the site-exchange rates between different sites were evaluated.

  12. Glass Transition Kinetics of 2714A amorphous alloy

    NASA Astrophysics Data System (ADS)

    Shanker Rao, T.; Lilly Shanker Rao, T.; Shaker, A. M.; Venkataraman, K.

    2018-03-01

    The present study is related to the kinetics of onset crystallization, Tx and peak crystallization Tp of cobalt based metallic glass 2714A (Co65Si15B14Fe4Ni2) using Differential Scanning Calorimetry (DSC). Non-isothermal measurements were performed at different heating rates (2, 4, 6, 8 and 10 K/min).The experimental results of the crystallization were studied by two most frequently used methods, i.e., Moynihan and Kissinger. The onset crystallization was also studied by VFT and Lasock’s approaches in addition to the above two methods. The activation energy of crystallization Ec was found to be 622.86 and 638.28 kJ/mol and Ex the activation energy of onset crystallization to be 676.34 and 688.93 kJ/mol respectively. Here Tx is used as a substitution of Tg to calculate the fragility index m of the cobalt based metallic glass in the absence of Tg. The fragility index, m which is a measure of glass forming ability (GFA) is also calculated and the value falls between 20 and 60. This indicates the studied metallic glass is an intermediate strong glass.

  13. Glass binder development for a glass-bonded sodalite ceramic waste form

    NASA Astrophysics Data System (ADS)

    Riley, Brian J.; Vienna, John D.; Frank, Steven M.; Kroll, Jared O.; Peterson, Jacob A.; Canfield, Nathan L.; Zhu, Zihua; Zhang, Jiandong; Kruska, Karen; Schreiber, Daniel K.; Crum, Jarrod V.

    2017-06-01

    This paper discusses work to develop Na2O-B2O3-SiO2 glass binders for immobilizing LiCl-KCl eutectic salt waste in a glass-bonded sodalite waste form following electrochemical reprocessing of used metallic nuclear fuel. Here, five new glasses with ∼20 mass% Na2O were designed to generate waste forms with high sodalite. The glasses were then used to produce ceramic waste forms with a surrogate salt waste. The waste forms made using these new glasses were formulated to generate more sodalite than those made with previous baseline glasses for this type of waste. The coefficients of thermal expansion for the glass phase in the glass-bonded sodalite waste forms made with the new binder glasses were closer to the sodalite phase in the critical temperature region near and below the glass transition temperature than previous binder glasses used. These improvements should result in lower probability of cracking in the full-scale monolithic ceramic waste form, leading to better long-term chemical durability.

  14. Glass binder development for a glass-bonded sodalite ceramic waste form

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

    Riley, Brian J.; Vienna, John D.; Frank, Steven M.

    This paper discusses work to develop Na 2O-B 2O 3-SiO 2 glass binders for immobilizing LiCl-KCl eutectic salt waste in a glass-bonded sodalite waste form following electrochemical reprocessing of used metallic nuclear fuel. In this paper, five new glasses with ~20 mass% Na 2O were designed to generate waste forms with high sodalite. The glasses were then used to produce ceramic waste forms with a surrogate salt waste. The waste forms made using these new glasses were formulated to generate more sodalite than those made with previous baseline glasses for this type of waste. The coefficients of thermal expansion formore » the glass phase in the glass-bonded sodalite waste forms made with the new binder glasses were closer to the sodalite phase in the critical temperature region near and below the glass transition temperature than previous binder glasses used. Finally, these improvements should result in lower probability of cracking in the full-scale monolithic ceramic waste form, leading to better long-term chemical durability.« less

  15. Glass binder development for a glass-bonded sodalite ceramic waste form

    DOE PAGES

    Riley, Brian J.; Vienna, John D.; Frank, Steven M.; ...

    2017-06-01

    This paper discusses work to develop Na 2O-B 2O 3-SiO 2 glass binders for immobilizing LiCl-KCl eutectic salt waste in a glass-bonded sodalite waste form following electrochemical reprocessing of used metallic nuclear fuel. In this paper, five new glasses with ~20 mass% Na 2O were designed to generate waste forms with high sodalite. The glasses were then used to produce ceramic waste forms with a surrogate salt waste. The waste forms made using these new glasses were formulated to generate more sodalite than those made with previous baseline glasses for this type of waste. The coefficients of thermal expansion formore » the glass phase in the glass-bonded sodalite waste forms made with the new binder glasses were closer to the sodalite phase in the critical temperature region near and below the glass transition temperature than previous binder glasses used. Finally, these improvements should result in lower probability of cracking in the full-scale monolithic ceramic waste form, leading to better long-term chemical durability.« less

  16. Folding of a LysM Domain: Entropy-Enthalpy Compensation in the Transition State of an Ideal Two-state Folder

    PubMed Central

    Nickson, Adrian A.; Stoll, Kate E.; Clarke, Jane

    2008-01-01

    Protein-engineering methods (Φ-values) were used to investigate the folding transition state of a lysin motif (LysM) domain from Escherichia coli membrane-bound lytic murein transglycosylase D. This domain consists of just 48 structured residues in a symmetrical βααβ arrangement and is the smallest αβ protein yet investigated using these methods. An extensive mutational analysis revealed a highly robust folding pathway with no detectable transition state plasticity, indicating that LysM is an example of an ideal two-state folder. The pattern of Φ-values denotes a highly polarised transition state, with significant formation of the helices but no structure within the β-sheet. Remarkably, this transition state remains polarised after circularisation of the domain, and exhibits an identical Φ-value pattern; however, the interactions within the transition state are uniformly weaker in the circular variant. This observation is supported by results from an Eyring analysis of the folding rates of the two proteins. We propose that the folding pathway of LysM is dominated by enthalpic rather than entropic considerations, and suggest that the lower entropy cost of formation of the circular transition state is balanced, to some extent, by the lower enthalpy of contacts within this structure. PMID:18538343

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

    DOE PAGES

    Gainaru, Catalin; Agapov, Alexander L.; Fuentes-Landete, Violeta; ...

    2014-11-24

    Here we present the discovery of an unusually large isotope effect in the structural relaxation and the glass transition temperature T g of water. Dielectric relaxation spectroscopy of low-density as well as of vapor deposited amorphous water reveal T g differences of 10±2K between H 2O and D 2O, sharply contrasting with other hydrogen bonded liquids for which H/D exchange increases T g 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 newmore » 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.« less

  18. Elastic moduli of a Brownian colloidal glass former

    NASA Astrophysics Data System (ADS)

    Fritschi, S.; Fuchs, M.

    2018-01-01

    The static, dynamic and flow-dependent shear moduli of a binary mixture of Brownian hard disks are studied by an event-driven molecular dynamics simulation. Thereby, the emergence of rigidity close to the glass transition encoded in the static shear modulus G_∞ is accessed by three methods. Results from shear stress auto-correlation functions, elastic dispersion relations, and the elastic response to strain deformations upon the start-up of shear flow are compared. This enables one to sample the time-dependent shear modulus G(t) consistently over several decades in time. By that a very precise specification of the glass transition point and of G_∞ is feasible. Predictions by mode coupling theory of a finite shear modulus at the glass transition, of α-scaling in fluid states close to the transition, and of shear induced decay in yielding glass states are tested and broadly verified.

  19. 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.

  20. Effect of powder to liquid ratio on tensile strength and glass transition temperature of alumina filled poly methyl methacrylate (PMMA) denture base material.

    PubMed

    Mohamed, S H; Arifin, A; Mohd Ishak, Z A; Nizam, A; Samsudin, A R

    2004-05-01

    The aim of this study was to evaluate the mechanical properties and glass transition temperature (Tg) of a denture base material prepared from high molecular weight poly methyl methacrylate (PMMA) and alumina (Al2O3). The glass transition temperature was studied by using differential scanning calorimetry (DSC). The effect of powder-to-liquid ratio was investigated. The result showed that the tensile properties and the Tg were slightly effected by the powder-to-liquid ratio. The ratio of 2.2:1 by weight of powder to liquid was found to be the best ratio for mixing the material to give the best result in this formulation.

  1. Optical transitions of Er3+/Yb3+ codoped TeO2-WO3-Bi2O3 glass.

    PubMed

    Shen, Xiang; Nie, Qiuhua; Xu, Tiefeng; Gao, Yuan

    2005-10-01

    Optical absorption and emission properties of the Er3+/Yb3+ codoped TeO2-WO3-Bi2O3 (TWB) glass has been investigated. The transition probabilities, excited state lifetimes, and the branching ratios have been predicted for Er3+ based on the Judd-Ofelt theory. The broad 1.5 microm fluorescence was observed under 970 nm excitation, and its full width at half maximum (FWHM) is 77 nm. The emission cross-section is calculated using the McCumber theory, and the peak emission cross-section is 1.03 x 10(-21) cm2 at 1.531 microm. This value is much larger than those of the silicate and phosphate glasses. Efficient green and weak red upconversion luminescence from Er3+ centers in the glass sample was observed at room temperature, and the upconversion excitation processes have been analyzed.

  2. Melting, glass transition, and apparent heat capacity of α-D-glucose by thermal analysis.

    PubMed

    Magoń, A; Pyda, M

    2011-11-29

    The thermal behaviors of α-D-glucose in the melting and glass transition regions were examined utilizing the calorimetric methods of standard differential scanning calorimetry (DSC), standard temperature-modulated differential scanning calorimetry (TMDSC), quasi-isothermal temperature-modulated differential scanning calorimetry (quasi-TMDSC), and thermogravimetric analysis (TGA). The quantitative thermal analyses of experimental data of crystalline and amorphous α-D-glucose were performed based on heat capacities. The total, apparent and reversingheat capacities, and phase transitions were evaluated on heating and cooling. The melting temperature (T(m)) of a crystalline carbohydrate such as α-D-glucose, shows a heating rate dependence, with the melting peak shifted to lower temperature for a lower heating rate, and with superheating of around 25K. The superheating of crystalline α-D-glucose is observed as shifting the melting peak for higher heating rates, above the equilibrium melting temperature due to of the slow melting process. The equilibrium melting temperature and heat of fusion of crystalline α-D-glucose were estimated. Changes of reversing heat capacity evaluated by TMDSC at glass transition (T(g)) of amorphous and melting process at T(m) of fully crystalline α-D-glucose are similar. In both, the amorphous and crystalline phases, the same origin of heat capacity changes, in the T(g) and T(m) area, are attributable to molecular rotational motion. Degradation occurs simultaneously with the melting process of the crystalline phase. The stability of crystalline α-D-glucose was examined by TGA and TMDSC in the melting region, with the degradation shown to be resulting from changes of mass with temperature and time. The experimental heat capacities of fully crystalline and amorphous α-D-glucose were analyzed in reference to the solid, vibrational, and liquid heat capacities, which were approximated based on the ATHAS scheme and Data Bank. Copyright

  3. Electrochemical determination of the glass transition temperature of thin polyelectrolyte brushes at solid-liquid interfaces by impedance spectroscopy.

    PubMed

    Alonso-García, Teodoro; Rodríguez-Presa, María José; Gervasi, Claudio; Moya, Sergio; Azzaroni, Omar

    2013-07-16

    Devising strategies to assess the glass transition temperature (Tg) of polyelectrolyte assemblies at solid-electrolyte interfaces is very important to understand and rationalize the temperature-dependent behavior of polyelectrolyte films in a wide range of settings. Despite the evolving perception of the importance of measuring Tg under aqueous conditions in thin film configurations, its straightforward measurement poses a challenging situation that still remains elusive in polymer and materials science. Here, we describe a new method based on electrochemical impedance spectroscopy (EIS) to estimate the glass transition temperature of planar polyelectrolyte brushes at solid-liquid interfaces. To measure Tg, the charge transfer resistance (Rct) of a redox probe diffusing through the polyelectrolyte brush was measured, and the temperature corresponding to the discontinuous change in Rct was identified as Tg. Furthermore, we demonstrate that impedance measurements not only facilitate the estimation of Tg but also enable a reliable evaluation of the transport properties of the polymeric interface, i.e., determination of diffusion coefficients, close to the thermal transition. We consider that this approach bridges the gap between electrochemistry and the traditional tools used in polymer science and offers new opportunities to characterize the thermal behavior of complex polymeric interfaces and macromolecular assemblies.

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

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

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

    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, butmore » 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.« less

  5. On the approach to Mott's transition in glass-ceramic nanocomposite due to heat treatment

    NASA Astrophysics Data System (ADS)

    Mahdy, Iman A.; Heikal, Sh.; Abd-Rabo, A. S.; Abdel Ghany, A.; Bahgat, A. A.

    2015-07-01

    In the present work, the glass-ceramic nanocomposite (GCNC) of the composition 30[0.75 BaTiO3+0.25 PbTiO3]+70 V2O5 (mol. %) was prepared from the parent glass by isothermal heat treatment (HT) at 723 K for different time intervals 0.25, 0.5, 1.5, 2, and 2.5 h, respectively. The bulk density and some related parameters were calculated. X-ray diffraction and Hi-Resolution Transmission Electron Microscope (HRTEM) were used to identify different phases as well as particle size of the precipitated nanocrystals during the heat treatment process. The DC electrical conductivity was enhanced three orders of magnitudes (3×103) by increasing HT time. The resistivity measurements on the other hand as a function of time show an approach to nonmetallic-metallic transition for the prepared NCGC samples. Mott's VRH conduction mechanism was predicted as a result of the increase of the heat treatment time.

  6. Comparison of a model vapor deposited glass films to equilibrium glass films

    NASA Astrophysics Data System (ADS)

    Flenner, Elijah; Berthier, Ludovic; Charbonneau, Patrick; Zamponi, Francesco

    Vapor deposition of particles onto a substrate held at around 85% of the glass transition temperature can create glasses with increased density, enthalpy, kinetic stability, and mechanical stability compared to an ordinary glass created by cooling. It is estimated that an ordinary glass would need to age thousands of years to reach the kinetic stability of a vapor deposited glass, and a natural question is how close to the equilibrium is the vapor deposited glass. To understand the process, algorithms akin to vapor deposition are used to create simulated glasses that have a higher kinetic stability than their annealed counterpart, although these glasses may not be well equilibrated either. Here we use novel models optimized for a swap Monte Carlo algorithm in order to create equilibrium glass films and compare their properties with those of glasses obtained from vapor deposition algorithms. This approach allows us to directly assess the non-equilibrium nature of vapor-deposited ultrastable glasses. Simons Collaboration on Cracking the Glass Problem and NSF Grant No. DMR 1608086.

  7. 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.

  8. Microinhomogeneities of glasses of the system PbO-SiO2

    NASA Astrophysics Data System (ADS)

    Golubkov, V. V.; Bogdanov, V. N.; Pakhnin, A. Ya.; Solovyev, V. A.; Zhivaeva, E. V.; Kabanov, V. O.; Yanush, O. V.; Nemilov, S. V.; Kisliuk, A.; Soltwisch, M.; Quitmann, D.

    1999-03-01

    Small angle x-ray scattering (SAXS) and Rayleigh-Mandelstam-Brillouin (RMB) light scattering as well as ultrasonic sound velocities have been studied in glasses of the system PbO-SiO2 which has an unusually wide range of glass forming ability. The results of scattering are compared with calculations based on the concept of frozen-in equilibrium thermal fluctuations as the origin of static microinhomogeneities (MIH) in glasses. MIH of compositions seem to be the main source of scattering, and the calculations are found to be in qualitative agreement with both SAXS and RMB measurements. Glasses with PbO content above 40 mol.% are more homogeneous than ideal solutions of PbO and SiO2 whereas MIH in glasses with smaller PbO content are comparable with those expected for ideal solutions of PbO and SiO2. In the latter range SAXS measurements indicate the existence of medium-range order with correlation length of 5-7 Å.

  9. 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

  10. Glass transition in thaumatin crystals revealed through temperature-dependent radiation-sensitivity measurements.

    PubMed

    Warkentin, Matthew; Thorne, Robert E

    2010-10-01

    The temperature-dependence of radiation damage to thaumatin crystals between T = 300 and 100 K is reported. The amount of damage for a given dose decreases sharply as the temperature decreases from 300 to 220 K and then decreases more gradually on further cooling below the protein-solvent glass transition. Two regimes of temperature-activated behavior were observed. At temperatures above ∼200 K the activation energy of 18.0 kJ mol(-1) indicates that radiation damage is dominated by diffusive motions in the protein and solvent. At temperatures below ∼200 K the activation energy is only 1.00 kJ mol(-1), which is of the order of the thermal energy. Similar activation energies describe the temperature-dependence of radiation damage to a variety of solvent-free small-molecule organic crystals over the temperature range T = 300-80 K. It is suggested that radiation damage in this regime is vibrationally assisted and that the freezing-out of amino-acid scale vibrations contributes to the very weak temperature-dependence of radiation damage below ∼80 K. Analysis using the radiation-damage model of Blake and Phillips [Blake & Phillips (1962), Biological Effects of Ionizing Radiation at the Molecular Level, pp. 183-191] indicates that large-scale conformational and molecular motions are frozen out below T = 200 K but become increasingly prevalent and make an increasing contribution to damage at higher temperatures. Possible alternative mechanisms for radiation damage involving the formation of hydrogen-gas bubbles are discussed and discounted. These results have implications for mechanistic studies of proteins and for studies of the protein glass transition. They also suggest that data collection at T ≃ 220 K may provide a viable alternative for structure determination when cooling-induced disorder at T = 100 is excessive.

  11. Mechanical Properties of Stable Glasses Using Nanoindentation

    NASA Astrophysics Data System (ADS)

    Wolf, Sarah; Liu, Tianyi; Jiang, Yijie; Ablajan, Keyume; Zhang, Yue; Walsh, Patrick; Turner, Kevin; Fakhraai, Zahra

    Glasses with enhanced stability over ordinary, liquid quenched glasses have been formed via the process of Physical Vapor Deposition (PVD) by using a sufficiently slow deposition rate and a substrate temperature slightly below the glass transition temperature. These stable glasses have been shown to exhibit higher density, lower enthalpy, and better kinetic stability over ordinary glass, and are typically optically birefringent, due to packing and orientational anisotropy. Given these exceptional properties, it is of interest to further investigate how the properties of stable glasses compare to those of ordinary glass. In particular, the mechanical properties of stable glasses remain relatively under-investigated. While the speed of sound and elastic moduli have been shown to increase with increased stability, little is known about their hardness and fracture toughness compared to ordinary glasses. In this study, glasses of 9-(3,5-di(naphthalen-1-yl)phenyl)anthracene were deposited at varying temperatures relative to their glass transition temperature, and their mechanical properties measured by nanoindentation. Hardness and elastic modulus of the glasses were compared across substrate temperatures. After indentation, the topography of these films were studied using Atomic Force Microscopy (AFM) in order to further compare the relationship between thermodynamic and kinetic stability and mechanical failure. Z.F. and P.W. acknowledge funding from NSF(DMREF-1628407).

  12. Systematic expansion in the order parameter for replica theory of the dynamical glass transition.

    PubMed

    Jacquin, Hugo; Zamponi, Francesco

    2013-03-28

    It has been shown recently that predictions from mode-coupling theory for the glass transition of hard-spheres become increasingly bad when dimensionality increases, whereas replica theory predicts a correct scaling. Nevertheless if one focuses on the regime around the dynamical transition in three dimensions, mode-coupling results are far more convincing than replica theory predictions. It seems thus necessary to reconcile the two theoretic approaches in order to obtain a theory that interpolates between low-dimensional, mode-coupling results, and "mean-field" results from replica theory. Even though quantitative results for the dynamical transition issued from replica theory are not accurate in low dimensions, two different approximation schemes--small cage expansion and replicated hyper-netted-chain (RHNC)--provide the correct qualitative picture for the transition, namely, a discontinuous jump of a static order parameter from zero to a finite value. The purpose of this work is to develop a systematic expansion around the RHNC result in powers of the static order parameter, and to calculate the first correction in this expansion. Interestingly, this correction involves the static three-body correlations of the liquid. More importantly, we separately demonstrate that higher order terms in the expansion are quantitatively relevant at the transition, and that the usual mode-coupling kernel, involving two-body direct correlation functions of the liquid, cannot be recovered from static computations.

  13. Electronic structure and glass forming ability in early and late transition metal alloys

    NASA Astrophysics Data System (ADS)

    Babić, E.; Ristić, R.; Figueroa, I. A.; Pajić, D.; Skoko, Ž.; Zadro, K.

    2018-03-01

    A correlation between the change in magnetic susceptibility (Δχexp) upon crystallisation of Cu-Zr and Hf metallic glasses (MG) with their glass forming ability (GFA) observed recently, is found to apply to Cu-Ti and Zr-Ni alloys, too. In particular, small Δχexp, which reflects similar electronic structures, ES, of glassy and corresponding crystalline alloys, corresponds to high GFA. Here, we studied Δχexp for five Cu-Ti and four Cu-Zr and Ni-Zr MGs. The fully crystalline final state of all alloys was verified from X-ray diffraction patterns. The variation of GFA with composition in Cu-Ti, Cu-Zr and Cu-Hf MGs was established from the variation of the corresponding critical casting thickness, dc. Due to the absence of data for dc in Ni-Zr MGs their GFA was described using empirical criteria, such as the reduced glass transition temperature. A very good correlation between Δχexp and dc (and/or other criteria for GFA) was observed for all alloys studied. The correlation between the ES and GFA showed up best for Cu-Zr and NiZr2 alloys where direct data for the change in ES (ΔES) upon crystallisation are available. The applicability of the Δχexp (ΔES) criterion for high GFA (which provides a simple way to select the compositions with high GFA) to other metal-metal MGs (including ternary and multicomponent bulk MGs) is briefly discussed.

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

    PubMed

    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 (g)of 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: T(g) (bulk) - T(g)(23 nm) = 10 degrees 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( degrees ) 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.

  15. 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

  16. Initial stage of physical ageing in network glasses

    NASA Astrophysics Data System (ADS)

    Golovchak, R.; Ingram, A.; Kozdras, A.; Vlcek, M.; Roiland, C.; Bureau, B.; Shpotyuk, O.

    2012-11-01

    An atomistic view on Johari-Goldstein secondary β-relaxation processes responsible for structural relaxation far below the glass transition temperature (Tg ) in network glasses is developed for the archetypal chalcogenide glass, As20Se80, using positron annihilation lifetime, differential scanning calorimetry, Raman scattering and nuclear magnetic resonance techniques. Increased density fluctuations are shown to be responsible for the initial stage of physical ageing in these materials at the temperatures below Tg . They are correlated with changes in thermodynamic parameters of structural relaxation through the glass-to-supercooled liquid transition interval. General shrinkage, occurred during the next stage of physical ageing, is shown to be determined by the ability of system to release these redundant open volumes from the glass bulk through the densification process of glass network.

  17. Dynamical heterogeneities and mechanical non-linearities: Modeling the onset of plasticity in polymer in the glass transition.

    PubMed

    Masurel, R J; Gelineau, P; Lequeux, F; Cantournet, S; Montes, H

    2017-12-27

    In this paper we focus on the role of dynamical heterogeneities on the non-linear response of polymers in the glass transition domain. We start from a simple coarse-grained model that assumes a random distribution of the initial local relaxation times and that quantitatively describes the linear viscoelasticity of a polymer in the glass transition regime. We extend this model to non-linear mechanics assuming a local Eyring stress dependence of the relaxation times. Implementing the model in a finite element mechanics code, we derive the mechanical properties and the local mechanical fields at the beginning of the non-linear regime. The model predicts a narrowing of distribution of relaxation times and the storage of a part of the mechanical energy --internal stress-- transferred to the material during stretching in this temperature range. We show that the stress field is not spatially correlated under and after loading and follows a Gaussian distribution. In addition the strain field exhibits shear bands, but the strain distribution is narrow. Hence, most of the mechanical quantities can be calculated analytically, in a very good approximation, with the simple assumption that the strain rate is constant.

  18. Structural properties and glass transition in Aln clusters

    NASA Astrophysics Data System (ADS)

    Sun, D. Y.; Gong, X. G.

    1998-02-01

    We have studied the structural and dynamical properties of several Aln clusters by the molecular-dynamics method combined with simulated annealing. The well-fitted glue potential is used to describe the interatomic interaction. The obtained atomic structures for n=13, 55, and 147 are in agreement with results from ab initio calculations. Our results have demonstrated that the disordered cluster Al43 can be considered as a glass cluster. The obtained thermal properties of glass cluster Al43 are clearly different from the results for high-symmetry clusters, its melting behavior has properties similar to those of a glass solid. The present studies also show that the surface melting behavior does not exist in the studied Aln clusters.

  19. Glass binder development for a glass-bonded sodalite ceramic waste form

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

    Riley, Brian J.; Vienna, John D.; Frank, Steven M.

    This paper discusses work to develop Na2O-B2O3-SiO2 glass binders for immobilizing LiCl-KCl eutectic salt waste in a glass-bonded sodalite waste form following electrochemical reprocessing of used metallic nuclear fuel. Here, five new glasses with high Na2O contents were designed to generate waste forms having higher sodalite contents and fewer stress fractures. The structural, mechanical, and thermal properties of the new glasses were measured using variety of analytical techniques. The glasses were then used to produce ceramic waste forms with surrogate salt waste. The materials made using the glasses developed during this study were formulated to generate more sodalite than materialsmore » made with previous baseline glasses used. The coefficients of thermal expansion for the glass phase in the glass-bonded sodalite waste forms made with the new binder glasses were closer to the sodalite phase in the critical temperature region near and below the glass transition temperature. These improvements should result in lower probability of cracking in the full-scale monolithic ceramic waste form, leading to better long-term chemical durability. Additionally, a model generated during this study for predicting softening temperature of silicate binder glasses is presented.« less

  20. Prediction of glass transition temperature of freeze-dried formulations by molecular dynamics simulation.

    PubMed

    Yoshioka, Sumie; Aso, Yukio; Kojima, Shigeo

    2003-06-01

    To examine whether the glass transition temperature (Tg) of freeze-dried formulations containing polymer excipients can be accurately predicted by molecular dynamics simulation using software currently available on the market. Molecular dynamics simulations were carried out for isomaltodecaose, a fragment of dextran, and alpha-glucose, the repeated unit of dextran. in the presence or absence of water molecules. Estimated values of Tg were compared with experimental values obtained by differential scanning calorimetry (DSC). Isothermal-isobaric molecular dynamics simulations (NPTMD) and isothermal molecular dynamics simulations at a constant volume (NVTMD) were carried out using the software package DISCOVER (Material Studio) with the Polymer Consortium Force Field. Mean-squared displacement and radial distribution function were calculated. NVTMD using the values of density obtained by NPTMD provided the diffusivity of glucose-ring oxygen and water oxygen in amorphous alpha-glucose and isomaltodecaose, which exhibited a discontinuity in temperature dependence due to glass transition. Tg was estimated to be approximately 400K and 500K for pure amorphous a-glucose and isomaltodecaose, respectively, and in the presence of one water molecule per glucose unit, Tg was 340K and 360K, respectively. Estimated Tg values were higher than experimentally determined values because of the very fast cooling rates in the simulations. However, decreases in Tg on hydration and increases in Tg associated with larger fragment size could be demonstrated. The results indicate that molecular dynamics simulation is a useful method for investigating the effects of hydration and molecular weight on the Tg of lyophilized formulations containing polymer excipients. although the relationship between cooling rates and Tg must first be elucidated to predict Tg vales observed by DSC measurement. January 16.

  1. Experimental Verification of Boyle's Law and the Ideal Gas Law

    ERIC Educational Resources Information Center

    Ivanov, Dragia Trifonov

    2007-01-01

    Two new experiments are offered concerning the experimental verification of Boyle's law and the ideal gas law. To carry out the experiments, glass tubes, water, a syringe and a metal manometer are used. The pressure of the saturated water vapour is taken into consideration. For educational purposes, the experiments are characterized by their…

  2. Transition from a strong-yet-brittle to a stronger-and-ductile state by size reduction of metallic glasses.

    PubMed

    Jang, Dongchan; Greer, Julia R

    2010-03-01

    Amorphous metallic alloys, or metallic glasses, are lucrative engineering materials owing to their superior mechanical properties such as high strength and large elastic strain. However, their main drawback is their propensity for highly catastrophic failure through rapid shear banding, significantly undercutting their structural applications. Here, we show that when reduced to 100 nm, Zr-based metallic glass nanopillars attain ceramic-like strengths (2.25 GPa) and metal-like ductility (25%) simultaneously. We report separate and distinct critical sizes for maximum strength and for the brittle-to-ductile transition, thereby demonstrating that strength and ability to carry plasticity are decoupled at the nanoscale. A phenomenological model for size dependence and brittle-to-homogeneous deformation is provided.

  3. Dilatancy induced ductile-brittle transition of shear band in metallic glasses.

    PubMed

    Zeng, F; Jiang, M Q; Dai, L H

    2018-04-01

    Dilatancy-generated structural disordering, an inherent feature of metallic glasses (MGs), has been widely accepted as the physical mechanism for the primary origin and structural evolution of shear banding, as well as the resultant shear failure. However, it remains a great challenge to determine, to what degree of dilatation, a shear banding will evolve into a runaway shear failure. In this work, using in situ acoustic emission monitoring, we probe the dilatancy evolution at the different stages of individual shear band in MGs that underwent severely plastic deformation by the controlled cutting technology. A scaling law is revealed that the dilatancy in a shear band is linearly related to its evolution degree. A transition from ductile-to-brittle shear bands is observed, where the formers dominate stable serrated flow, and the latter lead to a runaway instability (catastrophe failure) of serrated flow. To uncover the underlying mechanics, we develop a theoretical model of shear-band evolution dynamics taking into account an atomic-scale deformation process. Our theoretical results agree with the experimental observations, and demonstrate that the atomic-scale volume expansion arises from an intrinsic shear-band evolution dynamics. Importantly, the onset of the ductile-brittle transition of shear banding is controlled by a critical dilatation.

  4. Dilatancy induced ductile-brittle transition of shear band in metallic glasses

    NASA Astrophysics Data System (ADS)

    Zeng, F.; Jiang, M. Q.; Dai, L. H.

    2018-04-01

    Dilatancy-generated structural disordering, an inherent feature of metallic glasses (MGs), has been widely accepted as the physical mechanism for the primary origin and structural evolution of shear banding, as well as the resultant shear failure. However, it remains a great challenge to determine, to what degree of dilatation, a shear banding will evolve into a runaway shear failure. In this work, using in situ acoustic emission monitoring, we probe the dilatancy evolution at the different stages of individual shear band in MGs that underwent severely plastic deformation by the controlled cutting technology. A scaling law is revealed that the dilatancy in a shear band is linearly related to its evolution degree. A transition from ductile-to-brittle shear bands is observed, where the formers dominate stable serrated flow, and the latter lead to a runaway instability (catastrophe failure) of serrated flow. To uncover the underlying mechanics, we develop a theoretical model of shear-band evolution dynamics taking into account an atomic-scale deformation process. Our theoretical results agree with the experimental observations, and demonstrate that the atomic-scale volume expansion arises from an intrinsic shear-band evolution dynamics. Importantly, the onset of the ductile-brittle transition of shear banding is controlled by a critical dilatation.

  5. 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.

  6. 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.

  7. Bonding Transition in SiO2 Glass at High Pressures: Applications to SiO2 Liquid in Earth's Interior

    NASA Astrophysics Data System (ADS)

    Yoo, C.; Lin, J.; Fukui, H.; Prendergast, D.; Okuchi, T.; Cai, Y.; Hiraoka, N.; Trave, A.; Eng, P.; Hu, M. Y.; Chow, P.

    2006-12-01

    SiO2 and MgSiO3 liquids are two major components in the magma deep inside the Earth. Knowledge of their electronic bonding characters at high pressures is essential to understanding the complex properties of the materials in the melts. The nature of pressure-induced bonding change in amorphous SiO2 has been an intriguing and long-standing problem that remains to be further understood. For example, previous infrared and X-ray diffraction studies suggested that a continuous transformation from the four- to six-fold coordinated silicon occurred in amorphous SiO2 at high pressures, whereas separate optical Raman studies attributed to a pressure-induced shift in the local ring statistics and a breakdown in the intermediate-range order. Here we have studied the oxygen near K-edge spectra of SiO2 glass to 51 GPa obtained using X-ray Raman scattering in a diamond-anvil cell, which directly probes the electronic bonding character of the sample. Our results provide conclusive evidence for a pressure-induced electronic bonding transition in SiO2 glass at high pressures. Although a progressive decrease in the mean Si-O-Si angle in the SiO4 tetrahedra is believed to be responsible for the irreversible densification in SiO2 glass at high pressures, our observed transition is reversible upon decompression. A similar transformation is also expected to occur in silicate glasses and melts, which will most definitely alter their physical, mechanical and transport properties in the magma chamber deep in the Earth's interior. This work was performed under the auspices of the U.S. DOE by UC/LLNL under Contract W-7405-Eng-48.

  8. An application for impedance spectroscopy in the characterisation of the glass transition during the lyophilization cycle: the example of a 10% w/v maltodextrin solution.

    PubMed

    Smith, Geoff; Arshad, Muhammad Sohail; Polygalov, Eugene; Ermolina, Irina

    2013-11-01

    Impedance spectroscopy has been used for the measurement of the glass transition of a 10 % maltodextrin solution contained within a glass vial, with externally attached electrodes. Features of the pseudo-relaxation process, associated with the composite impedance of the glass vial-solution assembly, were characterised by the peak amplitude, C(peak)(″), and peak frequency, f(peak), of the capacitance spectra and the equivalent circuit elements that model the impedance spectra (i.e. the solution resistance and solution capacitance) and monitored every 3 min during re-heating of the solution. The time derivatives of all four parameters studied provided a glass transition in close agreement with DSC measurements (-17 °C) and at a precision of ± 0.5 °C. The temperature dependencies of the solution resistance and peak frequency were then characterised with the Arrhenius and Vogel-Fulcher-Tammann fit functions, at temperatures below and above Tg, respectively. The energy of activation (below Tg) was estimated at ~20 kJ mol(-1), and the fragility index (If) of the glass forming liquid (above Tg) was estimated at 0.9. The significance of the fragility index to the development, optimisation and control of the freeze-drying cycle is highlighted. Copyright © 2013 Elsevier B.V. All rights reserved.

  9. 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. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Hybrid glasses from strong and fragile metal-organic framework liquids

    PubMed Central

    Bennett, Thomas D.; Tan, Jin-Chong; Yue, Yuanzheng; Baxter, Emma; Ducati, Caterina; Terrill, Nick J.; Yeung, Hamish H. -M.; Zhou, Zhongfu; Chen, Wenlin; Henke, Sebastian; Cheetham, Anthony K.; Greaves, G. Neville

    2015-01-01

    Hybrid glasses connect the emerging field of metal-organic frameworks (MOFs) with the glass formation, amorphization and melting processes of these chemically versatile systems. Though inorganic zeolites collapse around the glass transition and melt at higher temperatures, the relationship between amorphization and melting has so far not been investigated. Here we show how heating MOFs of zeolitic topology first results in a low density ‘perfect' glass, similar to those formed in ice, silicon and disaccharides. This order–order transition leads to a super-strong liquid of low fragility that dynamically controls collapse, before a subsequent order–disorder transition, which creates a more fragile high-density liquid. After crystallization to a dense phase, which can be remelted, subsequent quenching results in a bulk glass, virtually identical to the high-density phase. We provide evidence that the wide-ranging melting temperatures of zeolitic MOFs are related to their network topologies and opens up the possibility of ‘melt-casting' MOF glasses. PMID:26314784

  11. Hybrid glasses from strong and fragile metal-organic framework liquids.

    PubMed

    Bennett, Thomas D; Tan, Jin-Chong; Yue, Yuanzheng; Baxter, Emma; Ducati, Caterina; Terrill, Nick J; Yeung, Hamish H-M; Zhou, Zhongfu; Chen, Wenlin; Henke, Sebastian; Cheetham, Anthony K; Greaves, G Neville

    2015-08-28

    Hybrid glasses connect the emerging field of metal-organic frameworks (MOFs) with the glass formation, amorphization and melting processes of these chemically versatile systems. Though inorganic zeolites collapse around the glass transition and melt at higher temperatures, the relationship between amorphization and melting has so far not been investigated. Here we show how heating MOFs of zeolitic topology first results in a low density 'perfect' glass, similar to those formed in ice, silicon and disaccharides. This order-order transition leads to a super-strong liquid of low fragility that dynamically controls collapse, before a subsequent order-disorder transition, which creates a more fragile high-density liquid. After crystallization to a dense phase, which can be remelted, subsequent quenching results in a bulk glass, virtually identical to the high-density phase. We provide evidence that the wide-ranging melting temperatures of zeolitic MOFs are related to their network topologies and opens up the possibility of 'melt-casting' MOF glasses.

  12. 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. Copyright © 2014 Elsevier B.V. All rights reserved.

  13. Transition-metal alloying of γ'-Ni3Al : Effects on the ideal uniaxial compressive strength from first-principles calculations

    NASA Astrophysics Data System (ADS)

    Wen, Minru; Wang, Chong-Yu

    2018-01-01

    The addition of transition-metal (TM) elements into the γ' precipitate phase of a Ni-based single-crystal superalloy can significantly affect its mechanical properties, including the intrinsic mechanical property of compressive strength. Using first-principles density functional calculations, the effects of 3 d (Sc-Zn), 4 d (Y-Cd), and 5 d (Hf-Au) TM alloying elements on the ideal uniaxial compressive strength of γ'-Ni3Al were investigated. The stress-strain relationships of pure Ni3Al under [100], [110], and [111] compressive loads and the site occupancy behavior of TM elements in Ni3Al were previously studied using a total-energy method based on density functional theory. Our results showed that the capacity of TM elements for strengthening the ideal compressive strength was associated with the d -electron number. The alloying elements with half-filled d bands (i.e., Cr, Mo, W, Tc, and Re) manifested the greatest efficacy for improving the ideal strength of Ni3Al under a deformation along the weakest compressive direction. Furthermore, the charge redistribution of Ni3Al doped with 5 d elements were also analyzed to understand the strengthening mechanisms of TM elements in the γ'-Ni3Al phase.

  14. Glass Membrane For Controlled Diffusion Of Gases

    DOEpatents

    Shelby, James E.; Kenyon, Brian E.

    2001-05-15

    A glass structure for controlled permeability of gases includes a glass vessel. The glass vessel has walls and a hollow center for receiving a gas. The glass vessel contains a metal oxide dopant formed with at least one metal selected from the group consisting of transition metals and rare earth metals for controlling diffusion of the gas through the walls of the glass vessel. The vessel releases the gas through its walls upon exposure to a radiation source.

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

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

    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 ofmore » 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.« less

  16. Brillouin-scattering study of liquid-glass transitions in ternary mixtures of water, trehalose, and an ionic liquid

    NASA Astrophysics Data System (ADS)

    Takayama, Haruki; Shibata, Tomohiko; Ishii, Takahiro; Kojima, Seiji

    2013-04-01

    Ternary mixtures of water, sugar, and ionic liquid have been studied as new candidates for bioprotectants. To clarify the elastic properties and relaxation dynamics of the supercooled liquid and glassy states at low temperatures, the liquid-glass transitions were investigated by using a micro-Brillouin-scattering technique. The refractive index was measured accurately as a function of content and temperature to determine the sound velocity and the attenuation from Brillouin frequency shift and peak width. The relaxation times of structural relaxations related to liquidglass transitions were determined as functions of temperature. The Meyer-Neldel rule was found to hold for the activation energy and the prefactor of the Arrhenius law for the relaxation time.

  17. Recent advances and future challenges in the explanation and exploitation of the network glass transition of high sugar/biopolymer mixtures.

    PubMed

    Kasapis, Stefan

    2008-02-01

    Through the years, the concept of glassy phenomena evolved from non-science to a highly specialized subject following the appreciation that structural properties or product defects could be rationalized on the basis of this amorphous vitreous transition. Special reference will be made in this review to sugar glasses in the presence of biopolymers which, increasingly, are used to innovate (e.g., replace gelatin) in confections, ice cream, boiled down sweets, etc. Keeping in mind that the subject cuts across several conventional fields, this manuscript is written with several objectives in view. I deemed it necessary to provide a historic itinerary of the nature of the rubber-to-glass transition in association with the concepts of plasticizing and unfreezable water. That should facilitate comprehension and hopefully encourage young scientists to take an interest in the field that continues to offer considerable challenges, as well as opportunities. Second, the food scientist is exposed to the "sophisticated" synthetic polymer approach pioneered by J.D. Ferry and his colleagues via the WLF equation/free volume theoretical framework. Extension of this school of thought to biomaterials introduces the concept of mechanical or network glass transition temperature, which is contrasted to data obtained using differential scanning calorimetry. Applications of the network T(g) as a relevant indicator for evaluating the stability criteria and the quality-control aspects of foodstuffs are also discussed. All along, information available in the literature is critically presented ranging from the misuse of the WLF equation to a recent challenge to the theory mounted by the coupling model, which addresses in some detail the physics of interactions and the cooperativity of molecular mobility at the vicinity of T(g).

  18. Structural transition and orbital glass physics in near-itinerant CoV 2O 4

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

    Reig-i-Plessis, D.; Casavant, D.; Garlea, Vasile O.

    2016-01-25

    In this study, the ferrimagnetic spinel CoV 2O 4 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 ismore » characterized by a 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

  19. 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.

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

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

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

    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 ofmore » 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.« less

  1. Glass composition and solution speciation effects on stage III dissolution

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

    Trivelpiece, Cory L.; Rice, Jarret A.; Pantano, Carlo G.

    To understand and mitigate the onset of Stage III corrosion of multicomponent oxides waste glasses. Stage III refers to a resumption of the high initial rate of glass dissolution in some glass samples that have otherwise exhibited dissolution at the much lower residual rate for a long time (Stage II). Although the onset of Stage III is known to occur concurrently with the precipitation of particular alteration products, the root cause of the transition is still unknown. Certain glass compositions (notably AFCI) and high pH environmental conditions are also associated with this observed transition.

  2. Contrasting dynamics of fragile and non-fragile polyalcohols through the glass, and dynamical, transitions: A comparison of neutron scattering and dielectric relaxation data for sorbitol and glycerol.

    PubMed

    Migliardo, F; Angell, C A; Magazù, S

    2017-01-01

    Glycerol and sorbitol are glass-forming hydrogen-bonded systems characterized by intriguing properties which make these systems very interesting also from the applications point of view. The goal of this work is to relate the hydrogen-bonded features, relaxation dynamics, glass transition properties and fragility of these systems, in particular to seek insight into their very different liquid fragilities. The comparison between glycerol and sorbitol is carried out by collecting the elastic incoherent neutron scattering (EINS) intensity as a function of temperature and of the instrumental energy resolution. Intensity data vs temperature and resolution are analyzed in terms of thermal restraint and Resolution Elastic Neutron Scattering (RENS) approaches. The number of OH groups, which are related to the connecting sites, is a significant parameter both in the glass transition and in the dynamical transition. On the other hand, the disordered nature of sorbitol is confirmed by the existence of different relaxation processes. From the applications point of view, glycerol and sorbitol have remarkable bioprotectant properties which make these systems useful in different technological and industrial fields. Furthermore, polyols are rich in glassforming liquid phenomenology and highly deserving of study in their own right. The comparison of EINS and calorimetric data on glycerol and sorbitol helps provide a connection between structural relaxation, dynamical transition, glass transition, and fragility. The evaluation of the inflection point in the elastic intensity behavior as a function of temperature and instrumental energy resolution provides a confirmation of the validity of the RENS approach. This article is part of a Special Issue entitled "Science for Life" Guest Editor: Dr. Austen Angell, Dr. Salvatore Magazù and Dr. Federica Migliardo. Copyright © 2016. Published by Elsevier B.V.

  3. Edge localized linear ideal magnetohydrodynamic instability studies in an extended-magnetohydrodynamic code

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

    Burke, B. J.; Kruger, S. E.; Hegna, C. C.

    A linear benchmark between the linear ideal MHD stability codes ELITE [H. R. Wilson et al., Phys. Plasmas 9, 1277 (2002)], GATO [L. Bernard et al., Comput. Phys. Commun. 24, 377 (1981)], and the extended nonlinear magnetohydrodynamic (MHD) code, NIMROD [C. R. Sovinec et al.., J. Comput. Phys. 195, 355 (2004)] is undertaken for edge-localized (MHD) instabilities. Two ballooning-unstable, shifted-circle tokamak equilibria are compared where the stability characteristics are varied by changing the equilibrium plasma profiles. The equilibria model an H-mode plasma with a pedestal pressure profile and parallel edge currents. For both equilibria, NIMROD accurately reproduces the transition tomore » instability (the marginally unstable mode), as well as the ideal growth spectrum for a large range of toroidal modes (n=1-20). The results use the compressible MHD model and depend on a precise representation of 'ideal-like' and 'vacuumlike' or 'halo' regions within the code. The halo region is modeled by the introduction of a Lundquist-value profile that transitions from a large to a small value at a flux surface location outside of the pedestal region. To model an ideal-like MHD response in the core and a vacuumlike response outside the transition, separate criteria on the plasma and halo Lundquist values are required. For the benchmarked equilibria the critical Lundquist values are 10{sup 8} and 10{sup 3} for the ideal-like and halo regions, respectively. Notably, this gives a ratio on the order of 10{sup 5}, which is much larger than experimentally measured values using T{sub e} values associated with the top of the pedestal and separatrix. Excellent agreement with ELITE and GATO calculations are made when sharp boundary transitions in the resistivity are used and a small amount of physical dissipation is added for conditions very near and below marginal ideal stability.« less

  4. Gardner Transition in Physical Dimensions

    NASA Astrophysics Data System (ADS)

    Hicks, C. L.; Wheatley, M. J.; Godfrey, M. J.; Moore, M. A.

    2018-06-01

    The Gardner transition is the transition that at mean-field level separates a stable glass phase from a marginally stable phase. This transition has similarities with the de Almeida-Thouless transition of spin glasses. We have studied a well-understood problem, that of disks moving in a narrow channel, which shows many features usually associated with the Gardner transition. We show that some of these features are artifacts that arise when a disk escapes its local cage during the quench to higher densities. There is evidence that the Gardner transition becomes an avoided transition, in that the correlation length becomes quite large, of order 15 particle diameters, even in our quasi-one-dimensional system.

  5. XRD and FTIR studies the effect of heat treatment and doping the transition metal oxide on LiNbO3 and LiNb3O8 nano-crystallite phases in lithium borate glass system.

    PubMed

    Kashif, Ismail; Soliman, Ashia A; Sakr, Elham M; Ratep, Asmaa

    2013-09-01

    Glasses of various compositions in the system 90 Li2B4O7-10 Nb2O5 mixed with T.M ions (where T.M is the transition metal) were prepared by quenching technique. Heat-treatment of the parent glasses was performed at 540, 570 and 620 °C, for 5 and 16 h. The glass structure evolution during the controlled crystallization was examined by XRD and FT-IR spectroscopy analysis. The crystalline phases present in the glass ceramics were identified via X-ray diffraction as a function of heat treatment. The FT-IR data propose for these glasses and heat-treated glass network structures mainly built by: di-, tri-, tetra-, penta-and ortho-borate groups. It was found that the quantitative evolution of these various borate species in the glass structures is influenced by the transition metal. A detailed discussion relating to the N4 evolution with the T.M content was made. Copyright © 2013 Elsevier B.V. All rights reserved.

  6. Physicochemical characterization and drug-release properties of celecoxib hot-melt extruded glass solutions.

    PubMed

    Andrews, Gavin P; Abu-Diak, Osama; Kusmanto, Febe; Hornsby, Peter; Hui, Zhai; Jones, David S

    2010-11-01

    The interest in hot-melt extrusion (HME) as a drug delivery technology for the production of glass solutions is growing rapidly. HME glass solutions have a tendency to recrystallize during storage and also typically have a very dense structure, restricting the ingress of dissolution fluid and retarding drug release. In this study, we have used HME to manufacture glass solutions containing celecoxib (CX) and polyvinylpyrrolidone (PVP) and have assessed the use of supercritical carbon dioxide (scCO2) as a pore-forming agent to enhance drug release. Differential scanning calorimetry confirmed the formation of glass solutions following extrusion. All extrudates exhibited a single glass transition temperature (Tg), positioned between the Tg values of CX and PVP. The instability of glass solutions is a significant problem during storage. Stabilization may be improved through the appropriate choice of excipient to facilitate drug–polymer interactions. The Gordon–Taylor equation showed that the Tg values of all extrudates expected on ideal mixing were lower than those observed experimentally. This may be indicative of drug–polymer interactions that decrease free volume and elevate the Tg. Molecular interactions between CX and PVP were further confirmed using Fourier transform infrared and Raman spectroscopy. Storage stability of the extrudates was shown to be dependent on drug loading. Samples containing a higher CX loading were less stable, which we ascribed to decreased Tg and hence increased mobility within the drug–polymer matrix. The solubility of CX was improved through the formulation of extruded glass solutions, but release rate was relatively slow. Exposure of extrudates to scCO2 had no effect on the solid-state properties of CX but did produce a highly porous structure. The drug-release rate from extrudates after scCO2 exposure was significantly higher.

  7. Computational studies of the glass-forming ability of model bulk metallic glasses

    NASA Astrophysics Data System (ADS)

    Zhang, Kai; Wang, Minglei; Papanikolaou, Stefanos; Liu, Yanhui; Schroers, Jan; Shattuck, Mark D.; O'Hern, Corey S.

    2013-09-01

    Bulk metallic glasses (BMGs) are produced by rapidly thermally quenching supercooled liquid metal alloys below the glass transition temperature at rates much faster than the critical cooling rate Rc below which crystallization occurs. The glass-forming ability of BMGs increases with decreasing Rc, and thus good glass-formers possess small values of Rc. We perform molecular dynamics simulations of binary Lennard-Jones (LJ) mixtures to quantify how key parameters, such as the stoichiometry, particle size difference, attraction strength, and heat of mixing, influence the glass-formability of model BMGs. For binary LJ mixtures, we find that the best glass-forming mixtures possess atomic size ratios (small to large) less than 0.92 and stoichiometries near 50:50 by number. In addition, weaker attractive interactions between the smaller atoms facilitate glass formation, whereas negative heats of mixing (in the experimentally relevant regime) do not change Rc significantly. These results are tempered by the fact that the slowest cooling rates achieved in our simulations correspond to ˜1011 K/s, which is several orders of magnitude higher than Rc for typical BMGs. Despite this, our studies represent a first step in the development of computational methods for quantitatively predicting glass-formability.

  8. Universal behavior of the osmotically compressed cell and its analogy to the colloidal glass transition

    PubMed Central

    Zhou, E. H.; Trepat, X.; Park, C. Y.; Lenormand, G.; Oliver, M. N.; Mijailovich, S. M.; Hardin, C.; Weitz, D. A.; Butler, J. P.; Fredberg, J. J.

    2009-01-01

    Mechanical robustness of the cell under different modes of stress and deformation is essential to its survival and function. Under tension, mechanical rigidity is provided by the cytoskeletal network; with increasing stress, this network stiffens, providing increased resistance to deformation. However, a cell must also resist compression, which will inevitably occur whenever cell volume is decreased during such biologically important processes as anhydrobiosis and apoptosis. Under compression, individual filaments can buckle, thereby reducing the stiffness and weakening the cytoskeletal network. However, the intracellular space is crowded with macromolecules and organelles that can resist compression. A simple picture describing their behavior is that of colloidal particles; colloids exhibit a sharp increase in viscosity with increasing volume fraction, ultimately undergoing a glass transition and becoming a solid. We investigate the consequences of these 2 competing effects and show that as a cell is compressed by hyperosmotic stress it becomes progressively more rigid. Although this stiffening behavior depends somewhat on cell type, starting conditions, molecular motors, and cytoskeletal contributions, its dependence on solid volume fraction is exponential in every instance. This universal behavior suggests that compression-induced weakening of the network is overwhelmed by crowding-induced stiffening of the cytoplasm. We also show that compression dramatically slows intracellular relaxation processes. The increase in stiffness, combined with the slowing of relaxation processes, is reminiscent of a glass transition of colloidal suspensions, but only when comprised of deformable particles. Our work provides a means to probe the physical nature of the cytoplasm under compression, and leads to results that are universal across cell type. PMID:19520830

  9. Experimental and computational prediction of glass transition temperature of drugs.

    PubMed

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

    2014-12-22

    Glass transition temperature (Tg) is an important inherent property of an amorphous solid material which is usually determined experimentally. In this study, the relation between Tg and melting temperature (Tm) was evaluated using a data set of 71 structurally diverse druglike compounds. Further, in silico models for prediction of Tg were developed based on calculated molecular descriptors and linear (multilinear regression, partial least-squares, principal component regression) and nonlinear (neural network, support vector regression) modeling techniques. The models based on Tm predicted Tg with an RMSE of 19.5 K for the test set. Among the five computational models developed herein the support vector regression gave the best result with RMSE of 18.7 K for the test set using only four chemical descriptors. Hence, two different models that predict Tg of drug-like molecules with high accuracy were developed. If Tm is available, a simple linear regression can be used to predict Tg. However, the results also suggest that support vector regression and calculated molecular descriptors can predict Tg with equal accuracy, already before compound synthesis.

  10. Effect of In-Situ Cure on Measurement of Glass Transition Temperatures in High-Temperature Thermosetting Polymers (Briefing Charts)

    DTIC Science & Technology

    2015-05-20

    TEMPERATURES IN HIGH-TEMPERATURE THERMOSETTING POLYMERS 5a. CONTRACT NUMBER In-House 5b. GRANT NUMBER 5c. PROGRAM ELEMENT NUMBER 6. AUTHOR(S) 5d...temperature thermosetting polymer via dynamic mechanical analysis alone. These difficulties result from the residual cure of samples heated beyond their...98) Prescribed by ANSI Std. 239.18 Effect of In-Situ Cure on Measurement of Glass Transition Temperatures in High-Temperature Thermosetting

  11. Formation of vortex line around the glass transition in YBa{sub 2}Cu{sub 3}O{sub 7-{delta}} films

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

    Nojima, T.; Kakinuma, A.; Kuwasawa, Y.

    1996-12-01

    Two components of current-induced electric fields in ab plane, E{sub x} and E{sub y}, have been measured simultaneously on YBCO(123) films around the glass transition temperature T{sub g} in magnetic fields H with components (H{sub 0}, H{sub 0}, 0.1H{sub 0}), where x and y axes are parallel to the direction of the current density and c axis, respectively. In this condition, a finite transverse field E{sub y} almost equal to E{sub x} can be observed if the vortex lines form and move along the Lorentz force. In each H, the ratio {vert_bar}E{sub y}/E{sub x}{vert_bar} at a low current limit, whichmore » is zero far above T{sub g}, increases in the critical region and transfers to unity below T{sub g}. The authors results indicate that the vortices become lines with long range correlation along H direction at the vortex glass transition without receiving the effect of the intrinsic pinning.« less

  12. Structure, glass transition temperature and spectroscopic properties of 10Li2O-xP2O5-(89-x)TeO2-1CuO (5≤x≤25 mol%) glass system.

    PubMed

    Upender, G; Babu, J Chinna; Mouli, V Chandra

    2012-04-01

    X-ray diffraction (XRD), field emission scanning electron microscope (FESEM), energy dispersive X-ray spectrometry (EDS), differential scanning calorimetry (DSC), infrared (IR), Raman, electron paramagnetic resonance (EPR) and optical absorption studies on 10Li2O-xP2O5-(89-x)TeO2-1CuO glasses (where x=5, 10, 15, 20 and 25 mol%) have been carried out. The amorphous nature of the glasses was confirmed using XRD and FESEM measurements. The glass transition temperature (Tg) of glass samples have been estimated from DSC traces and found that the Tg increases with increasing P2O5 content. Both the IR and Raman studies have been showed that the present glass system consists of [TeO3], [TeO4], [PO3] and [PO4] units. The spin-Hamiltonian parameters such as g∥, g⊥, and A∥ have been determined from EPR spectra and it was found that the Cu2+ ion is present in tetragonal distorted octahedral site with [Formula: see text] as the ground state. Bonding parameters and bonding symmetry of Cu2+ ions have been calculated by correlating EPR and optical data and were found to be composition dependent. Copyright © 2012 Elsevier B.V. All rights reserved.

  13. Cooperative behavior of molecular motions giving rise to two glass transitions in the same supercooled mesophase of a smectogenic liquid crystal dimer

    NASA Astrophysics Data System (ADS)

    López, David O.; Salud, Josep; de la Fuente, María Rosario; Sebastián, Nerea; Diez-Berart, Sergio

    2018-01-01

    In the present work, a detailed analysis of the glassy behavior and the relaxation dynamics of the liquid crystal dimer α-(4-cyanobiphenyl-4'-yloxy)-ω-(1-pyrenimine-benzylidene-4'-oxy) heptane (CBO7O.Py) throughout both nematic and smectic-A mesophases by means of broadband dielectric spectroscopy has been performed. CBO7O.Py shows three different dielectric relaxation modes and two glass transition (Tg) temperatures: The higher Tg is due to the freezing of the molecular motions responsible for the relaxation mode with the lowest frequency (μ1 L); the lower Tg is due to the motions responsible for the two relaxation modes with highest frequencies (μ1 H and μ2), which converge just at their corresponding Tg. It is shown how the three modes follow a critical-like description via the dynamic scaling model. The two modes with lowest frequencies (μ1 L and μ1 H) are cooperative in the whole range of the mesophases, whereas the highest frequency mode (μ2) is cooperative just below some crossover temperature. In terms of fragility, at the glass transition, the ensemble (μ1 H+μ2 ) presents a value of the steepness index and μ1 L a different one, meaning that fragility is a property intrinsic to the molecular motion itself. Finally, the steepness index seems to have a universal behavior with temperature for the dielectric relaxation modes of liquid crystal dimers, being almost constant at high temperatures and increasing drastically when cooling the compound down to the glass transition from a temperature about 3/4 TN I .

  14. Spectral investigations of Sm{sup 3+}-doped oxyfluorosilicate glasses

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

    Ramachari, D.; Rama Moorthy, L., E-mail: lrmphysics@yahoo.co.in; Department of Physics, Chadalawada Ramanamma Engineering College, Renigunta Road, Tirupati 517506

    2013-09-01

    Graphical abstract: The figure shows the emission spectra of Sm{sup 3+} doped KNSZL glass for different concentrations. Among the four emission transitions {sup 4}G{sub 5/2} → {sup 6}H{sub 5/2}, {sup 4}G{sub 5/2} → {sup 6}H{sub 7/2}, {sup 4}G{sub 5/2} → {sup 6}H{sub 9/2} and {sup 4}G{sub 5/2} → {sup 6}H{sub 11/2}, the {sup 4}G{sub 5/2} → {sup 6}H{sub 7/2} transition of KNSZLSm10 glass is more intense compared with all the transitions. The insert figure shows, the color coordinates (0.59, 0.41) of KNSZLSm10 glass is located on the perimeter of the chromaticity diagram at 592 nm which appears to be closestmore » to the orange color. From these results the KNSZLSm10 glass could be useful for optical amplifiers, waveguides, telecommunications and orange LEDs. - Highlights: • From the DTA, the undoped KNSZL glass more precisely in fiberdrawing. • The XRD pattern confirmed the KNbO{sub 3} nanocrystallites of undoped KNSZL glass. • FTIR and Raman data of KNSZLSm10 glass revealed structural properties. • Judd–Ofelt analysis and decay measurements were carried out. • The optical gain parameter of the investigated glass is 18.13 × 10{sup −25} cm{sup 2} s. - Abstract: Sm{sub 2}O{sub 3}-doped oxyfluorosilicate glasses were prepared by melt-quenching method. The differential thermal analysis and X-ray diffraction were carried out to investigate the glass transition temperature and structure of precursor glass. Infrared spectroscopy, Raman, optical absorption, photoluminescence and decay measurements were carried out for Sm{sup 3+}-doped oxyfluorosilicate glasses. From the absorption spectrum, the Judd–Ofelt intensity parameters have been evaluated to predict the radiative properties for the emission levels of Sm{sup 3+} ions. The lifetimes of {sup 4}G{sub 5/2} level are found to decrease from 1.17 to 0.93 ms due to the energy transfer, when the concentration of Sm{sup 3+} ions increases from 0.1 to 2.0 mol%. The optical gain parameter (18.13 × 10

  15. Effect of a counterion on the glass transition temperature (T(g)') during lyophilization of ganciclovir salt forms.

    PubMed

    Kumar, Lokesh; Baheti, Ankit; Bansal, Arvind K

    2011-02-07

    This manuscript deals with the effect of a counterion on the glass transition temperature for lyophilization of ganciclovir salts. Salt forms of ganciclovir, namely, sodium, potassium, rubidium, and cesium salts, were prepared by an in situ technique and analyzed by modulated differential scanning calorimetry (MDSC) for the determination of the critical process parameter for lyophilization. Nonionized ganciclovir and its salt forms showed a glass transition (T(g)') in the reversing MDSC signal, confirming their amorphous nature. T(g)' of the nonionized ganciclovir and ganciclovir sodium, potassium, rubidium, and cesium salts followed the order: sodium salt (-34.94°C) > nonionized ganciclovir (-40.15°C) > potassium salt (-46.23°C) > rubidium salt (-49.95°C) > cesium salt (-53.62°C). The analysis of the freezable water content for ganciclovir and its salts showed the trend: pure water > nonionized ganciclovir > potassium salt ∼ sodium salt > rubidium salt > cesium salt. This showed that a majority of water in the salts is present as an unfrozen fraction, thus leading to a lowering of T(g)' because of the plasticizing effect of unfrozen water. Density functional theory (DFT) further suggested a positive contribution of the strength of intra- and intermolecular force of interactions to the T(g)' value, with a higher intramolecular and intermolecular force of interaction leading to a higher T(g)'.

  16. Growth and characterization of amorphous selenium: An exploration into the glass transition temperature

    NASA Astrophysics Data System (ADS)

    Schaefers, Justin Kyle

    The glass transition temperature (Tg) of alpha-Se films and its correlation to percent As inclusion was explored using such characterization tools as Raman spectroscopy, spectroscopic ellipsometry, atomic force microscopy, and microphotography. The films were deposited under ultra high vacuum conditions in a dedicated molecular beam epitaxy chamber onto semi-insulating GaAs (100) substrates. After deposition, the samples were thermally annealed in 5°C increments until they began to crystallize, as evident in the characterizations performed. It was discovered that not only is Tg directly related to percent As, but that the film thickness is as well. Higher than previously reported values, Tg was found to be 80°C for 0% As, 110°C for 2% As, and 125°C for 5% As. In addition, instead of producing polycrystalline films containing all the allotropes of Se as a result of the annealing process, films of the trigonal allotrope of crystalline selenium (t-Se) were produced through the annealing process. The transition from the amorphous phase to the trigonal phase has never been reported prior to this dissertation. Finally, it was also discovered that the MBE deposition of the films is truly epitaxial in nature.

  17. Fractal free energy landscapes in structural glasses.

    PubMed

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

    2014-04-24

    Glasses are amorphous solids whose constituent particles are caged by their neighbours and thus cannot flow. This sluggishness is often ascribed to the free energy landscape containing multiple minima (basins) separated by high barriers. Here we show, using theory and numerical simulation, that the landscape is much rougher than is classically assumed. Deep in the glass, it undergoes a 'roughness transition' to fractal basins, which brings about isostaticity and marginal stability on approaching jamming. Critical exponents for the basin width, the weak force distribution and the spatial spread of quasi-contacts near jamming can be analytically determined. Their value is found to be compatible with numerical observations. This advance incorporates the jamming transition of granular materials into the framework of glass theory. Because temperature and pressure control what features of the landscape are experienced, glass mechanics and transport are expected to reflect the features of the topology we discuss here.

  18. Temperature Dependence of Arn+ Cluster Backscattering from Polymer Surfaces: a New Method to Determine the Surface Glass Transition Temperature.

    PubMed

    Poleunis, Claude; Cristaudo, Vanina; Delcorte, Arnaud

    2018-01-01

    In this work, time-of-flight secondary ion mass spectrometry (ToF-SIMS) was used to study the intensity variations of the backscattered Ar n + clusters as a function of temperature for several amorphous polymer surfaces (polyolefins, polystyrene, and polymethyl methacrylate). For all these investigated polymers, our results show a transition of the ratio Ar 2 + /(Ar 2 + + Ar 3 + ) when the temperature is scanned from -120 °C to +125 °C (the exact limits depend on the studied polymer). This transition generally spans over a few tens of degrees and the temperature of the inflection point of each curve is always lower than the bulk glass transition temperature (T g ) reported for the considered polymer. Due to the surface sensitivity of the cluster backscattering process (several nanometers), the presented analysis could provide a new method to specifically evaluate a surface transition temperature of polymers, with the same lateral resolution as the gas cluster beam. Graphical abstract ᅟ.

  19. Inhomogeneous and homogeneous linewidths in Er 3+-doped chalcogenide glasses

    NASA Astrophysics Data System (ADS)

    Bigot, L.; Jurdyc, A.-M.; Jacquier, B.; Adam, J.-L.

    2003-10-01

    The erbium 4I 13/2- 4I 15/2 transition around 1.5 μm is of prim interest for telecommunications and depends on the erbium ions surrounding. In glasses, the broadening of a transition comes from two contributions: inhomogeneous (due to the disorder) and homogeneous (due to the electron phonon interaction) broadening. Resonant Fluorescence Line Narrowing (RFLN) is a useful tool to separate this two parameters. We will show in this paper that the 4I 13/2- 4I 15/2 transition in chalcogenide glass (GeGaSSb) presents a strong homogeneous character and a smaller inhomogeneous contribution compared to aluminosilicate and fluoride glasses. Consequences on gain saturation will also be discussed.

  20. Ion transport mechanism in glasses: non-Arrhenius conductivity and nonuniversal features.

    PubMed

    Murugavel, S; Vaid, C; Bhadram, V S; Narayana, C

    2010-10-28

    In this article, we report non-Arrhenius behavior in the temperature-dependent dc conductivity of alkali ion conducting silicate glasses well below their glass transition temperature. In contrast to the several fast ion-conducting and binary potassium silicate glasses, these glasses show a positive deviation in the Arrhenius plot. The observed non-Arrhenius behavior is completely reproducible in nature even after prolonged annealing close to the glass transition temperature of the respective glass sample. These results are the manifestation of local structural changes of the silicate network with temperature and give rise to different local environments into which the alkali ions hop, revealed by in situ high-temperature Raman spectroscopy. Furthermore, the present study provides new insights into the strong link between the dynamics of the alkali ions and different sites associated with it in the glasses.

  1. Preparation and properties of Ge4Se96 glass

    NASA Astrophysics Data System (ADS)

    Xu, Junfeng; Sun, Guozhen; Liu, Zhenting; Wang, Yaling; Jian, Zengyun

    2018-03-01

    The chalcogenide glass Ge4Se96 was prepared by melt-quenched method. The characteristic temperatures (the strain point, annealing point, glass transition point, yielding point and soften point) were determined by thermal analysis. The result shows that the glass transition point is 52 °C; the average thermal expansion coefficient is ΔL/L0 = (0.0557∗T-1.7576)/1000. The specific heat of Ge4Se96 glass was measured by stepwise method. The difference in specific heat between amorphous structure and undercooled liquid was determined as ΔCp = 0.1812-5.20 × 10-4T-4.92 × 10-7T2 JK-1 g-1. Based on the result of ΔCp, the Gibbs energy and the entropy curves were calculated, and the Kauzmann temperature was determined as Tk = 233.5 K, which is between that for pure Se glass (216 K) and that for Ge7.4Se92.6 glass (250 K). It indicates that for Ge-Se glass with low Ge content, the Kauzmann temperature increases with increasing the content of Ge.

  2. Calorimetric indications of a cooperativity onset in the crossover region of dynamic glass transition for benzoin isobutylether

    NASA Astrophysics Data System (ADS)

    Kahle, S.; Schröter, K.; Hempel, E.; Donth, E.

    1999-10-01

    Heat capacity spectroscopy (HCS), dielectric spectroscopy, and shear viscosity data are reported for liquid benzoin isobutylether (BIBE). Dielectric and viscosity peculiarities indicate the crossover region of dynamic glass transition at T=(-8±8) °C where the extrapolated Johari Goldstein β relaxation intersects the main transition trace in an Arrhenius plot. Although HCS does not reach the crossover frequency of order ω=2×106 rad/s, the linear decrease of the square root of cooperativity as calculated from HCS data at lower frequencies indicates a cooperativity onset in the crossover temperature-frequency range. As BIBE belongs to another dielectric crossover scenario as the substances where such an onset could previously be observed, it seems that the cooperativity onset is a general property of the crossover region.

  3. Glass formability in medium-sized molecular systems/pharmaceuticals. I. Thermodynamics vs. kinetics.

    PubMed

    Tu, Wenkang; Li, Xiangqian; Chen, Zeming; Liu, Ying Dan; Labardi, Massimiliano; Capaccioli, Simone; Paluch, M; Wang, Li-Min

    2016-05-07

    Scrutinizing critical thermodynamic and kinetic factors for glass formation and the glass stability of materials would benefit the screening of the glass formers for the industry of glassy materials. The present work aims at elucidating the factors that contribute to the glass formation by investigating medium-sized molecules of pharmaceuticals. Glass transition related thermodynamics and kinetics are performed on the pharmaceuticals using calorimetric, dielectric, and viscosity measurements. The characteristic thermodynamic and kinetic parameters of glass transition are found to reproduce the relations established for small-molecule glass formers. The systematic comparison of the thermodynamic and kinetic contributions to glass formation reveals that the melting-point viscosity is the crucial quantity for the glass formation. Of more interest is the finding of a rough correlation between the melting-point viscosity and the entropy of fusion normalized by the number of beads of the pharmaceuticals, suggesting the thermodynamics can partly manifest its contribution to glass formation via kinetics.

  4. Glass formability in medium-sized molecular systems/pharmaceuticals. I. Thermodynamics vs. kinetics

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

    Tu, Wenkang; Li, Xiangqian; Chen, Zeming

    Scrutinizing critical thermodynamic and kinetic factors for glass formation and the glass stability of materials would benefit the screening of the glass formers for the industry of glassy materials. The present work aims at elucidating the factors that contribute to the glass formation by investigating medium-sized molecules of pharmaceuticals. Glass transition related thermodynamics and kinetics are performed on the pharmaceuticals using calorimetric, dielectric, and viscosity measurements. The characteristic thermodynamic and kinetic parameters of glass transition are found to reproduce the relations established for small-molecule glass formers. The systematic comparison of the thermodynamic and kinetic contributions to glass formation reveals thatmore » the melting-point viscosity is the crucial quantity for the glass formation. Of more interest is the finding of a rough correlation between the melting-point viscosity and the entropy of fusion normalized by the number of beads of the pharmaceuticals, suggesting the thermodynamics can partly manifest its contribution to glass formation via kinetics.« less

  5. "Ideal" tearing and the transition to fast reconnection in the weakly collisional MHD and EMHD regimes

    NASA Astrophysics Data System (ADS)

    Del Sarto, Daniele; Pucci, Fulvia; Tenerani, Anna; Velli, Marco

    2016-03-01

    This paper discusses the transition to fast growth of the tearing instability in thin current sheets in the collisionless limit where electron inertia drives the reconnection process. It has been previously suggested that in resistive MHD there is a natural maximum aspect ratio (ratio of sheet length and breadth to thickness) which may be reached for current sheets with a macroscopic length L, the limit being provided by the fact that the tearing mode growth time becomes of the same order as the Alfvén time calculated on the macroscopic scale. For current sheets with a smaller aspect ratio than critical the normalized growth rate tends to zero with increasing Lundquist number S, while for current sheets with an aspect ratio greater than critical the growth rate diverges with S. Here we carry out a similar analysis but with electron inertia as the term violating magnetic flux conservation: previously found scalings of critical current sheet aspect ratios with the Lundquist number are generalized to include the dependence on the ratio de2/L2, where de is the electron skin depth, and it is shown that there are limiting scalings which, as in the resistive case, result in reconnecting modes growing on ideal time scales. Finite Larmor radius effects are then included, and the rescaling argument at the basis of "ideal" reconnection is proposed to explain secondary fast reconnection regimes naturally appearing in numerical simulations of current sheet evolution.

  6. Glass-Derived Superconductive Ceramic

    NASA Technical Reports Server (NTRS)

    Bansal, Narottam P.; Farrell, D. E.

    1992-01-01

    Critical superconducting-transition temperature of 107.2 K observed in specimen made by annealing glass of composition Bi1.5Pb0.5Sr2Ca2Cu3Ox for 243 h at 840 degrees C. PbO found to lower melting temperature and viscosity of glass, possibly by acting as fluxing agent. Suggested partial substitution of lead into bismuth oxide planes of crystalline phase having Tc of 110 K stabilizes this phase and facilitates formation of it.

  7. Anharmonic Vibrations of an "Ideal" Hooke's Law Oscillator

    ERIC Educational Resources Information Center

    Thomchick, John; McKelvey, J. P.

    1978-01-01

    Presents a model describing the vibrations of a mass connected to fixed supports by "ideal" Hooke's law springs which may serve as a starting point in the study of the properties of irons in a crystal undergoing soft mode activated transition. (SL)

  8. Transition from Arrhenius to non-Arrhenius temperature dependence of structural relaxation time in glass-forming liquids: continuous versus discontinuous scenario.

    PubMed

    Popova, V A; Surovtsev, N V

    2014-09-01

    The temperature dependences of α relaxation time τ(α)(T) of three glass-forming liquids (salol, o-terphenyl, and α-picoline) were investigated by a depolarized light scattering technique. A detailed description of τ(α)(T) near T(A), the temperature of the transition from the Arrhenius law at high temperatures to a non-Arrhenius behavior of τ(α)(T) at lower temperatures, was done. It was found that this transition is quite sharp. If the transition is described as switching from the Arrhenius law to the Vogel-Fulcher-Tammann law, it occurs within the temperature range of about 15 K or less. Most of the known expressions for τ(α)(T) cannot describe this sharp transition. Our analysis revealed that this transition can be described either as a discontinuous transition in the spirit of the frustration-limited domain theory [D. Kivelson, G. Tarjus, X. Zhao, and S. A. Kivelson, Phys. Rev. E 53, 751 (1996)], implying a phase transition, or by a phenomenological expression recently suggested [B. Schmidtke, N. Petzold, R. Kahlau, M. Hofmann, and E. A. Rössler, Phys. Rev. E 86, 041507 (2012)], where the activation energy includes the term depending exponentially on temperature.

  9. Hopping and the Stokes-Einstein relation breakdown in simple glass formers.

    PubMed

    Charbonneau, Patrick; Jin, Yuliang; Parisi, Giorgio; Zamponi, Francesco

    2014-10-21

    One of the most actively debated issues in the study of the glass transition is whether a mean-field description is a reasonable starting point for understanding experimental glass formers. Although the mean-field theory of the glass transition--like that of other statistical systems--is exact when the spatial dimension d → ∞, the evolution of systems properties with d may not be smooth. Finite-dimensional effects could dramatically change what happens in physical dimensions,d = 2, 3. For standard phase transitions finite-dimensional effects are typically captured by renormalization group methods, but for glasses the corrections are much more subtle and only partially understood. Here, we investigate hopping between localized cages formed by neighboring particles in a model that allows to cleanly isolate that effect. By bringing together results from replica theory, cavity reconstruction, void percolation, and molecular dynamics, we obtain insights into how hopping induces a breakdown of the Stokes-Einstein relation and modifies the mean-field scenario in experimental systems. Although hopping is found to supersede the dynamical glass transition, it nonetheless leaves a sizable part of the critical regime untouched. By providing a constructive framework for identifying and quantifying the role of hopping, we thus take an important step toward describing dynamic facilitation in the framework of the mean-field theory of glasses.

  10. Organic Glasses with Tunable Liquid-Crystalline Order

    NASA Astrophysics Data System (ADS)

    Teerakapibal, Rattavut; Huang, Chengbin; Gujral, Ankit; Ediger, Mark D.; Yu, Lian

    2018-02-01

    Liquid crystals (LCs) are known to undergo rapid ordering transitions with virtually no hysteresis. We report a remarkable counterexample, itraconazole, where the nematic to smectic transition is avoided at a cooling rate exceeding 20 K /s . The smectic order trapped in a glass is the order reached by the equilibrium liquid before the kinetic arrest of the end-over-end molecular rotation. This is attributed to the fact that smectic ordering requires orientational ordering and suggests a general condition for preparing organic glasses with tunable LC order for electronic applications.

  11. Volume Phase Masks in Photo-Thermo-Refractive Glass

    DTIC Science & Technology

    2014-10-06

    development when forming the nanocrystals. Fig. 1.1 shows the refractive index change curves for some common glass melts when exposed to a beam at 325 nm...integral curve to the curve for the ideal phase mask. If there is a deviation in the experimental curve from the ideal curve , whether the overlap...redevelopments of the sample. Note that the third point on the spherical curve and the third and fourth points on the coma y curve have larger error bars than

  12. Effect of variation in the glass-former network structure on the relaxation properties of conductive Ag+ ions in AgI-based fast ion conducting glasses

    NASA Astrophysics Data System (ADS)

    Hanaya, Minoru; Nakayama, Michiko; Hatate, Atsuo; Oguni, Masaharu

    1995-08-01

    Heat capacities and ac conductivities of AgI-based fast ion conducting glasses of AgI-Ag2O-P2O5 and AgI-Ag2O-B2O3 systems with different P-O or B-O network structures but with the same AgI concentration of 1.55×104 mol m-3 were measured in the temperature range 14-400 K and in the temperature and frequency ranges 100-200 K and 10 Hz-1 MHz, respectively. The β-glass transition due to a freezing-in of the rearrangement of Ag+ ions was observed by adiabatic calorimetry for the glasses in the liquid-nitrogen temperature region, and the conductometry was suggested to see the same mode of Ag+-ion motion as the calorimetry. It was found that the development of the network structure of the glass former at constant AgI concentration resulted in the decrease of the β-glass transition temperature and the activation energy for the diffusional motion of Ag+ ions and in the increase of the heat-capacity jump associated with the glass transition. The results support the amorphous AgI aggregate model for the structure of the conductive region in the glasses with relatively high AgI compositions, indicating that Ag+-ion conductivity is mainly dominated by the degree of development of the AgI aggregate region dependent on the glass-former network structure as well as the AgI composition.

  13. Glass transition dynamics and conductivity scaling in ionic deep eutectic solvents: The case of (acetamide + lithium nitrate/sodium thiocyanate) melts.

    PubMed

    Tripathy, Satya N; Wojnarowska, Zaneta; Knapik, Justyna; Shirota, Hideaki; Biswas, Ranjit; Paluch, Marian

    2015-05-14

    A detailed investigation on the molecular dynamics of ionic deep eutectic solvents (acetamide + lithium nitrate/sodium thiocyanate) is reported. The study was carried out employing dielectric relaxation spectroscopy covering seven decades in frequency (10(-1)-10(6) Hz) and in a wide temperature range from 373 K down to 173 K, accessing the dynamic observables both in liquid and glassy state. The dielectric response of the ionic system has been presented in the dynamic window of modulus formalism to understand the conductivity relaxation and its possible connection to the origin of localized motion. Two secondary relaxation processes appear below glass transition temperature. Our findings provide suitable interpretation on the nature of secondary Johari-Goldstein process describing the ion translation and orientation of dipoles in a combined approach using Ngai's coupling model. A nearly constant loss feature is witnessed at shorter times/lower temperatures. We also discuss the ac conductivity scaling behavior using Summerfield approach and random free energy barrier model which establish the time-temperature superposition principle. These experimental observations have fundamental importance on theoretical elucidation of the conductivity relaxation and glass transition phenomena in molten ionic conductors.

  14. Devitrification properties of lead borate glasses

    NASA Astrophysics Data System (ADS)

    Bajaj, Anu; Khanna, Atul; Krishnan, K.; Aggarwal, Suresh K.

    2013-06-01

    Lead borate glasses containing 30 to 60 mol% PbO were prepared by melt quenching technique and devitrified by long duration heat treament in the supercooled region. Glasses crystallized on heating above their glass transition temperature, and the crystalline phases produced on devitrification were characterized by XRD and DSC analyses. Glass with 30 mol% PbO slowly formed a solid solution of Pb6B10O21 and Pb5B8O17 crystalline phases, while glasses with 40 and 50 mol% PbO formed a mixture of Pb6B10O21, Pb5B8O17 and the remanent glassy phase. Glasses with higher PbO concentration of 56 to 60 mol% devitrified completely and produced only Pb5B8O17 crystalline phase. Lead borate glasses with PbO concentration of 40 to 50 mol% showed maximum thermal stability against devitrification, the ease of crystallization of glasses was correlated with the fraction of tetrahedral borons in them.

  15. Predict the glass transition temperature and plasticization of β-cyclodextrin/water binary system by molecular dynamics simulation.

    PubMed

    Zhou, Guohui; Zhao, Tianhai; Wan, Jie; Liu, Chengmei; Liu, Wei; Wang, Risi

    2015-01-12

    The glass transition temperature, diffusion behavior and plasticization of β-cyclodextrin (β-CD), and three amorphous β-CD/water mixtures (3%, 5% and 10% [w/w] water, respectively) were investigated by molecular dynamics simulation, which were performed using Condensed-phase Optimized Molecular Potentials for Atomistic Simulation Studies (COMPASS) force field and isothermal-isobaric ensembles. The specific volumes of four amorphous cells were obtained as a function of temperature. The glass transition temperatures (T(g)) were estimated to be 334.25 K, 325.12 K, 317.32 K, and 305.41 K for amorphous β-CD containing 0%, 3%, 5% and 10% w/w water, respectively, which compares well with the values observed in published literature. The radial distribution function was computed to elucidate the intermolecular interactions between amorphous β-CD and water, which acts as a plasticizer. These results indicate that the hydrogen bond interactions of oxygen in hydroxyl ions was higher than oxygen in acetal groups in β-CD amorphous mixtures with that in water, due to less accessibility of ring oxygens to the surrounding water molecules. The mobility of water molecules was investigated over various temperature ranges, including the rubbery and glassy phases of the β-CD/water mixtures, by calculating the diffusion coefficients and the fractional free volume. In β-CD amorphous models, the higher mobility of water molecules was observed at temperatures above Tg, and almost no change was observed at temperatures below T(g). Copyright © 2014 Elsevier Ltd. All rights reserved.

  16. A novel approach for analyzing glass-transition temperature vs. composition patterns: application to pharmaceutical compound+polymer systems.

    PubMed

    Kalogeras, Ioannis M

    2011-04-18

    In medicine, polymer-based materials are commonly used as excipients of poorly water-soluble drugs. The success of the encapsulation, as well as the physicochemical stability of the products, is often reflected on their glass transition temperature (T(g)) vs. composition (w) dependencies. The shape of the T(g)(w) patterns is critically influenced by polymer's molecular mass, drug molecule's shape and molecular volume, the type and degree of shielding of hydrogen-bonding capable functional groups, as well as aspects of the preparation process. By altering mixture's T(g) the amorphous solid form of the active ingredient may be retained at ambient or body temperatures, with concomitant improvements in handling, solubility, dissolution rate and oral bioavailability. Given the importance of the problem, the glass transitions observed in pharmaceutical mixtures have been extensively analyzed, aiming to appraise the state of mixing and intermolecular interactions. Here, accumulated experimental information on related systems is re-evaluated and comparably discussed under the light of a more effective and system-inclusive T(g)(w) equation. The present analysis indicates that free volume modifications and conformational changes of the macromolecular chains dominate, over enthalpic effects of mixing, in determining thermal characteristics and crystallization inhibition/retardation. Moreover, hydrogen-bonding and ion-dipole heterocontacts--although favorable of a higher degree of mixing--appear less significant compared to the steric hindrances and the antiplasticization proffered by the higher viscosity component. Copyright © 2011 Elsevier B.V. All rights reserved.

  17. Effect of carbon nanotube dispersion on glass transition in cross-linked epoxy-carbon nanotube nanocomposites: role of interfacial interactions.

    PubMed

    Khare, Ketan S; Khare, Rajesh

    2013-06-20

    We have used atomistic molecular simulations to study the effect of nanofiller dispersion on the glass transition behavior of cross-linked epoxy-carbon nanotube (CNT) nanocomposites. Specific chemical interactions at the interface of CNTs and cross-linked epoxy create an interphase region, whose impact on the properties of their nanocomposites increases with an increasing extent of dispersion. To investigate this aspect, we have compared the volumetric, structural, and dynamical properties of three systems: neat cross-linked epoxy, cross-linked epoxy nanocomposite containing dispersed CNTs, and cross-linked epoxy nanocomposite containing aggregated CNTs. We find that the nanocomposite containing dispersed CNTs shows a depression in the glass transition temperature (Tg) by ~66 K as compared to the neat cross-linked epoxy, whereas such a large depression is absent in the nanocomposite containing aggregated CNTs. Our results suggest that the poor interfacial interactions between the CNTs and the cross-linked epoxy matrix lead to a more compressible interphase region between the CNTs and the bulk matrix. An analysis of the resulting dynamic heterogeneity shows that the probability of percolation of immobile domains becomes unity near the Tg calculated from volumetric properties. Our observations also lend support to the conceptual analogy between polymer nanocomposites and the nanoconfinement of polymer thin films.

  18. High-Temperature Thermal Diffusivity Measurements of Silicate Glasses

    NASA Astrophysics Data System (ADS)

    Pertermann, M.; Hofmeister, A. M.; Whittington, A. G.; Spera, F. J.; Zayac, J.

    2005-12-01

    Transport of heat in geologically relevant materials is of great interest because of its key role in heat transport, magmatism and volcanic activity on Earth. To better understand the thermal properties of magmatic materials at high temperatures, we measured the thermal diffusivity of four synthetic end-member silicate glasses with the following compositions: albite (NaAlSi3O8), orthoclase (KAlSi3O8), anorthite (CaAl2Si2O8), and diopside (CaMgSi2O6). Thermal diffusivity measurements were conducted with the laser-flash technique and data were acquired from room temperature to a maximum temperature near 1100°C, depending on the glass transition temperature. The presence of sub-mm sized bubbles in one of the orthoclase samples had no discernable effect on measured diffusivities. At room temperature, the three feldspar-type glasses have thermal diffusivity (D) values of 0.58-0.61 mm2/s, whereas the diopside glass has 0.52 mm2/s. With increasing temperature, D decreases by 5-10% (relative) for all samples and becomes virtually constant at intermediate temperatures. At higher temperatures, the anorthite and diopside glasses exhibit significant drops in thermal diffusivity over a 50-100°C interval, correlating with previously published heat capacity changes near the glass transition for these compositions. For anorthite, D (in mm2/s) decreases from 0.48 at 750-860°C to 0.36 at 975-1075°C; for diopside, D changes from 0.42 at 630-750°C to 0.30 at 850-910°C, corresponding to relative drops of 24 and 29%, respectively. Albite and orthoclase glasses do not exhibit this change and also lack significant changes in heat capacity near the glass transition. Instead, D is constant at 400-800°C for albite, and for orthoclase values go through a minimum at 500-600°C before increasing slightly towards 1100°C but it never exceeds the room temperature D. Our data on thermal diffusivity correlate closely with other thermophysical properties. Thus, at least in case of simple

  19. Protein Internal Dynamics Associated With Pre-System Glass Transition Temperature Endothermic Events: Investigation of Insulin and Human Growth Hormone by Solid State Hydrogen/Deuterium Exchange.

    PubMed

    Fang, Rui; Grobelny, Pawel J; Bogner, Robin H; Pikal, Michael J

    2016-11-01

    Lyophilized proteins are generally stored below their glass transition temperature (T g ) to maintain long-term stability. Some proteins in the (pure) solid state showed a distinct endotherm at a temperature well below the glass transition, designated as a pre-T g endotherm. The pre-T g endothermic event has been linked with a transition in protein internal mobility. The aim of this study was to investigate the internal dynamics of 2 proteins, insulin and human growth hormone (hGH), both of which exhibit the pre-T g endothermic event with onsets at 50°C-60°C. Solid state hydrogen/deuterium (H/D) exchange of both proteins was characterized by Fourier transform infrared spectroscopy over a temperature range from 30°C to 80°C. A distinct sigmoidal transition in the extent of H/D exchange had a midpoint of 56.1 ± 1.2°C for insulin and 61.7 ± 0.9°C for hGH, suggesting a transition to greater mobility in the protein molecules at these temperatures. The data support the hypothesis that the pre-T g event is related to a transition in internal protein mobility associated with the protein dynamical temperature. Exceeding the protein dynamical temperature is expected to activate protein internal motion and therefore may have stability consequences. Copyright © 2016 American Pharmacists Association®. Published by Elsevier Inc. All rights reserved.

  20. Investigating the atomic level influencing factors of glass forming ability in NiAl and CuZr metallic glasses

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

    Sedighi, Sina; Kirk, Donald Walter; Singh, Chandra Veer, E-mail: chandraveer.singh@utoronto.ca

    2015-09-21

    Bulk metallic glasses are a relatively new class of amorphous metal alloy which possess unique mechanical and magnetic properties. The specific concentrations and combinations of alloy elements needed to prevent crystallization during melt quenching remains poorly understood. A correlation between atomic properties that can explain some of the previously identified glass forming ability (GFA) anomalies of the NiAl and CuZr systems has been identified, with these findings likely extensible to other transition metal–transition metal and transition metal–metalloid (TM–M) alloy classes as a whole. In this work, molecular dynamics simulation methods are utilized to study thermodynamic, kinetic, and structural properties ofmore » equiatomic CuZr and NiAl metallic glasses in an attempt to further understand the underlying connections between glass forming ability, nature of atomic level bonding, short and medium range ordering, and the evolution of structure and relaxation properties in the disordered phase. The anomalous breakdown of the fragility parameter as a useful GFA indicator in TM–M alloy systems is addressed through an in-depth investigation of bulk stiffness properties and the evolution of (pseudo)Gruneisen parameters over the quench domain, with the efficacy of other common glass forming ability indicators similarly being analyzed through direct computation in respective CuZr and NiAl systems. Comparison of fractional liquid-crystal density differences in the two systems revealed 2-3 times higher values for the NiAl system, providing further support for its efficacy as a general purpose GFA indicator.« less

  1. Thermodynamic sorption analysis and glass transition temperature of faba bean (Vicia faba L.) protein.

    PubMed

    Alpizar-Reyes, E; Castaño, J; Carrillo-Navas, H; Alvarez-Ramírez, J; Gallardo-Rivera, R; Pérez-Alonso, C; Guadarrama-Lezama, A Y

    2018-03-01

    Freeze-dried faba bean ( Vicia faba L.) protein adsorption isotherms were determined at 25, 35 and 40 °C and fitted with the Guggenheim-Anderson-de Boer model. The pore radius of protein was in the range of 0.87-6.44 nm, so that they were considered as micropores and mesopores. The minimum integral entropy ranged between 4.33 and 4.44 kg H 2 O/100 kg d.s., was regarded as the point of maximum of stability. The glass transition temperature of the protein equilibrated at the different conditions of storage was determined, showing that the protein remained in glassy state for all cases. The protein showed compact and rigid structures, evidenced by microscopy analysis.

  2. UV light induced red emission in Eu3+-doped zincborophosphate glasses

    NASA Astrophysics Data System (ADS)

    Hima Bindu, S.; Siva Raju, D.; Vinay Krishna, V.; Rajavardhana Rao, T.; Veerabrahmam, K.; Linga Raju, Ch.

    2016-12-01

    This paper reports the preparation of transparent zincborophosphate (ZBP) glasses doped with Eu3+ ions by the conventional melt quenching technique. The prepared glasses were characterized using powder XRD, FTIR, optical absorption, photoluminescence and decay curves. Judd-Ofelt (JO) intensity parameters calculated under various constraints using absorption and emission spectra. These JO intensity parameters have been used to predict the radiative properties such as radiative life time, branching ratios and stimulated emission cross section of the 5D0→7FJ (J = 0-4) transitions. Decay curves for the 5D0 level of Eu3+ ions shows single exponential for all concentrations. Luminescence properties of 5D0→7F2 transitions of Eu3+ions have revealed that the present ZBP:Eu3+ glasses have significant in optical applications at around 613 nm. An intense red luminescence has been observed due to 5D0→7F2 transition of Eu3+ ion in these glasses. From the CIE color coordinate diagram, it is observed that the present glass system is prominent material for red emission.

  3. Generalized localization model of relaxation in glass-forming liquids

    PubMed Central

    Cicerone, Marcus T.; Zhong, Qin; Tyagi, Madhusudan

    2012-01-01

    Glassy solidification is characterized by two essential phenomena: localization of the solidifying material’s constituent particles and a precipitous increase in its structural relaxation time τ. Determining how these two phenomena relate is key to understanding glass formation. Leporini and coworkers have recently argued that τ universally depends on a localization length-scale (the Debye-Waller factor) in a way that depends only upon the value of at the glass transition. Here we find that this ‘universal’ model does not accurately describe τ in several simulated and experimental glass-forming materials. We develop a new localization model of solidification, building upon the classical Hall-Wolynes and free volume models of glass formation, that accurately relates τ to in all systems considered. This new relationship is based on a consideration of the the anisotropic nature of particle localization. The model also indicates the presence of a particle delocalization transition at high temperatures associated with the onset of glass formation. PMID:23393495

  4. Investigation of luminescence and laser transition of Dy3+ ion in P2O5sbnd PbOsbnd Bi2O3sbnd R2O3 (R = Al, Ga, In) glasses

    NASA Astrophysics Data System (ADS)

    Ram, G. Chinna; Narendrudu, T.; Suresh, S.; Kumar, A. Suneel; Rao, M. V. Sambasiva; Kumar, V. Ravi; Rao, D. Krishna

    2017-04-01

    P2O5sbnd PbOsbnd Bi2O3sbnd R2O3 (R = Al, Ga, In) glasses doped with Dy2O3 were prepared by melt quenching technique. The prepared glasses were characterized by XRD, optical absorption, FTIR, luminescence studies. Judd-Ofelt parameters have been evaluated for three glass systems from optical absorption spectra and in turn radiative parameters for excited luminescent levels of Dy3+ ion are also calculated. Emission cross section and branching ratio values are observed to high for 6H13/2 level for Dy3+ ion. The yellow to blue intensity ratios and CIE chromaticity coordinates were calculated. Decay curves exhibit non exponential behavior. Quantum efficiency of prepared glasses was measured by using radiative and calculated life times. IR studies, J-O parameters and Y/B ratio values indicate that more asymmetry around Dy3+ ions in Ga2O3 mixed glass was observed. Chromaticity coordinates lie near ideal white light region. These coordinates and CCT values have revealed that all the prepared glasses emit quality white light especially the glasses mixed with Ga2O3 are suitable for development of white LEDs.

  5. Coffee-rings and glasses: Colloids out of equilibrium

    NASA Astrophysics Data System (ADS)

    Yunker, Peter Joseph

    This thesis describes experiments that utilize colloids to explore nonequilibrium phenomena. Specifically, the deposition of particles during evaporation and the glass transition are explored. In the first set of experiments, we found that particle shape has a profound effect on particle deposition. We evaporated drops of colloidal suspensions containing micron-sized particles that range in shape from isotropic spheres to very anisotropic ellipsoids. For sessile drops, i.e., drops sitting on a solid surface, spheres are deposited in a ring-like stain, while ellipsoids are deposited uniformly. We also confined drops between glass plates and allowed them to evaporate. During evaporation, colloidal particles coat the air-water interface, forming colloidal monolayer membranes (CMMs). As particle anisotropy increases, CMM bending rigidity was found to increase. This increase in bending rigidity provides a new mechanism that produces a uniform deposition of ellipsoids and a heterogeneous deposition of spheres. In the second set of experiments, we employed colloidal suspensions to investigate the character of glassy materials. "Anisotropic glasses'' were investigated with ellipsoidal particles confined to two-dimensional chambers at high packing fractions; this system enabled the study of the effects of particle shape on the vibrational properties of colloidal glasses. Low frequency modes in glasses composed of slightly anisotropic particles are found to have predominantly rotational character. Conversely, low frequency modes in glasses of highly anisotropic particles exhibit a mix of rotational and translational character. Aging effects in glasses were explored using suspensions of temperature-sensitive microgel spheres. We devised a method to rapidly quench from liquid to glass states, and then observed the resultant colloidal glasses as they aged. Particle rearrangements in glasses occur collectively, i.e., many particles move in a correlated manner. During aging, we

  6. Reversibility between glass and melting transitions of poly(oxyethylene)

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

    Qui, Wulin; Pyda, Marek; Nowak-Pyda, Elisabieta

    2005-01-01

    The heat capacities, C{sub p}, of poly(oxyethylene), POE, with molar masses from 1500 to 900,000 Da, were analyzed by differential scanning calorimetry (DSC), quasi-isothermal, temperature-modulated DSC (TMDSC), and wide-angle X-ray diffraction (WAXD). There is no change in crystal structure before melting, but the lattice parameters increase rapidly in the melting region. Perfected extended-chain and once- or twice-folded crystals of the oligomers with a molar mass above 1100 Da melt practically fully irreversibly and permit direct measurement of the thermodynamic C{sub p}. The folded-chain crystals of high molar mass show some locally reversible melting. The reversing, apparent C{sub p} depends onmore » molar mass and amplitude and frequency of modulation. After separation from the latent heat effects, the reversible, thermodynamic C{sub p} depends on the melting temperature for low molar masses and increases beyond the vibrational C{sub p} due to conformational motion. Molar masses of 8000-20,000 have almost the same C{sub p}. These observations permit a quantitative discussion of the thermodynamic C{sub p} and the locally reversible melting of the globally metastable POE in the melting range. The increase in C{sub p} between 250 K and the melting temperature is interpreted as a glass transition within the crystal.« less

  7. Unique sodium phosphosilicate glasses designed through extended topological constraint theory.

    PubMed

    Zeng, Huidan; Jiang, Qi; Liu, Zhao; Li, Xiang; Ren, Jing; Chen, Guorong; Liu, Fude; Peng, Shou

    2014-05-15

    Sodium phosphosilicate glasses exhibit unique properties with mixed network formers, and have various potential applications. However, proper understanding on the network structures and property-oriented methodology based on compositional changes are lacking. In this study, we have developed an extended topological constraint theory and applied it successfully to analyze the composition dependence of glass transition temperature (Tg) and hardness of sodium phosphosilicate glasses. It was found that the hardness and Tg of glasses do not always increase with the content of SiO2, and there exist maximum hardness and Tg at a certain content of SiO2. In particular, a unique glass (20Na2O-17SiO2-63P2O5) exhibits a low glass transition temperature (589 K) but still has relatively high hardness (4.42 GPa) mainly due to the high fraction of highly coordinated network former Si((6)). Because of its convenient forming and manufacturing, such kind of phosphosilicate glasses has a lot of valuable applications in optical fibers, optical amplifiers, biomaterials, and fuel cells. Also, such methodology can be applied to other types of phosphosilicate glasses with similar structures.

  8. Revealing the Link between Structural Relaxation and Dynamic Heterogeneity in Glass-Forming Liquids

    NASA Astrophysics Data System (ADS)

    Wang, Lijin; Xu, Ning; Wang, W. H.; Guan, Pengfei

    2018-03-01

    Despite the use of glasses for thousands of years, the nature of the glass transition is still mysterious. On approaching the glass transition, the growth of dynamic heterogeneity has long been thought to play a key role in explaining the abrupt slowdown of structural relaxation. However, it still remains elusive whether there is an underlying link between structural relaxation and dynamic heterogeneity. Here, we unravel the link by introducing a characteristic time scale hiding behind an identical dynamic heterogeneity for various model glass-forming liquids. We find that the time scale corresponds to the kinetic fragility of liquids. Moreover, it leads to scaling collapse of both the structural relaxation time and dynamic heterogeneity for all liquids studied, together with a characteristic temperature associated with the same dynamic heterogeneity. Our findings imply that studying the glass transition from the viewpoint of dynamic heterogeneity is more informative than expected.

  9. Glass transition temperature of polymer nano-composites with polymer and filler interactions

    NASA Astrophysics Data System (ADS)

    Hagita, Katsumi; Takano, Hiroshi; Doi, Masao; Morita, Hiroshi

    2012-02-01

    We systematically studied versatile coarse-grained model (bead spring model) to describe filled polymer nano-composites for coarse-grained (Kremer-Grest model) molecular dynamics simulations. This model consists of long polymers, crosslink, and fillers. We used the hollow structure as the filler to describe rigid spherical fillers with small computing costs. Our filler model consists of surface particles of icosahedra fullerene structure C320 and a repulsive force from the center of the filler is applied to the surface particles in order to make a sphere and rigid. The filler's diameter is 12 times of beads of the polymers. As the first test of our model, we study temperature dependence of volumes of periodic boundary conditions under constant pressures through NPT constant Andersen algorithm. It is found that Glass transition temperature (Tg) decrease with increasing filler's volume fraction for the case of repulsive interaction between polymer and fillers and Tg weakly increase for attractive interaction.

  10. GLASS TRANSITION AND DEGREE OF CONVERSION OF A LIGHT-CURED ORTHODONTIC COMPOSITE

    PubMed Central

    Sostena, Michela M. D. S.; Nogueira, Renata A.; Grandini, Carlos R.; Moraes, João Carlos Silos

    2009-01-01

    Objective: This study evaluated the glass transition temperature (Tg) and degree of conversion (DC) of a light-cured (Fill Magic) versus a chemically cured (Concise) orthodontic composite. Material and Methods: Anelastic relaxation spectroscopy was used for the first time to determine the Tg of a dental composite, while the DC was evaluated by infrared spectroscopy. The light-cured composite specimens were irradiated with a commercial LED light-curing unit using different exposure times (40, 90 and 120 s). Results: Fill Magic presented lower Tg than Concise (35-84°C versus 135°C), but reached a higher DC. Conclusions: The results of this study suggest that Fill Magic has lower Tg than Concise due to its higher organic phase content, and that when this light-cured composite is used to bond orthodontic brackets, a minimum energy density of 7.8 J/cm2 is necessary to reach adequate conversion level and obtain satisfactory adhesion. PMID:20027428

  11. Impact of the glass transition on exciton dynamics in polymer thin films

    NASA Astrophysics Data System (ADS)

    Ehrenreich, Philipp; Proepper, Daniel; Graf, Alexander; Jores, Stefan; Boris, Alexander V.; Schmidt-Mende, Lukas

    2017-11-01

    In the development of organic electronics, unlimited design possibilities of conjugated polymers offer a wide variety of mechanical and electronic properties. Thereby, it is crucially important to reveal universal physical characteristics that allow efficient and forward developments of new chemical compounds. In particular for organic solar cells, a deeper understanding of exciton dynamics in polymer films can help to improve the charge generation process further. For this purpose, poly(3-hexylthiophene) (P3HT) is commonly used as a model system, although exciton decay kinetics have found different interpretations. Using temperature-dependent time-resolved photoluminescence spectroscopy in combination with low-temperature spectroscopic ellipsometry, we can show that P3HT is indeed a model system in which excitons follow a simple diffusion/hopping model. Based on our results we can exclude the relevance of hot-exciton emission as well as a dynamic torsional relaxation upon photoexcitation on a ps time scale. Instead, we depict the glass transition temperature of polymers to strongly affect exciton dynamics.

  12. MgCu metallic glass

    NASA Astrophysics Data System (ADS)

    Durandurdu, Murat

    2018-03-01

    We generate an amorphous MgCu model using the rapid solidification of the melt through a first-principles molecular dynamics approach within a generalised gradient approximation and reveal, for the first time, its structural features and mechanical properties in details. The liquid and glassy MgCu are found to acquire slightly distinct local structures. Yet in both forms of MgCu, most Cu atoms have a tendency to form the ideal and defective icosahedrons while Mg atoms are arranged in complex configurations. The mean coordination number of Cu and Mg at 300 K is 11.31 and 13.73, respectively. The short-range order of MgCu glass is projected to be different than the known crystalline MgCu and Mg2Cu phases. The mechanical properties of MgCu glass and the CsCl-type MgCu crystal are computed and compared. On the basis of the enthalpy analyses, a possible pressure-induced crystallisation of the MgCu glass into a CsCl-type structure is proposed to occur at around 11 GPa.

  13. Moisture sorption isotherms and glass transition temperature of elecampe (Inula helenium L.) and burdock (Arctium lappa L.) roots at 25°C.

    PubMed

    Cervenka, L; Kubínová, J; Juszczak, L; Witczak, M

    2012-02-01

    Sorption isotherms of elecampe (Inula helenium L.) and burdock (Arctium lappa L.) root samples were obtained at 25 °C. Elecampe exhibited hysteresis loop in the range of 0.35-0.90 a(w) , whereas burdock roots showed significant differences between adsorption and desorption isotherms from 0.65 to 0.80 a(w) . Blahovec-Yanniotis was considered to give the best fit over the whole range of a(w) tested. Various parameters describing the properties of sorbed water derived from GAB, Henderson and Blahovec-Yanniotis models have been discussed. Differential scanning calorimetric method was used to measure the glass transition temperature (T (g)) of root samples in relation to water activity. The safe moisture content was determined in 12.01 and 14.96 g/100 g d. b. for burdock and elecampe root samples at 25 °C, respectively. Combining the T (g) line with sorption isotherm in one plot, it was found that the glass transition temperature concept overestimated the temperature stability for both root samples.

  14. Antimony oxide based glasses, novel laser materials

    NASA Astrophysics Data System (ADS)

    Ouannes, Karima; Lebbou, Kheirreddine; Walsh, Brian M.; Poulain, Marcel; Alombert-Goget, Guillaume; Guyot, Yannick

    2017-03-01

    Glasses based on Sb2O3 make one of the major classes of heavy metal oxide glasses. This paper concerns two antimonite glasses, 88Sb2O3-10Na2O-2Bi2O3 (SNB2) and 60Sb2O3-20WO3-19Na2O-1Bi2O3 (SWNB1), doped with 0.25 mol% Er2O3. Bulk samples have been prepared and their absorption and fluorescence spectra have been recorded. Differential scanning calorimeter (DSC) measurements emphasize a thermal stability range ΔT > 100 °C that expresses a good stability against devitrification. Both FTIR and Raman spectra provide information on the structural organization of the glasses. The maximum phonon energies are 700 cm-1 and 920 cm-1 for SNB2 and SWNB1 glasses, respectively. The spectroscopic analysis of the absorption and emission properties of the Er3+ ions in the SNB2 and SWNB1 glasses has been performed. The Judd-Ofelt theory has been applied to interpret the local environment of the Er3+ ion site and covalency of the Ersbnd O bond, but also to determine the radiative lifetime (τr) for 4I13/2 → 4I15/2 emission transition. The emission cross-sections for the 4I13/2 → 4I15/2 transition (1528 nm) were calculated using McCumber and Füchtbauer-Ladenburg theories. We discuss the potential application of these glasses.

  15. Spin-glass polyamorphism induced by a magnetic field in LaMnO3 single crystal

    NASA Astrophysics Data System (ADS)

    Eremenko, V. V.; Sirenko, V. A.; Baran, A.; Čižmár, E.; Feher, A.

    2018-05-01

    We present experimental evidence of field-driven transition in spin-glass state, similar to pressure-induced transition between amorphous phases in structural and metallic glasses, attributed to the polyamorphism phenomena. Cusp in temperature dependences of ac magnetic susceptibility of weakly disordered LaMnO3 single crystal is registered below the temperature of magnetic ordering. Frequency dependence of the cusp temperature proves its spin-glass origin. The transition induced by a magnetic field in spin-glass state, is manifested by peculiarity in dependence of cusp temperature on applied magnetic field. Field dependent maximum of heat capacity is observed in the same magnetic field and temperature range.

  16. Sealing glass ampoules with CO2 lasers.

    PubMed

    Jiao, Junke; Wang, Xinbing; Tang, Wenlong

    2008-12-10

    Glass ampoules were always sealed by melting in the presence of a flame to create closures. Some poisonous gases were generated in this sealing process that pollute the injection drug and are physically harmful. In this study, CO(2) lasers were proposed for sealing glass ampoules. Because of the clean noncontact sealing process with lasers, there was nearly no pollution of the injection drug. To study in detail the principle of this sealing process, a mathematical model was put forward, and the temperature and the thermal stress field around the ampoule's neck were calculated by ANSYS software. Through experimental study, 1 ml and 5 ml ampoules were sealed successfully by a dual-laser-beam method. The results show that a laser source is an ideal heat source for sealing glass ampoules.

  17. Traction and lubricant film temperature as related to the glass transition temperature and solidification. [using infrared spectroscopy on EHD contacts

    NASA Technical Reports Server (NTRS)

    Lauer, J. L.; Peterkin, M. E.

    1978-01-01

    Does a traction fluid have to be a glass or solid under operating conditions. Infrared spectra on dynamic EHD contacts of several types of fluid were used to determine the surface and oil-film temperatures. Polarized spectral runs were made to study molecular alignment. Static glass transition pressures at appropriate temperatures were between 0.1 and 2.0 GPa, with the traction fluid showing the highest. In the EHD contact region, the traction fluid showed both the highest film temperatures as well as the greatest degree of molecular alignment. A plot of the difference between the film and surface temperatures vs shear rate resulted in a master plot valid for all the fluids. From this work, the authors propose a model of 'fluid' traction, where friction between parallel rough molecules provides the traction.

  18. Effect of tacticity on the structure and glass transition temperature of polystyrene adsorbed onto solid surfaces

    NASA Astrophysics Data System (ADS)

    Negash, Solomon; Tatek, Yergou B.; Tsige, Mesfin

    2018-04-01

    We have carried out atomistic (all-atom) molecular dynamics simulations to investigate the effect of tacticity on the structure and glass transition temperature (Tg) of polystyrene (PS) thin films adsorbed on two distinct types of solid substrates. The systems consist of thin films made of atactic, isotactic, and syndiotactic PS chains supported by graphite or hydroxylated α-quartz substrates, which are known to be atomically flat but chemically and structurally different. We have observed a marked dependence of the film structure on substrate type as well as on tacticity. For instance, rings' orientation near substrate surfaces depends on substrate type for atactic PS and isotactic PS films, while no such dependence is observed for syndiotactic PS films whose interfacial structure seems to result from their propensity to adopt the trans conformation rather than their specific interaction with the substrates. Moreover, our results indicate that glass transition temperatures of substrate supported polystyrene films are higher compared to those of the corresponding free-standing films. More specifically, PS films on graphite exhibit larger Tg values than those on α-quartz, and we have noticed that syndiotactic PS has the largest Tg irrespective of the substrate type. Furthermore, the local Tg in the region of the film in contact with the substrates shows a strong tacticity and substrate dependence, whereas no dependencies were found for the local Tg in the middle of the film. Substrate-film interaction energy and chains' dynamics near substrate-film interfaces were subsequently investigated in order to substantiate the obtained Tgs, and it was found that films with higher Tgs are strongly adsorbed on the substrates and/or exhibit smaller interfacial chains' dynamics essentially due to steric hindrance.

  19. The Twinkling Fractal Theory of the Glass Transition: Applications to Soft Matter

    NASA Astrophysics Data System (ADS)

    Wool, Richard

    2012-02-01

    The Twinkling Fractal Theory (TFT) of the glass transition has recently been demonstrated experimentally [J.F. Stanzione et al., J. Non Cryst. Sol., (2011, 357,311]. The hard to-soft matter transition is characterized by the presence of solid fractal clusters with liquid-like pools that are dynamically interchanging via their anharmonic intermolecular potentials with Boltzmann energy populations with a characteristic temperature dependent vibrational density of states g(φ) ˜ φ^df . The twinkling fractal frequencies φ cover a range of 10^12 Hz to 10-10Hz and the fractal solid clusters of size R have a lifetime τ ˜ R^Df/df, where the fractal dimension Df 2.4 and the fracton dimension df = 4/3. Here we explore its application to a number of soft matter issues. These include (a) Confinement effects on Tg reduction in thin films of thickness h, where by virtue of large cluster exclusion, δTg ˜ 1/h^Df/df; (b) Tg gradients near bulk surfaces, where the smaller clusters on the surface have a faster relaxation time; (c) Effect of twinkling surfaces on cell growth, where at T Tg + 20 C, there exists a twinkling fractal range that leads to bell-shaped enhancement of cell growth and chemical up-regulation via the twinkling surfaces ``communicating `` with the cells through their vibrations; and (d) adhesion above and below Tg where topological fluctuations associated with g(φ) promotes the development of nano-nails at the interface.

  20. Orientation dynamics in isotropic phases of model oligofluorenes: glass or liquid crystal.

    PubMed

    Somma, E; Chi, C; Loppinet, B; Grinshtein, J; Graf, R; Fytas, G; Spiess, H W; Wegner, G

    2006-05-28

    Orientation molecular dynamics were investigated in a series of "defect-free" oligofluorenes by depolarized dynamic light scattering and dynamic NMR spectroscopy. Typical liquid crystalline pretransitional dynamics were observed upon cooling the isotropic phase to the liquid crystalline phase with strong increase of the scattered intensity and slowing down of the characteristic time of the probed collective relaxation. This is well accounted for by the Landau-de Gennes theory, however, with a strong temperature dependence of the viscosity coefficient, reflecting the proximity of the glass transition. For the trimer the two transitions almost overlap and the molecular orientation coincide with the alpha-relaxation associated with the glass transition. The NMR measurements confirm that the time scale of the dynamics is completely governed by the glass process, yet the geometry of the motion is anisotropic, yielding order parameters ranging from 0.15 to 0.25 for the long axis in the liquid crystalline phase. The glass transition is therefore geometrically restricted with poorly ordered mesophase which is consistent with the weak transverse phonons in the light scattering experiment down to Tg+20 K.

  1. A characteristic energy scale in glasses

    NASA Astrophysics Data System (ADS)

    Lerner, Edan; Bouchbinder, Eran

    2018-06-01

    Intrinsically generated structural disorder endows glassy materials with a broad distribution of various microscopic quantities—such as relaxation times and activation energies—without an obvious characteristic scale. At the same time, macroscopic glassy responses—such as Newtonian (linear) viscosity and nonlinear plastic deformation—are widely interpreted in terms of a characteristic energy scale, e.g., an effective temperature-dependent activation energy in Arrhenius relations. Nevertheless, despite its fundamental importance, such a characteristic energy scale has not been robustly identified. Inspired by the accumulated evidence regarding the crucial role played by disorder- and frustration-induced soft quasilocalized excitations in determining the properties and dynamics of glasses, we propose that the bulk average of the glass response to a localized force dipole defines such a characteristic energy scale. We show that this characteristic glassy energy scale features remarkable properties: (i) It increases dramatically in underlying inherent structures of equilibrium supercooled states approaching the glass transition temperature Tg, significantly surpassing the corresponding increase in the macroscopic shear modulus, dismissing the common view that structural variations in supercooled liquids upon vitrification are minute. (ii) Its variation with annealing and system size is very similar in magnitude and form to that of the energy of the softest non-phononic vibrational mode, thus establishing a nontrivial relation between a rare glassy fluctuation and a bulk average response. (iii) It exhibits striking dependence on spatial dimensionality and system size due to the long-ranged fields associated with quasilocalization, which are speculated to be related to peculiarities of the glass transition in two dimensions. In addition, we identify a truly static growing lengthscale associated with the characteristic glassy energy scale and discuss possible

  2. A characteristic energy scale in glasses.

    PubMed

    Lerner, Edan; Bouchbinder, Eran

    2018-06-07

    Intrinsically generated structural disorder endows glassy materials with a broad distribution of various microscopic quantities-such as relaxation times and activation energies-without an obvious characteristic scale. At the same time, macroscopic glassy responses-such as Newtonian (linear) viscosity and nonlinear plastic deformation-are widely interpreted in terms of a characteristic energy scale, e.g., an effective temperature-dependent activation energy in Arrhenius relations. Nevertheless, despite its fundamental importance, such a characteristic energy scale has not been robustly identified. Inspired by the accumulated evidence regarding the crucial role played by disorder- and frustration-induced soft quasilocalized excitations in determining the properties and dynamics of glasses, we propose that the bulk average of the glass response to a localized force dipole defines such a characteristic energy scale. We show that this characteristic glassy energy scale features remarkable properties: (i) It increases dramatically in underlying inherent structures of equilibrium supercooled states approaching the glass transition temperature T g , significantly surpassing the corresponding increase in the macroscopic shear modulus, dismissing the common view that structural variations in supercooled liquids upon vitrification are minute. (ii) Its variation with annealing and system size is very similar in magnitude and form to that of the energy of the softest non-phononic vibrational mode, thus establishing a nontrivial relation between a rare glassy fluctuation and a bulk average response. (iii) It exhibits striking dependence on spatial dimensionality and system size due to the long-ranged fields associated with quasilocalization, which are speculated to be related to peculiarities of the glass transition in two dimensions. In addition, we identify a truly static growing lengthscale associated with the characteristic glassy energy scale and discuss possible

  3. A Comparative Cathodoluminescence Emission Study of Feldspathic Glasses in SNC Meteorites and Quenched Melts of These Glasses

    NASA Astrophysics Data System (ADS)

    Kubny, A.; Jagoutz, E.

    2001-12-01

    In this study the cathodoluminescence (electron-excited luminescence) emission spectra were measured in the range 200 to 900 nm of individual feldspathic glass grains in the SNC meteorites Shergotty 101, Shergotty 232, ALHA 84001, EETA 79001-47, EETA 79001-276, and Dar al Gani 476 and those of quenched melts of the feldspathic glass grains. The quenching experiments of the original feldspathic glasses were conducted at 1500° C and atmospheric pressure. The aim of this CL emission study was the characterization of feldspathic glasses of SNC meteorites by comparison of the diagnostic spectral features of the feldspathic glasses of SNC meteorites with those of their quenched melts. In the CL emission spectra of the studied feldspathic glasses generally broad bands in the blue (ca. 460 nm), green (ca. 560 nm), and red (ca. 700 nm) can appear. These emission bands are assigned to structural defects (Al-O--Al centers), and the structural incorporation of Mn2+ and Fe3+ , respectively. The blue emission band at about 460 nm attributed to Al-O--Al centers is observed in the spectra of the original feldspathic glasses whereas it is not present (or only in low relative intensity) in the spectra of the quenched melts. The green emission band at 550 to 575 nm assigned to electronic transitions of Mn2+ in M sites is observed in the spectra of the original feldspathic glasses. It is shifted to longer wavelengths of 590 to 605 nm in the spectra of the quenched melts. The occurrence of the red emission band at about 700 nm attributed to electronic transition of Fe3+ in the spectra of the quenched melts of the feldspathic glasses indicates the presence of structural units which allow the occupancy of Fe3+ on tetrahedral sites. The results obtained by CL emission spectroscopy confirm results of Raman spectroscopic studies that the stuctures of feldspathic glasses of the studied SNC meteorites are modified by melting and quenching at atmospheric pressure. Additionally, comparison

  4. Effect of Loading Rates and Surface Conditions on the Flexural Strength of Borosilicate Glass

    DTIC Science & Technology

    2009-01-01

    strength of etched soda - lime glass rods.32 According to this model, an idealized surface crack is uniformly attacked by acid at every point so that this...R. Lin, ‘‘Effect of Polymer Coatings on the Strength and Fatigue Behavior of Indented Soda - Lime Glass ,’’ Glass Technol., 32 [2] 51–4 (1991). 10J. J...Scott Glaesemann, K. Jakus, and J. E. Ritter Jr., ‘‘Strength Variability of Indented Soda - Lime Glass ,’’ J. Am. Ceram. Soc., 70 [6] 441–4 (1987). 12C

  5. Layered chalcogenide glass structures for IR lenses

    NASA Astrophysics Data System (ADS)

    Gibson, Daniel; Bayya, Shyam; Sanghera, Jas; Nguyen, Vinh; Scribner, Dean; Maksimovic, Velimir; Gill, John; Yi, Allen; Deegan, John; Unger, Blair

    2014-07-01

    A technique for fabricating novel infrared (IR) lenses can enable a reduction in the size and weight of IR imaging optics through the use of layered glass structures. These structures can range from having a few thick glass layers, mimicking cemented doublets and triplets, to having many thin glass layers approximating graded index (GRIN) lenses. The effectiveness of these structures relies on having materials with diversity in refractive index (large Δn) and dispersion and similar thermo-viscous behavior (common glass transition temperature, ΔTg = 10°C). A library of 13 chalcogenide glasses with broad IR transmission (NIR through LWIR bands) was developed to satisfy these criteria. The lens fabrication methodology, including glass design and synthesis, sheet fabrication, preform making, lens molding and surface finishing are presented.

  6. Engineered glass seals for solid-oxide fuel cells

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

    Surdoval, Wayne; Lara-Curzio, Edgar; Stevenson, Jeffry

    2017-02-07

    A seal for a solid oxide fuel cell includes a glass matrix having glass percolation therethrough and having a glass transition temperature below 650.degree. C. A deformable second phase material is dispersed in the glass matrix. The second phase material can be a compliant material. The second phase material can be a crushable material. A solid oxide fuel cell, a precursor for forming a seal for a solid oxide fuel cell, and a method of making a seal for a solid oxide fuel cell are also disclosed.

  7. Two Glass Transitions Associated to Different Dynamic Disorders in the Nematic Glassy State of a Non-Symmetric Liquid Crystal Dimer Dopped with γ-Alumina Nanoparticles

    PubMed Central

    Diez-Berart, Sergio; López, David O.; Salud, Josep; Diego, José Antonio; Sellarès, Jordi; Robles-Hernández, Beatriz; de la Fuente, María Rosario; Ros, María Blanca

    2015-01-01

    In the present work, the nematic glassy state of the non-symmetric LC dimer α-(4-cyanobiphenyl-4′-yloxy)-ω-(1-pyrenimine-benzylidene-4′-oxy) undecane is studied by means of calorimetric and dielectric measurements. The most striking result of the work is the presence of two different glass transition temperatures: one due to the freezing of the flip-flop motions of the bulkier unit of the dimer and the other, at a lower temperature, related to the freezing of the flip-flop and precessional motions of the cyanobiphenyl unit. This result shows the fact that glass transition is the consequence of the freezing of one or more coupled dynamic disorders and not of the disordered phase itself. In order to avoid crystallization when the bulk sample is cooled down, the LC dimer has been confined via the dispersion of γ-alumina nanoparticles, in several concentrations.

  8. Reorientational dynamics in molecular liquids as revealed by dynamic light scattering: from boiling point to glass transition temperature.

    PubMed

    Schmidtke, B; Petzold, N; Kahlau, R; Rössler, E A

    2013-08-28

    We determine the reorientational correlation time τ of a series of molecular liquids by performing depolarized light scattering experiments (double monochromator, Fabry-Perot interferometry, and photon correlation spectroscopy). Correlation times in the range 10(-12) s-100 s are compiled, i.e., the full temperature interval between the boiling point and the glass transition temperature T(g) is covered. We focus on low-T(g) liquids for which the high-temperature limit τ ≅ 10(-12) s is easily accessed by standard spectroscopic equipment (up to 440 K). Regarding the temperature dependence three interpolation formulae of τ(T) with three parameters each are tested: (i) Vogel-Fulcher-Tammann equation, (ii) the approach recently discussed by Mauro et al. [Proc. Natl. Acad. Sci. U.S.A. 106, 19780 (2009)], and (iii) our approach decomposing the activation energy E(T) in a constant high temperature value E∞ and a "cooperative part" E(coop)(T) depending exponentially on temperature [Schmidtke et al., Phys. Rev. E 86, 041507 (2012)]. On the basis of the present data, approaches (i) and (ii) are insufficient as they do not provide the correct crossover to the high-temperature Arrhenius law clearly identified in the experimental data while approach (iii) reproduces the salient features of τ(T). It allows to discuss the temperature dependence of the liquid's dynamics in terms of a E(coop)(T)/E∞ vs. T/E∞ plot and suggests that E∞ controls the energy scale of the glass transition phenomenon.

  9. From boiling point to glass transition temperature: transport coefficients in molecular liquids follow three-parameter scaling.

    PubMed

    Schmidtke, B; Petzold, N; Kahlau, R; Hofmann, M; Rössler, E A

    2012-10-01

    The phenomenon of the glass transition is an unresolved problem in condensed matter physics. Its prominent feature, the super-Arrhenius temperature dependence of the transport coefficients, remains a challenge to be described over the full temperature range. For a series of molecular glass formers, we combined τ(T) collected from dielectric spectroscopy and dynamic light scattering covering a range 10(-12) s < τ(T) < 10(2) s. Describing the dynamics in terms of an activation energy E(T), we distinguish a high-temperature regime characterized by an Arrhenius law with a constant activation energy E(∞) and a low-temperature regime for which E(coop)(T) ≡ E(T)-E(∞) increases exponentially while cooling. A scaling is introduced, specifically E(coop)(T)/E(∞) [proportionality] exp[-λ(T/T(A)-1)], where λ is a fragility parameter and T(A) a reference temperature proportional to E(∞). In order to describe τ(T) still the attempt time τ(∞) has to be specified. Thus, a single interaction parameter E(∞) describing the high-temperature regime together with λ controls the temperature dependence of low-temperature cooperative dynamics.

  10. Structural origin underlying poor glass forming ability of Al metallic glass

    NASA Astrophysics Data System (ADS)

    Li, F.; Liu, X. J.; Hou, H. Y.; Chen, G.; Chen, G. L.

    2011-07-01

    We performed molecular dynamics simulations to study the glass formation and local atomic structure of rapidly quenched Al. Both potential energy and structural parameters indicate that the glass transition temperature of amorphous Al is as low as 300 K, which may lead to the poor thermal stability of the amorphous Al as it is prone to crystallize even at room temperature. Voronoi polyhedra analysis reveals that the most popular polyhedron is the deformed body-centered cubic (bcc) cluster characterized by the index < 0, 3, 6, 4 > in the amorphous Al, while the icosahedron with the index < 0, 0, 12, 0 > is always predominant in bulk metallic glass formers with excellent glass forming ability (GFA). Moreover, these deformed-bcc short-range orders can make up medium-range orders via the linkage of vertex-, edge-, face-, intercrossed-shared atoms, which are believed to more easily transform into face-centered cubic (fcc) Al nanocrystal compared with the icosahedral clusters in terms of the symmetrical similarity between bcc and fcc structures. This finding could unveil the structural origin of poor GFA of Al-based alloys.

  11. Intense red photoluminescence from Mn2+-doped (Na+; Zn2+) sulfophosphate glasses and glass ceramics as LED converters.

    PubMed

    Da, Ning; Peng, Mingying; Krolikowski, Sebastian; Wondraczek, Lothar

    2010-02-01

    We report on intense red fluorescence from Mn(2+)-doped sulfophosphate glasses and glass ceramics of the type ZnO-Na(2)O-SO(3)-P(2)O(5). As a hypothesis, controlled internal crystallization of as-melted glasses is achieved on the basis of thermally-induced bimodal separation of an SO(3)-rich phase. Crystal formation is then confined to the relict structure of phase separation. The whole synthesis procedure is performed in air at glasses, increasing MnO content results in decreasing network polymerization. Stable glasses and continuously increasing emission intensity are observed for relatively high dopant concentration of up to 3 mol.%. Recrystallization of the glass results in strongly increasing emission intensity. Dynamic emission spectroscopy reveals only on type of emission centers in the glassy material, whereas three different centers are observed in the glass ceramic. These are attributed to octahedrally coordinated Mn(2+) in the residual glass phase and in crystalline phosphate and sulfate lattices, respectively. Relatively low crystal field strength results in almost ideal red emission, peaking around 625 nm. Excitation bands lie in the blue-to-green spectral range and exhibit strong overlap. The optimum excitation range matches the emission properties of GaN- and InGaN-based light emitting devices.

  12. Clinician roles and responsibilities during care transitions of older adults.

    PubMed

    Schoenborn, Nancy L; Arbaje, Alicia I; Eubank, Kathryn J; Maynor, Kenric; Carrese, Joseph A

    2013-02-01

    To identify the perceived roles and responsibilities of clinicians during care transitions of older adults. Qualitative study involving 1-hour in-depth semistructured interviews. Audiotapes of interviews were transcribed, coded, and analyzed, and themes and subthemes were generated. An acute care hospital, a skilled nursing facility, two community-based outpatient practices, and one home healthcare agency. Forty healthcare professionals directly involved in care transitions of older adults (18 physicians, 11 home healthcare administrative and field staff, four social workers, three nurse practitioners, three physician assistants, and one hospital case manager). Perspectives of healthcare professionals regarding clinicians' roles and responsibilities during care transitions were examined and described. Content analysis revealed several themes: components of clinicians' roles during care transitions; congruence between self- and others' perceived ideal roles but incongruence between ideal and routine roles; ambiguity in accountability in the postdischarge period; factors prompting clinicians to act closer to ideal roles; and barriers to performing ideal roles. A conceptual framework was created to summarize clinicians' roles during care transitions. This study reports differences between what healthcare professionals perceive as ideal roles of clinicians during care transitions and what clinicians actually do routinely. Certain patient and clinician factors prompt clinicians to act closer to the ideal roles. Multiple barriers interfere with consistent practice of ideal roles. Future investigations could evaluate interventions targeting various components of the conceptual framework and relevant outcomes. © 2013, Copyright the Authors Journal compilation © 2013, The American Geriatrics Society.

  13. Structural and Luminescent property of Holmium doped Borate Glasses

    NASA Astrophysics Data System (ADS)

    Usharani, V. L.; Eraiah, B.

    2018-02-01

    Holmium doped Lithium Lead Borate glasses of different compositions were prepared by melt quenching technique. Fourier transform infrared investigations on lithium lead borate glasses have been made to study the local order and vibrations of atoms in the glass network and it contains mainly BO3 and BO4 structural units. Photoluminescence techniques were employed to investigate the luminescent property of these glasses excited at 451nm. Blue emission have been observed from the transition 495 (5F3 → 5I8).

  14. Pressure-induced orientational glass phase in molecular para-hydrogen.

    PubMed

    Schelkacheva, T I; Tareyeva, E E; Chtchelkatchev, N M

    2009-02-01

    We propose a theoretical description of a possible orientational glass transition in solid molecular para-hydrogen and ortho-deuterium under pressure supposing that they are mixtures of J=0 and J=2 states of molecules. The theory uses the basic concepts and methods of standard spin-glass theory. We expect our orientational glass to correspond to the II' phase of the high-pressure hydrogen phase diagram.

  15. Blue light emission from trivalent cerium doped in sol-gel silica glass

    NASA Astrophysics Data System (ADS)

    Tokumitsu, Seika; Murakami, Yukon; Oda, Hisaya; Kawabe, Yutaka

    2017-02-01

    Rare earths in glass matrices are promising for active optical devices as amplifiers and lasers. Emission originating from d-f transitions in sol-gel glass has not been studied very often, while those based on f-f transitions were widely utilized. However, d-f emission in rare earths is very important because of their strong oscillator strength and broad emission widths suitable for the application to scintillators and solid-state lasers. Co-doping of aluminum in sol-gel synthesis was known to be effective for the emission enhancement of trivalent terbium and europium. Recently, we applied aluminum co-doping to cerium and europium systems in sol-gel glass to succeed in the observation of strong blue light emission originating from d-f transitions. Glass samples were prepared with conventional sol-gel process where tetramethylorthosilicate was hydrolyzed in the mixture of water, ethanol and dimethylformamide with nitric acid catalyst. After adding cerium nitrate and aluminum nitrate, the solution experienced drying followed by calcination at 1,050°C under air environment. When molar ratio of cerium to silicon was adjusted at 0.1% and Al concentration was varied in 0.1 2.0%, transparent glass products showed bright and broad blue photoluminescence under UV illumination. The fluorescence lifetimes were found to be about 50 90 ns, indicating that the emission was due to d-f transitions. Considering the simplicity of the process, blue phosphors based on sol-gel glass will be very promising for future applications.

  16. Distinctly Different Glass Transition Behaviors of Trehalose Mixed with Na2HPO 4 or NaH 2PO 4: Evidence for its Molecular Origin.

    PubMed

    Weng, Lindong; Elliott, Gloria D

    2015-07-01

    The present study is aimed at understanding how the interactions between sugar molecules and phosphate ions affect the glass transition temperature of their mixtures, and the implications for pharmaceutical formulations. The glass transition temperature (Tg) and the α-relaxation temperature (Tα) of dehydrated trehalose/sodium phosphate mixtures (monobasic or dibasic) were determined by differential scanning calorimetry and dynamic mechanical analysis, respectively. Molecular dynamics simulations were also conducted to investigate the microscopic interactions between sugar molecules and phosphate ions. The hydrogen-bonding characteristics and the self-aggregation features of these mixtures were quantified and compared. Thermal analysis measurements demonstrated that the addition of NaH2PO4 decreased both the glass transition temperature and the α-relaxation temperature of the dehydrated trehalose/NaH2PO4 mixture compared to trehalose alone while both Tg and Tα were increased by adding Na2HPO4 to pure trehalose. The hydrogen-bonding interactions between trehalose and HPO4(2-) were found to be stronger than both the trehalose-trehalose hydrogen bonds and those formed between trehalose and H2PO4(-). The HPO4(2-) ions also aggregated into smaller clusters than H2PO4(-) ions. The trehalose/Na2HPO4 mixture yielded a higher T g than pure trehalose because marginally self-aggregated HPO4(2-) ions established a strengthened hydrogen-bonding network with trehalose molecules. In contrast H2PO4(-) ions served only as plasticizers, resulting in a lower Tg of the mixtures than trehalose alone, creating large-sized ionic pockets, weakening interactions, and disrupting the original hydrogen-bonding network amongst trehalose molecules.

  17. Distinctly Different Glass Transition Behaviors of Trehalose Mixed with Na2HPO4 or NaH2PO4: Evidence for its Molecular Origin

    PubMed Central

    Weng, Lindong; Elliott, Gloria D.

    2015-01-01

    Purpose The present study is aimed at understanding how the interactions between sugar molecules and phosphate ions affect the glass transition temperature of their mixtures, and the implications for pharmaceutical formulations. Methods The glass transition temperature (Tg) and the α-relaxation temperature (Tα) of dehydrated trehalose/sodium phosphate mixtures (monobasic or dibasic) were determined by differential scanning calorimetry and dynamic mechanical analysis, respectively. Molecular dynamics simulations were also conducted to investigate the microscopic interactions between sugar molecules and phosphate ions. The hydrogen-bonding characteristics and the self-aggregation features of these mixtures were quantified and compared. Results Thermal analysis measurements demonstrated that the addition of NaH2PO4 decreased both the glass transition temperature and the α-relaxation temperature of the dehydrated trehalose/NaH2PO4 mixture compared to trehalose alone while both Tg and Tα were increased by adding Na2HPO4 to pure trehalose. The hydrogen-bonding interactions between trehalose and HPO42− were found to be stronger than both the trehalose-trehalose hydrogen bonds and those formed between trehalose and H2PO4−. The HPO42− ions also aggregated into smaller clusters than H2PO4− ions. Conclusions The trehalose/Na2HPO4 mixture yielded a higher Tg than pure trehalose because marginally self-aggregated HPO42− ions established a strengthened hydrogen-bonding network with trehalose molecules. In contrast H2PO4− ions served only as plasticizers, resulting in a lower Tg of the mixtures than trehalose alone, creating large-sized ionic pockets, weakening interactions, and disrupting the original hydrogen-bonding network amongst trehalose molecules. PMID:25537342

  18. Solubility of crystalline organic compounds in high and low molecular weight amorphous matrices above and below the glass transition by zero enthalpy extrapolation.

    PubMed

    Amharar, Youness; Curtin, Vincent; Gallagher, Kieran H; Healy, Anne Marie

    2014-09-10

    Pharmaceutical applications which require knowledge of the solubility of a crystalline compound in an amorphous matrix are abundant in the literature. Several methods that allow the determination of such data have been reported, but so far have only been applicable to amorphous polymers above the glass transition of the resulting composites. The current work presents, for the first time, a reliable method for the determination of the solubility of crystalline pharmaceutical compounds in high and low molecular weight amorphous matrices at the glass transition and at room temperature (i.e. below the glass transition temperature), respectively. The solubilities of mannitol and indomethacin in polyvinyl pyrrolidone (PVP) K15 and PVP K25, respectively were measured at different temperatures. Mixtures of undissolved crystalline solute and saturated amorphous phase were obtained by annealing at a given temperature. The solubility at this temperature was then obtained by measuring the melting enthalpy of the crystalline phase, plotting it as a function of composition and extrapolating to zero enthalpy. This new method yielded results in accordance with the predictions reported in the literature. The method was also adapted for the measurement of the solubility of crystalline low molecular weight excipients in amorphous active pharmaceutical ingredients (APIs). The solubility of mannitol, glutaric acid and adipic acid in both indomethacin and sulfadimidine was experimentally determined and successfully compared with the difference between their respective calculated Hildebrand solubility parameters. As expected from the calculations, the dicarboxylic acids exhibited a high solubility in both amorphous indomethacin and sulfadimidine, whereas mannitol was almost insoluble in the same amorphous phases at room temperature. This work constitutes the first report of the methodology for determining an experimentally measured solubility for a low molecular weight crystalline solute

  19. The relationship between structural and optical properties of Se-Ge-As glasses

    NASA Astrophysics Data System (ADS)

    Ghayebloo, M.; Rezvani, M.; Tavoosi, M.

    2018-05-01

    In this study, the structural and optical characterization of bulk Se-Ge-As glasses has been investigated. In this regards, six different Se60Ge40-xAsx (0 ≤ x ≤ 25) glasses were prepared by conventional melt quenching technique in quartz ampoule. The produced samples were characterized using X-ray diffraction (XRD), Raman spectroscopy, differential thermal analysis (DTA), ultraviolet-visible (UV-Vis) and Fourier transform infrared (FTIR) spectroscopy. The fundamental absorption edge for all the glasses was analyzed in terms of the theory proposed by Davis and Mott. According to achieved results, fully amorphous phase can easily form in different Se-Ge-As systems. The thermal and optical characteristic of Se60Ge40-xAsx glasses shows anomalous behavior at 5 mol% of As for the glass transition temperature, transmittance, absorption edge, optical energy gap and Urbach energy. The highest glass transition temperature, transmittance, optical energy gap and Urbach energy properties were achieved in Se60Ge35As5 glass as a result of the highest connectivity of cations and anions in glass network.

  20. Glass-ionomer-silver-cermet interim Class I restorations for permanent teeth.

    PubMed

    Croll, T P; Killian, C M

    1992-11-01

    Glass-ionomer-silver-cermet cement has proved to be a worthy alternative to silver amalgam for restoring certain Class I lesions in primary teeth. Such restorations are now known to last up to 8 years without need for repair or replacement. Cermet cement has also been used for interim restoration of permanent teeth in special cases, with ideal results. The procedure for placing a glass-ionomer-silver-cermet cement Class I restoration is described.

  1. Origin of embrittlement in metallic glasses

    PubMed Central

    Garrett, Glenn R.; Demetriou, Marios D.; Launey, Maximilien E.; Johnson, William L.

    2016-01-01

    Owing to their glassy nature, metallic glasses demonstrate a toughness that is extremely sensitive to the frozen-in configurational state. This sensitivity gives rise to “annealing embrittlement,” which is often severe and in many respects limits the technological advancement of these materials. Here, equilibrium configurations (i.e., “inherent states”) of a metallic glass are established around the glass transition, and the configurational properties along with the plane-strain fracture toughness are evaluated to associate the intrinsic glass toughness with the inherent state properties and identify the fundamental origin of embrittlement. The established correlations reveal a one-to-one correspondence between toughness and shear modulus continuous over a broad range of inherent states, suggesting that annealing embrittlement is controlled almost solely by an increasing resistance to shear flow. This annealing embrittlement sensitivity is shown to vary substantially between metallic glass compositions, and appears to correlate well with the fragility of the metallic glass. PMID:27573817

  2. Synthesis of styrene/isoprene/butadiene integrated rubber with wide glass transition temperature by reactive extrusion

    NASA Astrophysics Data System (ADS)

    Huang, Tianhua; Zheng, Anna; Zhan, Pengfei; Shi, Han; Li, Xiang; Guan, Yong; Wei, Dafu

    2018-05-01

    In this work, styrene/isoprene/butadiene integrated rubber (SIBR) was synthesized with n-butyllithium as the initiator and tetrahydrofuran as structure modifier in a co-rotating intermeshing twin-screw extruder. The content of diene in these terpolymers reached a surprising 70 wt% by feeding the monomers in two different sites of the twin-screw extruder. 1H-NMR, GPC and TEM results showed that the molecular structures of terpolymers changed with the variation of feeding site. Dynamic mechanical analysis of the vulcanized SIBR showed that the terpolymer had a wide glass transition region, which assured an excellent combination of high antiskid properties and low rolling resistance. Different from traditional solution polymerization, the present work provides a green approach to prepare the SIBR via bulk polymerization without solvent.

  3. Non-equilibrium phase transitions in a liquid crystal

    NASA Astrophysics Data System (ADS)

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

    2015-09-01

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

  4. Rare earth-doped lead borate glasses and transparent glass-ceramics: structure-property relationship.

    PubMed

    Pisarski, W A; Pisarska, J; Mączka, M; Lisiecki, R; Grobelny, Ł; Goryczka, T; Dominiak-Dzik, G; Ryba-Romanowski, W

    2011-08-15

    Correlation between structure and optical properties of rare earth ions in lead borate glasses and glass-ceramics was evidenced by X-ray-diffraction, Raman, FT-IR and luminescence spectroscopy. The rare earths were limited to Eu(3+) and Er(3+) ions. The observed BO(3)↔BO(4) conversion strongly depends on the relative PbO/B(2)O(3) ratios in glass composition, giving important contribution to the luminescence intensities associated to (5)D(0)-(7)F(2) and (5)D(0)-(7)F(1) transitions of Eu(3+). The near-infrared luminescence and up-conversion spectra for Er(3+) ions in lead borate glasses before and after heat treatment were measured. The more intense and narrowing luminescence lines suggest partial incorporation of Er(3+) ions into the orthorhombic PbF(2) crystalline phase, which was identified using X-ray diffraction analysis. Copyright © 2010 Elsevier B.V. All rights reserved.

  5. Iron phosphate glasses: Bulk properties and atomic scale structure

    NASA Astrophysics Data System (ADS)

    Joseph, Kitheri; Stennett, Martin C.; Hyatt, Neil C.; Asuvathraman, R.; Dube, Charu L.; Gandy, Amy S.; Govindan Kutty, K. V.; Jolley, Kenny; Vasudeva Rao, P. R.; Smith, Roger

    2017-10-01

    Bulk properties such as glass transition temperature, density and thermal expansion of iron phosphate glass compositions, with replacement of Cs by Ba, are investigated as a surrogate for the transmutation of 137Cs to 137Ba, relevant to the immobilisation of Cs in glass. These studies are required to establish the appropriate incorporation rate of 137Cs in iron phosphate glass. Density and glass transition temperature increases with the addition of BaO indicating the shrinkage and reticulation of the iron phosphate glass network. The average thermal expansion coefficient reduces from 19.8 × 10-6 K-1 to 13.4 × 10-6 K-1, when 25 wt. % of Cs2O was replaced by 25 wt. % of BaO in caesium loaded iron phosphate glass. In addition to the above bulk properties, the role of Ba as a network modifier in the structure of iron phosphate glass is examined using various spectroscopic techniques. The FeII content and average coordination number of iron in the glass network was estimated using Mössbauer spectroscopy. The FeII content in the un-doped iron phosphate glass and barium doped iron phosphate glasses was 20, 21 and 22 ± 1% respectively and the average Fe coordination varied from 5.3 ± 0.2 to 5.7 ± 0.2 with increasing Ba content. The atomic scale structure was further probed by Fe K-edge X-ray absorption spectroscopy. The average coordination number provided by extended X-ray absorption fine structure spectroscopy and X-ray absorption near edge structure was in good agreement with that given by the Mössbauer data.

  6. Hopping and the Stokes–Einstein relation breakdown in simple glass formers

    PubMed Central

    Charbonneau, Patrick; Jin, Yuliang; Parisi, Giorgio; Zamponi, Francesco

    2014-01-01

    One of the most actively debated issues in the study of the glass transition is whether a mean-field description is a reasonable starting point for understanding experimental glass formers. Although the mean-field theory of the glass transition—like that of other statistical systems—is exact when the spatial dimension d→∞, the evolution of systems properties with d may not be smooth. Finite-dimensional effects could dramatically change what happens in physical dimensions, d=2,3. For standard phase transitions finite-dimensional effects are typically captured by renormalization group methods, but for glasses the corrections are much more subtle and only partially understood. Here, we investigate hopping between localized cages formed by neighboring particles in a model that allows to cleanly isolate that effect. By bringing together results from replica theory, cavity reconstruction, void percolation, and molecular dynamics, we obtain insights into how hopping induces a breakdown of the Stokes–Einstein relation and modifies the mean-field scenario in experimental systems. Although hopping is found to supersede the dynamical glass transition, it nonetheless leaves a sizable part of the critical regime untouched. By providing a constructive framework for identifying and quantifying the role of hopping, we thus take an important step toward describing dynamic facilitation in the framework of the mean-field theory of glasses. PMID:25288722

  7. A macroscopic model that connects the molar excess entropy of a supercooled liquid near its glass transition temperature to its viscosity.

    PubMed

    Matsuoka, Hiroshi

    2012-11-28

    For a deeply supercooled liquid near its glass transition temperature, we suggest a possible way to connect the temperature dependence of its molar excess entropy to that of its viscosity by constructing a macroscopic model, where the deeply supercooled liquid is assumed to be a mixture of solid-like and liquid-like micro regions. In this model, we assume that the mole fraction x of the liquid-like micro regions tends to zero as the temperature T of the liquid is decreased and extrapolated to a temperature T(g)(*), which we assume to be below but close to the lowest glass transition temperature T(g) attainable with the slowest possible cooling rate for the liquid. Without referring to any specific microscopic nature of the solid-like and liquid-like micro regions, we also assume that near T(g), the molar enthalpy of the solid-like micro regions is lower than that of the liquid-like micro regions. We then show that the temperature dependence of x is directly related to that of the molar excess entropy. Close to T(g), we assume that an activated motion of the solid-like micro regions controls the viscosity and that this activated motion is a collective motion involving practically all of the solid-like micro-regions so that the molar activation free energy Δg(a) for the activated motion is proportional to the mole fraction, 1 - x, of the solid-like micro regions. The temperature dependence of the viscosity is thus connected to that of the molar excess entropy s(e) through the temperature dependence of the mole fraction x. As an example, we apply our model to a class of glass formers for which s(e) at temperatures near T(g) is well approximated by s(e) ∝ 1 - T(K)∕T with T(K) < T(g) ≅ T(g)(*) and find their viscosities to be well approximated by the Vogel-Fulcher-Tamman equation for temperatures very close to T(g). We also find that a parameter a appearing in the temperature dependence of x for a glass former in this class is a measure for its fragility. As this

  8. Comparing two tetraalkylammonium ionic liquids. II. Phase transitions.

    PubMed

    Lima, Thamires A; Paschoal, Vitor H; Faria, Luiz F O; Ribeiro, Mauro C C; Ferreira, Fabio F; Costa, Fanny N; Giles, Carlos

    2016-06-14

    Phase transitions of the ionic liquids n-butyl-trimethylammonium bis(trifluoromethanesulfonyl)imide, [N1114][NTf2], and methyl-tributylammonium bis(trifluoromethanesulfonyl)imide, [N1444][NTf2], were investigated by differential scanning calorimetry (DSC), X-ray diffraction (XRD) measurements, and Raman spectroscopy. XRD and Raman spectra were obtained as a function of temperature at atmospheric pressure, and also under high pressure at room temperature using a diamond anvil cell (DAC). [N1444][NTf2] experiences glass transition at low temperature, whereas [N1114][NTf2] crystallizes or not depending on the cooling rate. Both the ionic liquids exhibit glass transition under high pressure. XRD and low-frequency Raman spectra provide a consistent physical picture of structural ordering-disordering accompanying the thermal events of crystallization, glass transition, cold crystallization, pre-melting, and melting. Raman spectra in the high-frequency range of some specific cation and anion normal modes reveal conformational changes of the molecular structures along phase transitions.

  9. Medium-range structure and glass forming ability in Zr–Cu–Al bulk metallic glasses

    DOE PAGES

    Zhang, Pei; Maldonis, Jason J.; Besser, M. F.; ...

    2016-03-05

    Fluctuation electron microscopy experiments combined with hybrid reverse Monte Carlo modeling show a correlation between medium-range structure at the nanometer scale and glass forming ability in two Zr–Cu–Al bulk metallic glass (BMG) alloys. Both Zr 50Cu 35Al 15 and Zr 50Cu 45Al 5 exhibit two nanoscale structure types, one icosahedral and the other more crystal-like. In Zr 50Cu 35Al 15, the poorer glass former, the crystal-like structure is more stable under annealing below the glass transition temperature, T g, than in Zr 50Cu 45Al 5. Variable resolution fluctuation microscopy of the MRO clusters show that in Zr 50Cu 35Al 15more » on sub-Tg annealing, the crystal-like clusters shrink even as they grow more ordered, while icosahedral-like clusters grow. Furthermore, the results suggest that achieving better glass forming ability in this alloy system may depend more on destabilizing crystal-like structures than enhancing non-crystalline structures.« less

  10. 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.

  11. Effect of salt on the glass transition of condensed tapioca starch systems.

    PubMed

    Chuang, Lillian; Panyoyai, Naksit; Shanks, Robert A; Kasapis, Stefan

    2017-08-15

    This work examines the effect of including hydrated NaCl and CaCl 2 (up to 6% w/w) on the physicochemical properties of condensed tapioca starch. Samples were prepared by hot pressing at 120°C to produce condensed systems that covered a range of moisture contents from 7.34% w/w (23% relative humidity) to 19.52% w/w (75% relative humidity). Tensile storage modulus and heat flow measurements were taken using DMA and MDSC, which were accompanied by FTIR, WAXD and ESEM. Increasing the salt level enhances the mechanical strength of starch in the glassy state and shifts the glass transition temperature to a higher value. Antiplasticising effects of NaCl and CaCl 2 on the non-phosphorylated tapioca starch are indistinguishable from each other. Observations are complemented by intensification of absorbance peaks in FTIR spectra and a systematic change in shape and intensity of diffraction patterns with increasing addition of salt consistent with interactions between added ions and macromolecule. Copyright © 2017. Published by Elsevier Ltd.

  12. The descent into glass formation in polymer fluids.

    PubMed

    Freed, Karl F

    2011-03-15

    Glassy materials have been fundamental to technology since the dawn of civilization and remain so to this day: novel glassy systems are currently being developed for applications in energy storage, electronics, food, drugs, and more. Glass-forming fluids exhibit a universal set of transitions beginning at temperatures often in excess of twice the glass transition temperature T(g) and extending down to T(g), below which relaxation becomes so slow that systems no longer equilibrate on experimental time scales. Despite the technological importance of glasses, no prior theory explains this universal behavior nor describes the huge variations in the properties of glass-forming fluids that result from differences in molecular structure. Not surprisingly, the glass transition is currently regarded by many as the deepest unsolved problem in solid state theory. In this Account, we describe our recently developed theory of glass formation in polymer fluids. Our theory explains the origin of four universal characteristic temperatures of glass formation and their dependence on monomer-monomer van der Waals energies, conformational energies, and pressure and, perhaps most importantly, on molecular details, such as monomer structure, molecular weight, size of side groups, and so forth. The theory also provides a molecular explanation for fragility, a parameter that quantifies the rate of change with temperature of the viscosity and other dynamic mechanical properties at T(g). The fragility reflects the fluid's thermal sensitivity and determines the manner in which glass-formers can be processed, such as by extrusion, casting, or inkjet spotting. Specifically, the theory describes the change in thermodynamic properties and fragility of polymer glasses with variations in the monomer structure, the rigidity of the backbone and side groups, the cohesive energy, and so forth. The dependence of the structural relaxation time at lower temperatures emerges from the theory as the Vogel

  13. From Glass Formation to Icosahedral Ordering by Curving Three-Dimensional Space.

    PubMed

    Turci, Francesco; Tarjus, Gilles; Royall, C Patrick

    2017-05-26

    Geometric frustration describes the inability of a local molecular arrangement, such as icosahedra found in metallic glasses and in model atomic glass formers, to tile space. Local icosahedral order, however, is strongly frustrated in Euclidean space, which obscures any causal relationship with the observed dynamical slowdown. Here we relieve frustration in a model glass-forming liquid by curving three-dimensional space onto the surface of a 4-dimensional hypersphere. For sufficient curvature, frustration vanishes and the liquid "freezes" in a fully icosahedral structure via a sharp "transition." Frustration increases upon reducing the curvature, and the transition to the icosahedral state smoothens while glassy dynamics emerge. Decreasing the curvature leads to decoupling between dynamical and structural length scales and the decrease of kinetic fragility. This sheds light on the observed glass-forming behavior in Euclidean space.

  14. Experimental evidences of the Gardner phase in a granular glass

    NASA Astrophysics Data System (ADS)

    Dauchot, Olivier; Seguin, Antoine

    The constituent particles of a glass are caged by their neighbors and thus cannot relax density fluctuations. This is also true for hard particles under compression. The associated slowing down of the dynamics is related to a complex free energy landscape. It was recently shown theoretically that the hard sphere glass in infinite dimension undergoes a Gardner transition, at which the glass basin breaks into a hierarchy of marginally stable sub-basins. This was very recently confirmed in simulations of 2d and 3d hard sphere (HS) glasses. We present the first direct experimental evidences of the Gardner phase, taking advantage of a well controlled granular experiment, which has already proven to successfully probe the vicinity of the jamming transition in a bi-dimensional granular glass former. More precisely, we perform independent compressions of a carefully prepared granular glass and show that for large enough compression, the final state differs from one compression to another. To do so we compare the average cage size within one state, and the average distance separating the cages of the same particles across successive compression cycles. The latter plateaus to a constant value, when entering the Gardner phase.

  15. Optical, Structural, and Thermal Properties of Cerium-Doped Zinc Borophosphate Glasses.

    PubMed

    Choi, Su-Yeon; Ryu, Bong-Ki

    2015-11-01

    In this study, we verify the relationship between the optical properties and structure of cerium-doped zinc borophosphate glasses that have concurrence of non-bridging oxygen (NBO) and bridging oxygen (BO), Ce3+ and Ce4+, and BO3 structure and BO4 structure. We prepared cerium-doped zinc borophosphate glass with various compositions, given by xCeO2-(100-x)[50ZnO-10B2O3 -40P2O5] (x = 1 mol% to 6 mol%), and analyzed their optical band energy, glass transition temperature, crystallization temperature, density, and molar volume. Some of the techniques used for analysis were Fourier transform infrared (FT-IR) spectroscopy and X-ray photoelectron spectroscopy (XPS). In the investigated glasses, the optical band gap energy decreased from 3.28 eV to 1.73 eV. From these results, we can deduce the changes when transitions occur from BO to NBO, from Ce3+ to Ce4+, and from the BO3 structure to the BO4 structure with increasing CeO2 content using FT-IR and XPS analysis. We also verified the changes in structural and physical properties from quantitative properties such as glass transition temperature, crystallization temperature, density, and molar volume.

  16. Localization and Symmetry Breaking in the Quantum Quasiperiodic Ising Glass

    NASA Astrophysics Data System (ADS)

    Chandran, A.; Laumann, C. R.

    2017-07-01

    Quasiperiodic modulation can prevent isolated quantum systems from equilibrating by localizing their degrees of freedom. In this article, we show that such systems can exhibit dynamically stable long-range orders forbidden in equilibrium. Specifically, we show that the interplay of symmetry breaking and localization in the quasiperiodic quantum Ising chain produces a quasiperiodic Ising glass stable at all energy densities. The glass order parameter vanishes with an essential singularity at the melting transition with no signatures in the equilibrium properties. The zero-temperature phase diagram is also surprisingly rich, consisting of paramagnetic, ferromagnetic, and quasiperiodically alternating ground-state phases with extended, localized, and critically delocalized low-energy excitations. The system exhibits an unusual quantum Ising transition whose properties are intermediate between those of the clean and infinite randomness Ising transitions. Many of these results follow from a geometric generalization of the Aubry-André duality that we develop. The quasiperiodic Ising glass may be realized in near-term quantum optical experiments.

  17. Effect of drying methods of microencapsulated Lactobacillus acidophilus and Lactococcus lactis ssp. cremoris on secondary protein structure and glass transition temperature as studied by Fourier transform infrared and differential scanning calorimetry.

    PubMed

    Dianawati, Dianawati; Mishra, Vijay; Shah, Nagendra P

    2013-03-01

    Protective mechanisms of casein-based microcapsules containing mannitol on Lactobacillus acidophilus and Lactococcus lactis ssp. cremoris, changes in their secondary protein structures, and glass transition of the microcapsules were studied after spray- or freeze-drying and after 10 wk of storage in aluminum foil pouches containing different desiccants (NaOH, LiCl, or silica gel) at 25°C. An in situ Fourier transform infrared analysis was carried out to recognize any changes in fatty acids (FA) of bacterial cell envelopes, interaction between polar site of cell envelopes and microcapsules, and alteration of their secondary protein structures. Differential scanning calorimetry was used to determine glass transition of microcapsules based on glass transition temperature (T(g)) values. Hierarchical cluster analysis based on functional groups of cell envelopes and secondary protein structures was also carried out to classify the microencapsulated bacteria due to the effects of spray- or freeze-drying and storage for 10 wk. The results showed that drying process did not affect FA and secondary protein structures of bacteria; however, those structures were affected during storage depending upon the type of desiccant used. Interaction between exterior of bacterial cell envelopes and microencapsulant occurred after spray- or freeze-drying; however, these structures were maintained after storage in foil pouch containing sodium hydroxide. Method of drying and type of desiccants influenced the level of similarities of microencapsulated bacteria. Desiccants and method of drying affected glass transition, yet no T(g) ≤25°C was detected. This study demonstrated that the changes in FA and secondary structures of the microencapsulated bacteria still occurred during storage at T(g) above room temperature, indicating that the glassy state did not completely prevent chemical activities. Copyright © 2013 American Dairy Science Association. Published by Elsevier Inc. All rights

  18. Structural rejuvenation in bulk metallic glasses

    DOE PAGES

    Tong, Yang; Iwashita, T.; Dmowski, Wojciech; ...

    2015-01-05

    Using high-energy X-ray diffraction we study structural changes in bulk metallic glasses after uniaxial compressive homogeneous deformation at temperatures slightly below the glass transition. We observe that deformation results in structural disordering corresponding to an increase in the fictive, or effective, temperature. However, the structural disordering saturates after yielding. Lastly, examination of the experimental structure and molecular dynamics simulation suggests that local changes in the atomic connectivity network are the main driving force of the structural rejuvenation.

  19. Structural rejuvenation in bulk metallic glasses

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

    Tong, Yang; Iwashita, T.; Dmowski, Wojciech

    Using high-energy X-ray diffraction we study structural changes in bulk metallic glasses after uniaxial compressive homogeneous deformation at temperatures slightly below the glass transition. We observe that deformation results in structural disordering corresponding to an increase in the fictive, or effective, temperature. However, the structural disordering saturates after yielding. Lastly, examination of the experimental structure and molecular dynamics simulation suggests that local changes in the atomic connectivity network are the main driving force of the structural rejuvenation.

  20. Spectroscopic investigations on Pr³+ and Nd³+ doped strontium-lithium-bismuth borate glasses.

    PubMed

    Rajesh, D; Balakrishna, A; Seshadri, M; Ratnakaram, Y C

    2012-11-01

    Spectroscopic investigations on different concentrations (0.1, 0.5, 1.0, 1.5 and 2.0mol%) of Pr(3+) and Nd(3+) doped strontium lithium bismuth borate glasses have been done. X-ray diffraction, SEM with EDS, absorption and luminescence spectra were recorded for all the glass matrices and analyzed. X-ray diffraction profiles and SEM images conformed amorphous nature of investigated glass samples. EDS spectra of host glass and Pr(3+)doped glass matrices gave information about the chemical composition of glass samples. From the absorption spectra of Pr(3+) and Nd(3+) ions, Judd-Ofelt (J-O) intensity parameters (Ω(λ),λ=2, 4 and 6) have been calculated and compared with other glass matrices. The emission characteristics such as radiative lifetimes (τ(R)), measured and calculated branching ratios (β) and stimulated emission cross-sections (σ(P)) have been obtained for the observed emission transitions of Pr(3+) and Nd(3+) ions in the above glass matrix for all the concentrations. From the emission spectra of Pr(3+) and Nd(3+) doped glass matrices, the effect of concentration on the quenching of intensity of (1)D(2)→(3)H(4) transition of Pr(3+) ion and (4)F(3/2)→(4)I(9/2), (4)I(11/2) and (4)I(13/2) transitions of Nd(3+) have been studied and discussed. Copyright © 2012 Elsevier B.V. All rights reserved.

  1. Application of the thermorheologically complex nonlinear Adam-Gibbs model for the glass transition to molecular motion in hydrated proteins.

    PubMed

    Hodge, Ian M

    2006-08-01

    The nonlinear thermorheologically complex Adam Gibbs (extended "Scherer-Hodge") model for the glass transition is applied to enthalpy relaxation data reported by Sartor, Mayer, and Johari for hydrated methemoglobin. A sensible range in values for the average localized activation energy is obtained (100-200 kJ mol(-1)). The standard deviation in the inferred Gaussian distribution of activation energies, computed from the reported KWW beta-parameter, is approximately 30% of the average, consistent with the suggestion that some relaxation processes in hydrated proteins have exceptionally low activation energies.

  2. Spectroscopic and nonlinear optical studies of pure and Nd-doped lanthanum strontium borate glasses

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

    Harde, G. B.; Department of Physics, Sant Gadge Baba Amravati University, Amravati, Maharashtra, India-444602; Muley, G. G., E-mail: gajananggm@yahoo.co.in

    2016-05-06

    Borate glasses of the system xNd{sub 2}O{sub 3}-(1-x) La{sub 2}O{sub 3}-SrCO{sub 3}-10H{sub 3}BO{sub 3} (with x = 0 and 0.05) were prepared by using a convectional melt quenching technique. The amorphous nature of the quenched glasses has been confirmed by powder X-ray diffraction analysis. In order to study the spectroscopic and nonlinear optical properties of fabricated glasses, ultraviolet-visible transmission spectroscopy and open aperture z-scan measurements have been employed. In Nd doped glasses, the transition {sup 4}I{sub 9/2} → {sup 4}G{sub 5/2} + {sup 2}G{sub 7/2} has found more prominent than the other transitions. Optical band gap energies of glasses havemore » been determined and found less for Nd doped glass.« less

  3. Elastic properties and optical absorption studies of mixed alkali borogermanate glasses

    NASA Astrophysics Data System (ADS)

    Taqiullah, S. M.; Ahmmad, Shaik Kareem; Samee, M. A.; Rahman, Syed

    2018-05-01

    First time the mixed alkali effect (MAE) has been investigated in the glass system xNa2O-(30-x)Li2O-40B2O3- 30GeO2 (0≤x≤30 mol%) through density and optical absorption studies. The present glasses were prepared by melt quench technique. The density of the present glasses varies non-linearly exhibiting mixed alkali effect. Using the density data, the elastic moduli namely Young's modulus, bulk and shear modulus show strong linear dependence as a function of compositional parameter. From the absorption edge studies, the values of optical band gap energies for all transitions have been evaluated. It was established that the type of electronic transition in the present glass system is indirect allowed. The indirect optical band gap exhibit non-linear behavior with compositional parameter showing the mixed alkali effect.

  4. Dynamic spectral shifts of molecular anions in organic glasses. [Pulse radiolysis

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

    Huddleston, R.K.; Miller, J.R.

    1982-06-24

    Time-dependent spectra of the radical anions of pyromellitic dianhydride and p-dinitrobenzene have been observed after formation by pulse radiolysis in frozen 2-methyltetrahydrofuran and triacetin glasses. At temperatures near the glass transition, the spectra shift toward the blue over the entire observed time range 100 ns to 100 s), while at temperatures well below the glass transition, the spectral shifts can be stopped or greatly slowed. The magnitudes of the shifts are not large (typically approx. = to 10 nm), but because they are larger than the vibrational line widths, dramatic kinetics may be observed: the absorbance grows or decays bymore » more than a factor of five at some wavelengths. The observations are consistent with a solvent molecule reorientation mechanism for spectral shifts of molecular ions in low-temperature organic glasses. 6 figures.« less

  5. Light Management in Flexible Glass by Wood Cellulose Coating

    PubMed Central

    Fang, Zhi-Qiang; Zhu, Hong-Li; Li, Yuan-Yuan; Liu, Zhen; Dai, Jia-Qi; Preston, Colin; Garner, Sean; Cimo, Pat; Chai, Xin-Sheng; Chen, Gang; Hu, Liang-Bing

    2014-01-01

    Ultra-thin flexible glass with high transparency is attractive for a broad range of display applications; however, substrates with low optical haze are not ideal for thin film solar cells, since most of the light will go through the semiconductor layer without scattering, and the length of light travelling path in the active layer is small. By simply depositing a layer of TEMPO (2,2,6,6-tetramethylpiperidine-1-oxyl radical)-oxidized wood fibers (TOWFs), we are able to tailor the optical properties of flexible glass dramatically from exhibiting low haze (<1%) to high haze (~56%) without compromising the total forward transmittance (~90%). The influence of the TOWFs morphology on the optical properties of TOWFs-coated flexible glass is investigated. As the average fiber length decreases, the transmission haze of TOWF-coated flexible glass illustrates a decreasing trend. Earth-abundant natural materials for transparent, hazy, and flexible glass have tremendous applicability in the fabrication of flexible optoelectronics with tunable light scattering effects by enabling inexpensive and large-scale processes. PMID:25068486

  6. Rubber-Modified Epoxies. I. Cure, Transitions, and Morphology.

    DTIC Science & Technology

    1984-10-01

    thermosetting systems has been developed. An aromatic tetrafunctional diamine-cured diglycidyl ether of bis- phenol A epoxy resin [maximum glass transition...systems has been developed. An aromatic tetrafunctional diamine-cured digly- cidyl ether of bisphenol A epoxy resin [maximum glass transition...epoxy resins are brittle materials. The crack resistance can be improved by the addition of reactive liquid rubber to uncured neat epoxy systems (1-3

  7. Comparing two tetraalkylammonium ionic liquids. II. Phase transitions

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

    Lima, Thamires A.; Paschoal, Vitor H.; Faria, Luiz F. O.

    Phase transitions of the ionic liquids n-butyl-trimethylammonium bis(trifluoromethanesulfonyl)imide, [N{sub 1114}][NTf{sub 2}], and methyl-tributylammonium bis(trifluoromethanesulfonyl)imide, [N{sub 1444}][NTf{sub 2}], were investigated by differential scanning calorimetry (DSC), X-ray diffraction (XRD) measurements, and Raman spectroscopy. XRD and Raman spectra were obtained as a function of temperature at atmospheric pressure, and also under high pressure at room temperature using a diamond anvil cell (DAC). [N{sub 1444}][NTf{sub 2}] experiences glass transition at low temperature, whereas [N{sub 1114}][NTf{sub 2}] crystallizes or not depending on the cooling rate. Both the ionic liquids exhibit glass transition under high pressure. XRD and low-frequency Raman spectra provide a consistent physical picturemore » of structural ordering-disordering accompanying the thermal events of crystallization, glass transition, cold crystallization, pre-melting, and melting. Raman spectra in the high-frequency range of some specific cation and anion normal modes reveal conformational changes of the molecular structures along phase transitions.« less

  8. 2.3 µm laser potential of TeO2 based glasses

    NASA Astrophysics Data System (ADS)

    Denker, B. I.; Dorofeev, V. V.; Galagan, B. I.; Motorin, S. E.; Sverchkov, S. E.

    2017-09-01

    Tm3+ doped TeO2-based well-dehydrated glasses were synthesized and investigated. The analysis of their spectral and relaxation properties have showed that these glasses can be a suitable host for bulk and fiber lasers emitting at ~2.3 µm wavelength (3H4-3H5 Tm3+ transition). Laser action in the bulk glass sample was demonstrated.

  9. Designing heavy metal oxide glasses with threshold properties from network rigidity

    NASA Astrophysics Data System (ADS)

    Chakraborty, Shibalik; Boolchand, P.; Malki, M.; Micoulaut, M.

    2014-01-01

    Here, we show that a new class of glasses composed of heavy metal oxides involving transition metals (V2O5-TeO2) can surprisingly be designed from very basic tools using topology and rigidity of their underlying molecular networks. When investigated as a function of composition, such glasses display abrupt changes in network packing and enthalpy of relaxation at Tg, underscoring presence of flexible to rigid elastic phase transitions. We find that these elastic phases are fully consistent with polaronic nature of electronic conductivity at high V2O5 content. Such observations have new implications for designing electronic glasses which differ from the traditional amorphous electrolytes having only mobile ions as charge carriers.

  10. Designing heavy metal oxide glasses with threshold properties from network rigidity.

    PubMed

    Chakraborty, Shibalik; Boolchand, P; Malki, M; Micoulaut, M

    2014-01-07

    Here, we show that a new class of glasses composed of heavy metal oxides involving transition metals (V2O5-TeO2) can surprisingly be designed from very basic tools using topology and rigidity of their underlying molecular networks. When investigated as a function of composition, such glasses display abrupt changes in network packing and enthalpy of relaxation at Tg, underscoring presence of flexible to rigid elastic phase transitions. We find that these elastic phases are fully consistent with polaronic nature of electronic conductivity at high V2O5 content. Such observations have new implications for designing electronic glasses which differ from the traditional amorphous electrolytes having only mobile ions as charge carriers.

  11. Spectroscopic investigations of Nd3+ doped flouro- and chloro-borate glasses.

    PubMed

    Mohan, Shaweta; Thind, Kulwant Singh; Sharma, Gopi; Gerward, Leif

    2008-10-01

    Spectroscopic and physical properties of Nd3+ doped sodium lead flouro- and chloro-borate glasses of the type 20NaX-30PbO-49.5B2O3-0.5Nd2O3 (X=F and Cl) have been investigated. Optical absorption spectra have been used to determine the Slater Condon (F2, F4, and F6), spin orbit xi4f and Racah parameters (E1, E2, and E3). The oscillator strengths and the intensity parameters Omega2, Omega4 and Omega6 have been determined by the Judd-Ofelt theory, which in turn provide the radiative transition probability (A), total transition probability (A(T)), radiative lifetime (tauR) and branching ratio (beta) for the fluorescent level 4F3/2. The lasing efficiency of the prepared glasses has been characterized by the spectroscopic quality factor (Omega4/Omega6), the value of which is in the range of 0.2-1.5, typical for Nd3+ in different laser hosts. Nephelauxetic effect results in a red shift in the energy levels of Nd3+ for chloroborate glass. The radiative transition probability of the potential lasing transition 4F3/2-->4I11/2 of Nd3+ ions is found to be higher for flouroborate as compared to chloroborate glass.

  12. Structural relaxation driven increase in elastic modulus for a bulk metallic glass

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

    Arora, Harpreet Singh; Aditya, Ayyagari V.; Mukherjee, Sundeep, E-mail: sundeep.mukherjee@unt.edu

    2015-01-07

    The change in elastic modulus as a function of temperature was investigated for a zirconium-based bulk metallic glass. High temperature nano-indentation was done over a wide temperature range from room temperature to the glass-transition. At higher temperature, there was a transition from inhomogeneous to homogeneous deformation, with a decrease in serrated flow and an increase in creep displacement. Hardness was found to decrease, whereas elastic modulus was found to increase with temperature. The increase in elastic modulus for metallic glass at higher temperature was explained by diffusive rearrangement of atoms resulting in free volume annihilation. This is in contrast tomore » elastic modulus increase with temperature for silicate glasses due to compaction of its open three dimensional coordinated structure without any atomic diffusion.« less

  13. X-ray tomography of feed-to-glass transition of simulated borosilicate waste glasses

    DOE PAGES

    Harris, William H.; Guillen, Donna P.; Klouzek, Jaroslav; ...

    2017-05-10

    The feed composition of a high level nuclear waste (HLW) glass melter affects the overall melting rate by influencing the chemical, thermophysical, and morphological properties of a relatively insulating cold cap layer over the molten phase where the primary feed vitrification reactions occur. Data from X ray computed tomography imaging of melting pellets comprised of a simulated high-aluminum HLW feed heated at a rate of 10°C/min reveal the distribution and morphology of bubbles, collectively known as primary foam, within this layer for various SiO 2/(Li 2CO 3+H 3BO 3+Na 2CO 3) mass fractions at temperatures between 600°C and 1040°C. Tomore » track melting dynamics, cross-sections obtained through the central profile of the pellet were digitally segmented into primary foam and a condensed phase. Pellet dimensions were extracted using Photoshop CS6 tools while the DREAM.3D software package was used to calculate pellet profile area, average and maximum bubble areas, and two-dimensional void fraction. The measured linear increase in the pellet area expansion rates – and therefore the increase in batch gas evolution rates – with SiO 2/(Li 2CO 3+H 3BO 3+Na 2CO 3) mass fraction despite an exponential increase in viscosity of the final waste glass at 1050°C and a lower total amount of gas-evolving species suggest that the retention of primary foam with large average bubble size at higher temperatures results from faster reaction kinetics rather than increased viscosity. However, viscosity does affect the initial foam collapse temperature by supporting the growth of larger bubbles. Because the maximum bubble size is limited by the pellet dimensions, larger scale studies are needed to understand primary foam morphology at high temperatures. This temperature-dependent morphological data can be used in future investigations to synthetically generate cold cap structures for use in models of heat transfer within a HLW glass melter.« less

  14. X-ray tomography of feed-to-glass transition of simulated borosilicate waste glasses

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

    Harris, William H.; Guillen, Donna P.; Klouzek, Jaroslav

    The feed composition of a high level nuclear waste (HLW) glass melter affects the overall melting rate by influencing the chemical, thermophysical, and morphological properties of a relatively insulating cold cap layer over the molten phase where the primary feed vitrification reactions occur. Data from X ray computed tomography imaging of melting pellets comprised of a simulated high-aluminum HLW feed heated at a rate of 10°C/min reveal the distribution and morphology of bubbles, collectively known as primary foam, within this layer for various SiO 2/(Li 2CO 3+H 3BO 3+Na 2CO 3) mass fractions at temperatures between 600°C and 1040°C. Tomore » track melting dynamics, cross-sections obtained through the central profile of the pellet were digitally segmented into primary foam and a condensed phase. Pellet dimensions were extracted using Photoshop CS6 tools while the DREAM.3D software package was used to calculate pellet profile area, average and maximum bubble areas, and two-dimensional void fraction. The measured linear increase in the pellet area expansion rates – and therefore the increase in batch gas evolution rates – with SiO 2/(Li 2CO 3+H 3BO 3+Na 2CO 3) mass fraction despite an exponential increase in viscosity of the final waste glass at 1050°C and a lower total amount of gas-evolving species suggest that the retention of primary foam with large average bubble size at higher temperatures results from faster reaction kinetics rather than increased viscosity. However, viscosity does affect the initial foam collapse temperature by supporting the growth of larger bubbles. Because the maximum bubble size is limited by the pellet dimensions, larger scale studies are needed to understand primary foam morphology at high temperatures. This temperature-dependent morphological data can be used in future investigations to synthetically generate cold cap structures for use in models of heat transfer within a HLW glass melter.« less

  15. Glass capable of ionic conduction and method of preparation

    DOEpatents

    Susman, S.; Delbecq, C.J.; Volin, K.J.; Boehm, L.

    1984-02-21

    Sulfide glasses capable of conducting alkali metal ions are prepared from a nonmetal glass former such as GeS[sub 2], B[sub 2]S[sub 3] and SiS[sub 2] in mixture with a glass modifier such as Na[sub 2]S or another alkali metal sulfide. A molten mixture of the constituents is rapidly quenched to below the glass transition temperature by contact with a metal mold. The rapid quench is sufficient to prevent crystallization and permit solidification as an amorphous solid mixture. An oxygen-free atmosphere is maintained over the mixture to prevent oxidation. A new glass system of (1-X) Na[sub 2]O:XB[sub 2]S[sub 3] is disclosed. 4 figs.

  16. Glass capable of ionic conduction and method of preparation

    DOEpatents

    Susman, S.; Boehm, L.; Volin, K.J.; Delbecq, C.J.

    1982-05-06

    Sulfide glasses capable of conducting alkali metal ions are prepared from a nonmetal glass former such as GeS/sub 2/, B/sub 2/S/sub 2/ and SiS/sub 2/ in mixture with a glass modifier such as Na/sub 2/S or another alkali metal sulfide. A molten mixture of the constituents is rapidly quenched to below the glass transition temperature by contact with a metal mold. The rapid quench is sufficient to prevent crystallization and permit solidification as an amorphous solid mixture. An oxygen-free atmosphere is maintained over the mixture to prevent oxidation. A new glass system of (1 - X) Na/sub 2/O:XB/sub 2/S/sub 3/ is disclosed.

  17. Glass capable of ionic conduction and method of preparation

    DOEpatents

    Susman, Sherman; Delbecq, Charles J.; Volin, Kenneth J.; Boehm, Leah

    1984-01-01

    Sulfide glasses capable of conducting alkali metal ions are prepared from a nonmetal glass former such as GeS.sub.2, B.sub.2 S.sub.3 and SiS.sub.2 in mixture with a glass modifier such as Na.sub.2 S or another alkali metal sulfide. A molten mixture of the constituents is rapidly quenched to below the glass transition temperature by contact with a metal mold. The rapid quench is sufficient to prevent crystallization and permit solidification as an amorphous solid mixture. An oxygen-free atmosphere is maintained over the mixture to prevent oxidation. A new glass system of (1-X) Na.sub.2 O:XB.sub.2 S.sub.3 is disclosed.

  18. Glass capable of ionic conduction and method of preparation

    DOEpatents

    Susman, Sherman; Boehm, Leah; Volin, Kenneth J.; Delbacq, Charles J.

    1985-01-01

    Sulfide glasses capable of conducting alkali metal ions are prepared from a nonmetal glass former such as GeS.sub.2, B.sub.2 S.sub.3 and SiS.sub.2 in mixture with a glass modifier such as Na.sub.2 S or another alkali metal sulfide. A molten mixture of the constituents is rapidly quenched to below the glass transition temperature by contact with a metal mold. The rapid quench is sufficient to prevent crystallization and permit solidification as an amorphous solid mixture. An oxygen-free atmosphere is maintained over the mixture to prevent oxidation. A new glass system of (1-X) Na.sub.2 O:XB.sub.2 S.sub.3 is disclosed.

  19. Down- and up-conversion emissions in Er-doped transparent fluorotellurite glass-ceramics

    NASA Astrophysics Data System (ADS)

    Miguel, A.; Morea, R.; Gonzalo, J.; Fernandez, J.; Balda, R.

    2015-03-01

    In this work, we report the near infrared and upconversion emissions of Er3+-doped transparent fluorotellurite glassceramics obtained by heat treatment of the precursor Er-doped TeO2-ZnO-ZnF2 glass. Structural analysis shows that ErF3 nanocrystals nucleated in the glass-ceramic sample are homogeneously distributed in the glass matrix with a typical size of 45±10 nm. The comparison of the fluorescence properties of Er3+-doped precursor glass and glass-ceramic confirms the successful incorporation of the rare-earth into the nanocrystals. An enhancement of the red upconversion emission due to 4F9/2→4I15/2 transition together with weak emission bands due to transitions from 2H9/2, 4F3/2,5/2, and 4F7/2 levels to the ground state are observed under excitation at 801 nm in the glass-ceramic sample. The temporal evolution of the red emission together with the excitation upconversion spectrum suggest that energy transfer processes are responsible for the enhancement of the red emission.

  20. Ammonia-treated phosphate glasses useful for sealing to metals

    DOEpatents

    Brow, R.K.; Day, D.E.

    1991-09-03

    A method of improving surface-dependent properties of phosphate glass such as durability and wear resistance without significantly affecting its thermal expansion coefficient is provided which comprises annealing the glass in a dry ammonia atmosphere at temperatures approximating the transition temperature of the glass. The ammonia annealing treatment of the present invention is carried out for a time sufficient to allow incorporation of a thin layer of nitrogen into the surface of the phosphate glass, and the treatment improves the durability of the glass without the reduction in the thermal expansion coefficient that has restricted the effectiveness of prior ammonia treatments. The improved phosphate glass resulting from this method is superior in wear resistance, yet maintains suitable thermal expansion properties so that it may be used effectively in a variety of applications requiring hermetic glass-metal seals.

  1. Glass transition and composite formation in InF{sub 3}-containing oxyfluoroniobate system

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

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

    2016-05-18

    The glasses in the system MnNbOF{sub 5}-BaF{sub 2}-InF{sub 3} have been firstly synthesized and studied. The thermal parameters of these glasses are analyzed. It was stated that glass of the composition 40MnNbOF{sub 5}-40BaF{sub 2}-20InF{sub 3} 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 Ba{sub 3}In{sub 2}F{sub 12} and BaNbOF{sub 5}. 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 inmore » NbO{sub 2}F-BaF{sub 2} system: (NbO{sub n}F{sub m}) polyhedra joined oxygen bridges. Indium trifluoride forms InF{sub 6} polyhedra, which are embeded between oxyfluoroniobate ions, forming a common networks or forms its own layers from InF{sub 6} polyhedra. IR-spectroscopy method showed that at devitrification of the sample 30MnNbOF{sub 5}-50BaF{sub 2}-20InF{sub 3} the band position and shape change in going from glass state to crystalline. The bands in the range 900–700 cm{sup −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.« less

  2. Late Byzantine mineral soda high alumina glasses from Asia Minor: a new primary glass production group.

    PubMed

    Schibille, Nadine

    2011-04-19

    The chemical characterisation of archaeological glass allows the discrimination between different glass groups and the identification of raw materials and technological traditions of their production. Several lines of evidence point towards the large-scale production of first millennium CE glass in a limited number of glass making factories from a mixture of Egyptian mineral soda and a locally available silica source. Fundamental changes in the manufacturing processes occurred from the eight/ninth century CE onwards, when Egyptian mineral soda was gradually replaced by soda-rich plant ash in Egypt as well as the Islamic Middle East. In order to elucidate the supply and consumption of glass during this transitional period, 31 glass samples from the assemblage found at Pergamon (Turkey) that date to the fourth to fourteenth centuries CE were analysed by electron microprobe analysis (EPMA) and by laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS). The statistical evaluation of the data revealed that the Byzantine glasses from Pergamon represent at least three different glass production technologies, one of which had not previously been recognised in the glass making traditions of the Mediterranean. While the chemical characteristics of the late antique and early medieval fragments confirm the current model of glass production and distribution at the time, the elemental make-up of the majority of the eighth- to fourteenth-century glasses from Pergamon indicate the existence of a late Byzantine glass type that is characterised by high alumina levels. Judging from the trace element patterns and elevated boron and lithium concentrations, these glasses were produced with a mineral soda different to the Egyptian natron from the Wadi Natrun, suggesting a possible regional Byzantine primary glass production in Asia Minor.

  3. Late Byzantine Mineral Soda High Alumina Glasses from Asia Minor: A New Primary Glass Production Group

    PubMed Central

    Schibille, Nadine

    2011-01-01

    The chemical characterisation of archaeological glass allows the discrimination between different glass groups and the identification of raw materials and technological traditions of their production. Several lines of evidence point towards the large-scale production of first millennium CE glass in a limited number of glass making factories from a mixture of Egyptian mineral soda and a locally available silica source. Fundamental changes in the manufacturing processes occurred from the eight/ninth century CE onwards, when Egyptian mineral soda was gradually replaced by soda-rich plant ash in Egypt as well as the Islamic Middle East. In order to elucidate the supply and consumption of glass during this transitional period, 31 glass samples from the assemblage found at Pergamon (Turkey) that date to the fourth to fourteenth centuries CE were analysed by electron microprobe analysis (EPMA) and by laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS). The statistical evaluation of the data revealed that the Byzantine glasses from Pergamon represent at least three different glass production technologies, one of which had not previously been recognised in the glass making traditions of the Mediterranean. While the chemical characteristics of the late antique and early medieval fragments confirm the current model of glass production and distribution at the time, the elemental make-up of the majority of the eighth- to fourteenth-century glasses from Pergamon indicate the existence of a late Byzantine glass type that is characterised by high alumina levels. Judging from the trace element patterns and elevated boron and lithium concentrations, these glasses were produced with a mineral soda different to the Egyptian natron from the Wadi Natrun, suggesting a possible regional Byzantine primary glass production in Asia Minor. PMID:21526144

  4. Current-induced vortex motion and the vortex-glass transition in YBa{sub 2}Cu{sub 3}O{sub y} films

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

    Nojima, T.; Kakinuma, A.; Kuwasawa, Y.

    1997-12-01

    Measurements of current-voltage characteristics have been performed on YBa{sub 2}Cu{sub 3}O{sub y} films for two components of electric fields in the ab plane, E{sub x} and E{sub y}, in magnetic fields of the form (H{sub 0},H{sub 0},{delta}H{sub 0}), where x {parallel} the current density J, z {parallel} the c axis, and {delta}{lt}1. The simultaneous measurements of E{sub x} and E{sub y} under these conditions make it possible to analyze the situation of the vortex motion due to the Lorentz force. Our results indicate that vortices move as long-range correlated lines only below the glass transition temperature in a low-current limit.more » We also show that applying high-current density destroys line motion and induces a structural change of vortex lines in the glass state. {copyright} {ital 1997} {ital The American Physical Society}« less

  5. Ideal walking dynamics via a gauged NJL model

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

    Rantaharju, Jarno; Pica, Claudio; Sannino, Francesco

    According to the ideal walking technicolor paradigm, large mass anomalous dimensions arise in gauged Nambu–Jona-Lasinio (NJL) models when the four-fermion coupling is sufficiently strong to induce spontaneous symmetry breaking in an otherwise conformal gauge theory. Therefore, we study the SU(2) gauged NJL model with two adjoint fermions using lattice simulations. The model is in an infrared conformal phase at small NJL coupling while it displays a chirally broken phase at large NJL couplings. In the infrared conformal phase, we find that the mass anomalous dimension varies with the NJL coupling, reaching γm ~ 1 close to the chiral symmetry breakingmore » transition, de facto making the present model the first explicit realization of the ideal walking scenario.« less

  6. Ideal walking dynamics via a gauged NJL model

    DOE PAGES

    Rantaharju, Jarno; Pica, Claudio; Sannino, Francesco

    2017-07-25

    According to the ideal walking technicolor paradigm, large mass anomalous dimensions arise in gauged Nambu–Jona-Lasinio (NJL) models when the four-fermion coupling is sufficiently strong to induce spontaneous symmetry breaking in an otherwise conformal gauge theory. Therefore, we study the SU(2) gauged NJL model with two adjoint fermions using lattice simulations. The model is in an infrared conformal phase at small NJL coupling while it displays a chirally broken phase at large NJL couplings. In the infrared conformal phase, we find that the mass anomalous dimension varies with the NJL coupling, reaching γm ~ 1 close to the chiral symmetry breakingmore » transition, de facto making the present model the first explicit realization of the ideal walking scenario.« less

  7. Basic optical and radiation response properties of Lumilass-B fluorescent glass

    NASA Astrophysics Data System (ADS)

    Fujimoto, Yutaka; Yanagida, Takayuki

    2014-08-01

    The optical, scintillation, and dosimetric properties of Lumilass-B fluorescent glass were studied. The glass showed an ultraviolet absorption band that can be attributed to the transition from 4f7(8S7/2) ground state to the 4f65d excited state of Eu2+ ions in the glass matrix. When an X-ray excited the glass, the radioluminescence band appeared at 400 nm as in the PL spectrum. This is identified as the transition from the 5d excited state to the 4f7(8S7/2) ground state of Eu2+. The scintillation decay time under excitation with the pulsed X-ray was calculated to be about 630 ns. The irradiation dose response of the thermoluminescence (TL) and optically-stimulated luminescence (OSL) intensities was linear in the studied dose range at 0.25-200 mGy and 0.25-16 Gy, respectively.

  8. Tuning Glass Transition in Polymer Nanocomposites with Functionalized Cellulose Nanocrystals through Nanoconfinement.

    PubMed

    Qin, Xin; Xia, Wenjie; Sinko, Robert; Keten, Sinan

    2015-10-14

    Cellulose nanocrystals (CNCs) exhibit impressive interfacial and mechanical properties that make them promising candidates to be used as fillers within nanocomposites. While glass-transition temperature (Tg) is a common metric for describing thermomechanical properties, its prediction is extremely difficult as it depends on filler surface chemistry, volume fraction, and size. Here, taking CNC-reinforced poly(methyl-methacrylate) (PMMA) nanocomposites as a relevant model system, we present a multiscale analysis that combines atomistic molecular dynamics (MD) surface energy calculations with coarse-grained (CG) simulations of relaxation dynamics near filler-polymer interfaces to predict composite properties. We discover that increasing the volume fraction of CNCs results in nanoconfinement effects that lead to an appreciation of the composite Tg provided that strong interfacial interactions are achieved, as in the case of TEMPO-mediated surface modifications that promote hydrogen bonding. The upper and lower bounds of shifts in Tg are predicted by fully accounting for nanoconfinement and interfacial properties, providing new insight into tuning these aspects in nanocomposite design. Our multiscale, materials-by-design framework is validated by recent experiments and breaks new ground in predicting, without any empirical parameters, key structure-property relationships for nanocomposites.

  9. Constructing honeycomb micropatterns on nonplanar substrates with high glass transition temperature polymers.

    PubMed

    Ding, Jianyun; Gong, Jianliang; Bai, Hua; Li, Lei; Zhong, Yawen; Ma, Zhi; Svrcek, Vladimir

    2012-08-15

    In Qiao's previous report, only star polymers with T(g) (glass transition temperature) below 48°C were found forming homogeneous honeycomb coatings on the nonplanar substrates. The polymers with high T(g) are believed not able to duplicate nonplanar substrate due to their brittleness. This article presents a comprehensive study on the construction of macroporous polymeric films on various nonplanar substrates with static breath figure (BF) technique, using linear polymers with high T(g). Two kinds of linear polymers with high T(g), polystyrene-b-poly(acrylic acid) and polystyrene without polar end groups, are employed to prepare 3-dimensional macroporous films on different nonplanar substrates. Scanning electronic microscopy views on the side wall in addition to views in-plane prove that polymer films with BF array perfectly replicated the surface features of these substrates. The formation processes of macropores on these substrates are analyzed in detail, and it demonstrates that neither molecular topography nor T(g) of polymers is the critical factor contouring nonplanar substrate. A new hypothesis involving polymer plasticization and conformation during the solvent evaporation is formulated. Crown Copyright © 2012. Published by Elsevier Inc. All rights reserved.

  10. Composite Biomaterials Based on Sol-Gel Mesoporous Silicate Glasses: A Review

    PubMed Central

    Baino, Francesco; Fiorilli, Sonia; Vitale-Brovarone, Chiara

    2017-01-01

    Bioactive glasses are able to bond to bone and stimulate the growth of new tissue while dissolving over time, which makes them ideal materials for regenerative medicine. The advent of mesoporous glasses, which are typically synthesized via sol-gel routes, allowed researchers to develop a broad and versatile class of novel biomaterials that combine superior bone regenerative potential (compared to traditional melt-derived glasses) with the ability of incorporating drugs and various biomolecules for targeted therapy in situ. Mesoporous glass particles can be directly embedded as a bioactive phase within a non-porous (e.g., microspheres), porous (3D scaffolds) or injectable matrix, or be processed to manufacture a surface coating on inorganic or organic (macro)porous substrates, thereby obtaining hierarchical structures with multiscale porosity. This review provides a picture of composite systems and coatings based on mesoporous glasses and highlights the challenges for the future, including the great potential of inorganic–organic hybrid sol-gel biomaterials. PMID:28952496

  11. Structural changes during a liquid-liquid transition in the deeply undercooled Z r58.5C u15.6N i12.8A l10.3N b2.8 bulk metallic glass forming melt

    NASA Astrophysics Data System (ADS)

    Stolpe, Moritz; Jonas, Isabell; Wei, Shuai; Evenson, Zach; Hembree, William; Yang, Fan; Meyer, Andreas; Busch, Ralf

    2016-01-01

    Using high energy synchrotron x-ray radiation combined with electrostatic levitation, in situ structural analysis of a bulk metallic glass forming liquid is performed from above the liquidus temperature down to the glass transition. The data indicate a liquid-liquid transition (LLT) in the deeply undercooled state at T /Tg˜1.2 which manifests as a maximum in the heat capacity and an abrupt shift in the first peak position of the total structure factor in the absence of a pronounced density change. Analysis of the corresponding real-space data shows that the LLT involves changes in short- and medium-range order. The structural changes on the length scale of medium-range order imply a fragile-strong transition in agreement with experimental viscosity data.

  12. Scintillation and optical properties of TiO2-ZnO-Al2O3-B2O3 glasses and glass-ceramics

    NASA Astrophysics Data System (ADS)

    Usui, Yuki; Okada, Go; Kawaguchi, Noriaki; Masai, Hirokazu; Yanagida, Takayuki

    2018-04-01

    13TiO2-xZnO-17Al2O3-(70 - x)B2O3 (x = 17, 26, and 35) glasses were prepared by a melt-quenching method, and the obtained glass samples were heated at temperatures 30 °C above the glass transition temperature of corresponding glass in order to obtain glass-ceramics. The obtained glass-ceramic samples were confirmed to have anatase (x = 17) and rutile (x = 26 and 35) phases from X-ray diffraction analysis. Then, the scintillation and optical properties were evaluated and discussed the difference between the glass-ceramic and glass samples. In the scintillation spectra under X-ray irradiation, a broad emission peak was observed around 450 nm in all the samples, and the new peak around 500 nm appeared in the anatase-precipitated glass-ceramic. The intensities of the glass-ceramic samples were enhanced in comparison with the corresponding glasses because the glass-ceramics includes TiO2 crystallites with defect centers which act as effective emission centers. The scintillation decay curves of the glass and glass-ceramic samples were approximated by one and a sum of two exponential decay functions, respectively. The faster component of glass and glass-ceramic samples would be caused by the host emission, and the slower component of glass-ceramic sample would be ascribed to the emission of Ti3+.

  13. Analysis of water sorption isotherms of amorphous food materials by solution thermodynamics with relevance to glass transition: evaluation of plasticizing effect of water by the thermodynamic parameters.

    PubMed

    Shimazaki, Eriko; Tashiro, Akiko; Kumagai, Hitomi; Kumagai, Hitoshi

    2017-04-01

    Relation between the thermodynamic parameters obtained from water sorption isotherms and the degree of reduction in the glass transition temperature (T g ), accompanied by water sorption, was quantitatively studied. Two well-known glassy food materials namely, wheat gluten and maltodextrin were used as samples. The difference between the chemical potential of water in a solution and that of pure water ([Formula: see text]), the difference between the chemical potential of solid in a solution and that of a pure solid ([Formula: see text]), and the change in the integral Gibbs free energy ([Formula: see text]) were obtained by analyzing the water sorption isotherms using solution thermodynamics. The parameter [Formula: see text] correlated well with ΔT g (≡T g  - T g0 ; where T g0 is the glass transition temperature of dry material), which had been taken to be an index of plasticizing effect. This indicates that plasticizing effect of water on foods can be evaluated through the parameter [Formula: see text].

  14. Ion-conduction and rigidity/flexibility of glasses

    NASA Astrophysics Data System (ADS)

    Novita, D. I.; Boolchand, P.; Malki, M.; Micoulaut, M.

    2007-03-01

    The (AgI)x(AgPO3)1-x solid electrolyte glass system has been examined extensively although a consensus on the increase of electrical conductivity with x data has been elusive. Here we show that the variability of the data is likely due to water contamination. Our work is on specifically prepared dry samples which display glass transition temperatures Tg(x) that are at least 50 to 100 C higher than those reported hitherto. In Raman scattering the frequency of the P-Ot bonds in PO4 tetrahedra of long chains is found to systematically red-shift with increasing x, and to display thresholds near x= xc(1) =0.095(3)(stress-transition) and x =xc(2) = 0.379(5)(rigidity transition). Calorimetric measurements show a reversibility window in the 0.09 < x < 0.38 range. Room temperature electrical conductivity, σ(x), increases with x to display thresholds near xc(1) and xc(2), and a logarithmic increase at x> xc(2) with a power-law μ = 1.78(10) that is in good agreement with theoretical predictions^1. Properties of flexibility and rigidity of backbones commonplace in covalent systems^2 is a concept that extends to solid electrolyte glasses as well. ^1Richard Zallen, Physics of Amorphous Solids ^2 P. Boolchand et al. Phil. Mag 85, 3823 (2005)

  15. Mean-field theory of spin-glasses with finite coordination number

    NASA Technical Reports Server (NTRS)

    Kanter, I.; Sompolinsky, H.

    1987-01-01

    The mean-field theory of dilute spin-glasses is studied in the limit where the average coordination number is finite. The zero-temperature phase diagram is calculated and the relationship between the spin-glass phase and the percolation transition is discussed. The present formalism is applicable also to graph optimization problems.

  16. Not All Ideals are Equal: Intrinsic and Extrinsic Ideals in Relationships.

    PubMed

    Rodriguez, Lindsey M; Hadden, Benjamin W; Knee, C Raymond

    2015-03-01

    The ideal standards model suggests that greater consistency between ideal standards and actual perceptions of one's relationship predicts positive relationship evaluations; however, no research has evaluated whether this differs across types of ideals. A self-determination theory perspective was derived to test whether satisfaction of intrinsic ideals buffers the importance of extrinsic ideals. Participants (N=195) in committed relationships directly and indirectly reported the extent to which their partner met their ideal on two dimensions: intrinsic (e.g., warm, intimate) and extrinsic (e.g., attractive, successful). Relationship need fulfillment and relationship quality were also assessed. Hypotheses were largely supported, such that satisfaction of intrinsic ideals more strongly predicted relationship functioning, and satisfaction of intrinsic ideals buffered the relevance of extrinsic ideals for outcomes.

  17. Not All Ideals are Equal: Intrinsic and Extrinsic Ideals in Relationships

    PubMed Central

    Rodriguez, Lindsey M.; Hadden, Benjamin W.; Knee, C. Raymond

    2015-01-01

    The ideal standards model suggests that greater consistency between ideal standards and actual perceptions of one’s relationship predicts positive relationship evaluations; however, no research has evaluated whether this differs across types of ideals. A self-determination theory perspective was derived to test whether satisfaction of intrinsic ideals buffers the importance of extrinsic ideals. Participants (N=195) in committed relationships directly and indirectly reported the extent to which their partner met their ideal on two dimensions: intrinsic (e.g., warm, intimate) and extrinsic (e.g., attractive, successful). Relationship need fulfillment and relationship quality were also assessed. Hypotheses were largely supported, such that satisfaction of intrinsic ideals more strongly predicted relationship functioning, and satisfaction of intrinsic ideals buffered the relevance of extrinsic ideals for outcomes. PMID:25821396

  18. Thermal stability and Judd-Ofelt analysis of optical properties of Sm3+-doped sodium tellurite glasses

    NASA Astrophysics Data System (ADS)

    Mawlud, Saman Q.; Ameena, Mudhafar M.; Sahar, Md. Rahim; Mahraz, Zahra A. Said; Ahmed, Kasim Fawzy

    2017-09-01

    Series of glasses based on (70-x) TeO2 - 20Na2O - xSm2O3 (x=0, 0.3, 0.6, 1, 1.2, 1.5 mol%) have been prepared using melt-quenching technique. The nature of the glass has been confirmed using X-ray diffraction; it is found that the glass samples are amorphous in nature. The thermal stability of the glass has been determined by means of Differential Thermal Analysis (DTA). From the DTA curve, the glass transition temperature (Tg), crystallization temperature (Tc) and melting temperature (Tm) have been identified and thermal stability is also calculated. The absorption properties of these samples are obtained by using UV-Visible-NIR spectrometer, the recorded absorption spectra exhibit nine absorption transition bands peaks corresponding to the transitions from ground level 6H5/2→6P3/2, 4I11/2, 6F11/2, 6F9/2, 6F7/2, 6F5/2, 6F3/2, 6H15/2 and 6F1/2. The emission characteristic of this glass is characterized using Photoluminescence (PL) spectroscopy at excited wavelength 404 nm, the emission spectra consisted of four emission bands at 561.95 nm, 598.69 nm, 643.77 nm and 704.56 nm which were assigned as a transition 4G5/2→6H5/2, 6H7/2, 6H9/2 and 6H11/2 respectively. From f-f intensity model the experimental oscillator strengths, fexp and theoretical oscillator strength fcal were calculated. Using Judd-Ofelt theory and fit process of least square, the phenomenological intensity parameters Ωλ (λ=2,4,6) were obtained, In order to evaluate potential applications of Sm3+ ions in telluride glasses, the spectroscopic parameters: transition probability AR, branching ratio Br, radiative life time τr, emission pick cross section σλ for each band were calculated. The comparative studies with other Sm3+ doped different glasses showed that present glasses could be a potential candidate for lasers.

  19. Studies on Se75Te25-x In x chalcogenide glasses; a material for phase change memory

    NASA Astrophysics Data System (ADS)

    Srivastava, Archana; Tiwari, S. N.; Alvi, M. A.; Khan, Shamshad A.

    2018-01-01

    This research paper describes the non-isothermal crystallization during phase transformation in Se75Te25-x In x glasses synthesized by melt quenching method. For crystallization studies in these glasses, non-isothermal differential scanning calorimetry (DSC) measurements was done at constant heating rates of 5, 10, 15, 20 and 25 K min-1 in air atmosphere. The glass transition temperature (T g), on-set crystallization temperature (T c), peak crystallization temperature (T p) and melting temperatures (T m) were derived by DSC thermograms. Using various thermal parameters the activation energy of glass transition and crystallization were determined by using Kissinger, Moynihan and Ozawa approaches and found to be in good agreement. The value of the activation energy of glass transition (ΔE t) was found to be minimum for Se75Te19In6 alloys confirming its maximum probability of transition in a metastable state. Thermal stability parameters of Se75Te25-x In x were determined and found to be increased with indium content. High resolution x-ray diffraction and field emission scanning electron microscopy studies were employed for the study of phase transformation in Se75Te25-x In x glasses. The outcome of these studies shows that the investigated materials may be suitable for phase change memory devices.

  20. Silica and Germanate Glass High Power Fiber Laser Sources

    DTIC Science & Technology

    2014-01-01

    with bismuth germanate glasses. The lower phonon energy offers negligible nonradiative multiphonon relaxation of rare earth transitions up to 2.5µm...of the various emission transitions. [1] J.M.F. van Dijk, M.F.H. Schuurmans, “On the nonradiative and radiative decay rates and a modified