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Sample records for hyperquenched glassy water

  1. Structural study of low concentration LiCl aqueous solutions in the liquid, supercooled, and hyperquenched glassy states.

    PubMed

    Winkel, K; Seidl, M; Loerting, T; Bove, L E; Imberti, S; Molinero, V; Bruni, F; Mancinelli, R; Ricci, M A

    2011-01-14

    Neutron diffraction experiments on a solution of LiCl in water (R = 40) at ambient conditions and in the supercooled and hyperquenched states are reported and analyzed within the empirical potential structure refinement framework. Evidence for the modifications of the microscopic structure of the solvent in the presence of such a small amount of salt is found at all investigated thermodynamic states. On the other hand, it is evident that the structure of the hyperquenched salty sample is similar to that of pure low density amorphous water, although all the peaks of the radial distribution functions are broader in the present case. Changes upon supercooling or hyperquenching of the ion's hydration shells and contacts are of limited size and evidence for segregation phenomena at these states does not clearly show up, although the presence of water separated contacts between ion of the same sign is intriguing. PMID:21241128

  2. Pressure-induced transformations in computer simulations of glassy water

    NASA Astrophysics Data System (ADS)

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

    2013-11-01

    Glassy water occurs in at least two broad categories: low-density amorphous (LDA) and high-density amorphous (HDA) solid water. We perform out-of-equilibrium molecular dynamics simulations to study the transformations of glassy water using the ST2 model. Specifically, we study the known (i) compression-induced LDA-to-HDA, (ii) decompression-induced HDA-to-LDA, and (iii) compression-induced hexagonal ice-to-HDA transformations. We study each transformation for a broad range of compression/decompression temperatures, enabling us to construct a "P-T phase diagram" for glassy water. The resulting phase diagram shows the same qualitative features reported from experiments. While many simulations have probed the liquid-state phase behavior, comparatively little work has examined the transitions of glassy water. We examine how the glass transformations relate to the (first-order) liquid-liquid phase transition previously reported for this model. Specifically, our results support the hypothesis that the liquid-liquid spinodal lines, between a low-density and high-density liquid, are extensions of the LDA-HDA transformation lines in the limit of slow compression. Extending decompression runs to negative pressures, we locate the sublimation lines for both LDA and hyperquenched glassy water (HGW), and find that HGW is relatively more stable to the vapor. Additionally, we observe spontaneous crystallization of HDA at high pressure to ice VII. Experiments have also seen crystallization of HDA, but to ice XII. Finally, we contrast the structure of LDA and HDA for the ST2 model with experiments. We find that while the radial distribution functions (RDFs) of LDA are similar to those observed in experiments, considerable differences exist between the HDA RDFs of ST2 water and experiment. The differences in HDA structure, as well as the formation of ice VII (a tetrahedral crystal), are a consequence of ST2 overemphasizing the tetrahedral character of water.

  3. Pressure-induced transformations in computer simulations of glassy water.

    PubMed

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

    2013-11-14

    Glassy water occurs in at least two broad categories: low-density amorphous (LDA) and high-density amorphous (HDA) solid water. We perform out-of-equilibrium molecular dynamics simulations to study the transformations of glassy water using the ST2 model. Specifically, we study the known (i) compression-induced LDA-to-HDA, (ii) decompression-induced HDA-to-LDA, and (iii) compression-induced hexagonal ice-to-HDA transformations. We study each transformation for a broad range of compression/decompression temperatures, enabling us to construct a "P-T phase diagram" for glassy water. The resulting phase diagram shows the same qualitative features reported from experiments. While many simulations have probed the liquid-state phase behavior, comparatively little work has examined the transitions of glassy water. We examine how the glass transformations relate to the (first-order) liquid-liquid phase transition previously reported for this model. Specifically, our results support the hypothesis that the liquid-liquid spinodal lines, between a low-density and high-density liquid, are extensions of the LDA-HDA transformation lines in the limit of slow compression. Extending decompression runs to negative pressures, we locate the sublimation lines for both LDA and hyperquenched glassy water (HGW), and find that HGW is relatively more stable to the vapor. Additionally, we observe spontaneous crystallization of HDA at high pressure to ice VII. Experiments have also seen crystallization of HDA, but to ice XII. Finally, we contrast the structure of LDA and HDA for the ST2 model with experiments. We find that while the radial distribution functions (RDFs) of LDA are similar to those observed in experiments, considerable differences exist between the HDA RDFs of ST2 water and experiment. The differences in HDA structure, as well as the formation of ice VII (a tetrahedral crystal), are a consequence of ST2 overemphasizing the tetrahedral character of water. PMID:24320281

  4. Structural order in glassy water.

    PubMed

    Giovambattista, Nicolas; Debenedetti, Pablo G; Sciortino, Francesco; Stanley, H Eugene

    2005-06-01

    We investigate structural order in glassy water by performing classical molecular dynamics simulations using the extended simple point charge (SPC/E) model of water. We perform isochoric cooling simulations across the glass transition temperature at different cooling rates and densities. We quantify structural order by orientational and translational order metrics. Upon cooling the liquid into the glassy state, both the orientational order parameter Q and translational order parameter tau increase. At T=0 K, the glasses fall on a line in the Q-tau plane or order map. The position of this line depends only on density and coincides with the location in the order map of the inherent structures (IS) sampled upon cooling. We evaluate the energy of the IS, eIS(T), and find that both order parameters for the IS are proportional to eIS. We also study the structural order during the transformation of low-density amorphous ice (LDA) to high-density amorphous ice (HDA) upon isothermal compression and are able to identify distinct regions in the order map corresponding to these glasses. Comparison of the order parameters for LDA and HDA with those obtained upon isochoric cooling indicates major structural differences between glasses obtained by cooling and glasses obtained by compression. These structural differences are only weakly reflected in the pair correlation function. We also characterize the evolution of structural order upon isobaric annealing, leading at high pressure to very-high density amorphous ice (VHDA). PMID:16089741

  5. Hyperquenching for protein cryocrystallography

    PubMed Central

    Warkentin, Matthew; Berejnov, Viatcheslav; Husseini, Naji S.; Thorne, Robert E.

    2010-01-01

    When samples having volumes characteristic of protein crystals are plunge cooled in liquid nitrogen or propane, most cooling occurs in the cold gas layer above the liquid. By removing this cold gas layer, cooling rates for small samples and modest plunge velocities are increased to 1.5 × 104 K s−1, with increases of a factor of 100 over current best practice possible with 10 μm samples. Glycerol concentrations required to eliminate water crystallization in protein-free aqueous mixtures drop from ∼28% w/v to as low as 6% w/v. These results will allow many crystals to go from crystallization tray to liquid cryogen to X-ray beam without cryoprotectants. By reducing or eliminating the need for cryoprotectants in growth solutions, they may also simplify the search for crystallization conditions and for optimal screens. The results presented here resolve many puzzles, such as why plunge cooling in liquid nitrogen or propane has, until now, not yielded significantly better diffraction quality than gas-stream cooling. PMID:20461232

  6. Probing Properties of Glassy Water and Other Liquids with Site Selective Spectroscopies

    SciTech Connect

    Nhan Chuong Dang

    2005-08-12

    The standard non-photochemical hole burning (NPHB) mechanism, which involves phonon-assisted tunneling in the electronically excited state, was originally proposed to explain the light-induced frequency change of chemically stable molecules in glassy solids at liquid helium temperatures by this research group more than two decades ago. The NPHB mechanism was then further elucidated and the concept of intrinsic to glass configurational relaxation processes as pre-mediating step to the hole burning process was introduced. The latter provided the theoretical basis for NPHB to evolve into a powerful tool probing the dynamics and nature of amorphous media, which aside from ''simple'' inorganic glasses may include also ''complex'' biological systems such as living cells and cancerous/normal tissues. Presented in this dissertation are the experimental and theoretical results of hole burning properties of aluminum phthalocyanine tetrasulphonate (APT) in several different matrices: (1) hyperquenched glassy water (HGW); (2) cubic ice (I{sub c}); and (3) water confined into poly(2-hydroxyethylmethacrylate) (poly-HEMA). In addition, results of photochemical hole burning (PHB) studies obtained for phthalocyanine tetrasulphonate (PcT) in HGW and free base phthalocyanine (Pc) in ortho-dichlorobenzene (DCB) glass are reported. The goal of this dissertation was to provide further evidence supporting the NPHB mechanism and to provide more insight that leads to a better understanding of the kinetic events (dynamics) in glasses, and various dynamical processes of different fluorescent chromorphores in various amorphous solids and the liquid that exist above the glass transition temperature (T{sub g}). The following issues are addressed in detail: (1) time evolution of hole being burned under different conditions and in different hole burning systems; (2) temperature dependent hole profile; and (3) the structure/dynamics of water in confined space, which has been studied, in part

  7. Water sorption and diffusion in glassy polymers

    NASA Astrophysics Data System (ADS)

    Davis, Eric Mikel

    Water sorption and diffusion in glassy polymers is important in many fields, including drug delivery, desalination, energy storage and delivery, and packaging. Accurately measuring and understanding the underlying transport mechanisms of water in these glassy polymers is often complex due to both the nonequilibrium state of the polymer and the self-associating nature of water (e.g., hydrogen bonding). In this work, water sorption and diffusion in a number of glassy polymers were measured using gravimetric and spectroscopic techniques, including quartz spring microbalance, quartz crystal microbalance, and in situ time-resolved Fourier transform infrared-attenuated total reflectance (FTIR-ATR) spectroscopy. Non-Fickian diffusion was observed in all polymers studied, indicated by an initial stage of water uptake, followed by a second stage of continuous, gradual uptake of water at later experimental times. These phenomena were attributed to diffusion driven by a concentration gradient, as well as diffusion driven by slow polymer relaxation resulting in additional water ingress over time. In order to gain additional insight into these phenomena, which are a product of nonequilibrium state of the polymers, diffusion-relaxation models were developed and employed to determine the time scales for both diffusion and polymer relaxation, where the ratio of these values (Deborah number) confirmed the observed non-Fickian water diffusion. In addition, the solubility of water in these polymers was predicted using two nonequilibrium thermodynamic models: the nonequilibrium lattice fluid (NELF) model and the nonequilibrium statistical associating fluid theory (NE-SAFT), where excellent agreement between the NE-SAFT predictions and experimental data was obtained over the entire water vapor activity range explored. Furthermore, the states of water were analyzed using the Zimm-Lundberg clustering theory, as well as in situ FTIR-ATR spectroscopy, where the latter technique provides a

  8. Thermodynamics of Supercooled and Glassy Water

    NASA Astrophysics Data System (ADS)

    Debenedetti, Pablo G.

    1998-03-01

    The behavior of metastable water at low temperatures is unusual. The isothermal compressibility, the isobaric heat capacity, and the magnitude of the thermal expansion coefficient increase sharply upon supercooling, and structural relaxation becomes extremely sluggish at temperatures far above the glass transition(Angell, C.A., Annu. Rev. Phys. Chem., 34, 593, 1983)(Debenedetti, P.G., Metastable Liquids. Concepts and Principles, Princeton University Press, 1996). Water has two distinct glassy phases, low- and high-density amorphous ice (LDA, HDA). The transition between LDA and HDA is accompanied by sharp volume and enthalpy changes, and appears to be first-order(Mishima, O., L.D.Calvert, and E. Whalley, Nature, 314, 76, 1985)(Mishima, O., J. Chem. Phys., 100, 5910, 1994). The understanding of these observations in terms of an underlying global phase behavior remains incomplete(Speedy, R.J., J. Phys. Chem., 86, 982, 1982)(Poole, P.H., F. Sciortino, U. Essman, and H.E. Stanley, Nature, 360, 324, 1992)(Sastry, S., P.G. Debenedetti, F. Sciortino, and H.E. Stanley, Phys. Rev. E, 53, 6144, 1996)(Tanaka, H., Nature, 380, 328, 1996)(Xie, Y., K.F. Ludwig, G. Morales, D.E. Hare, and C.M. Sorensen, Phys. Rev. Lett., 71, 2050, 1993). Microscopic theories and computer simulations suggest several scenarios that can reproduce some experimental observations. Interesting and novel ideas have resulted from this body of theoretical work, such as the possibility of liquid-liquid immiscibility in a pure substance(Poole, P.H., F.Sciortino, T.Grande, H.E. Stanley, and C.A. Angell, Phys. Rev. Lett., 73, 1632, 1994)(Roberts, C.J., and P.G. Debenedetti, J. Chem. Phys., 105, 658, 1996)(Roberts, C.J., P.G. Debenedetti, and A.Z. Panagiotopoulos, Phys. Rev. Lett., 77, 4386, 1996)(Harrington, S., R. Zhang, P.H. Poole, F. Sciortino, and H.E. Stanley, Phys. Rev. Lett., 78, 2409, 1997). In this talk I will review the experimental facts, discuss their theoretical interpretation, and identify key

  9. Thermodynamics of water sorption in high performance glassy thermoplastic polymers

    PubMed Central

    Scherillo, Giuseppe; Petretta, Mauro; Galizia, Michele; La Manna, Pietro; Musto, Pellegrino; Mensitieri, Giuseppe

    2014-01-01

    Sorption thermodynamics of water in two glassy polymers, polyetherimide (PEI) and polyetheretherketone (PEEK), is investigated by coupling gravimetry and on line FTIR spectroscopy in order to gather information on the total amount of sorbed water as well as on the different species of water molecules absorbed within the polymers, addressing the issue of cross- and self-interactions occurring in the polymer/water systems. Water sorption isotherms have been determined at temperatures ranging from 30 to 70°C while FTIR spectroscopy has been performed only at 30°C. The experimental analysis provided information on the groups present on the polymer backbones involved in hydrogen bonding interactions with absorbed water molecules. Moreover, it also supplied qualitative indications about the different “populations” of water molecules present within the PEEK and a quantitative assessment of these “populations” in the case of PEI. The results of the experimental analysis have been interpreted using an equation of state theory based on a compressible lattice fluid model for the Gibbs energy of the polymer-water mixture, developed by extending to the case of out of equilibrium glassy polymers a previous model intended for equilibrium rubbery polymers. The model accounts for the non-equilibrium nature of glassy polymers as well as for mean field and for hydrogen bonding interactions, providing a satisfactory quantitative interpretation of the experimental data. PMID:24860802

  10. Non-Equilibrium Water-Glassy Polymer Dynamics

    NASA Astrophysics Data System (ADS)

    Davis, Eric; Minelli, Matteo; Baschetti, Marco; Sarti, Giulio; Elabd, Yossef

    2012-02-01

    For many applications (e.g., medical implants, packaging), an accurate assessment and fundamental understanding of the dynamics of water-glassy polymer interactions is of great interest. In this study, sorption and diffusion of pure water in several glassy polymers films, such as poly(styrene) (PS), poly(methyl methacrylate) (PMMA), poly(lactide) (PLA), were measured over a wide range of vapor activities and temperatures using several experimental techniques, including quartz spring microbalance (QSM), quartz crystal microbalance (QCM), and time-resolved Fourier transform infrared-attenuated total reflectance (FTIR-ATR) spectroscopy. Non-Fickian behavior (diffusion-relaxation phenomena) was observed by all three techniques, while FTIR-ATR spectroscopy also provides information about the distribution of the states of water and water transport mechanisms on a molecular-level. Specifically, the states of water are significantly different in PS compared to PMMA and PLA. Additionally, a purely predictive non-equilibrium lattice fluid (NELF) model was applied to predict the sorption isotherms of water in these glassy polymers.

  11. Liquid and Glassy Water: Two Materials of Interdisciplinary Interest

    NASA Astrophysics Data System (ADS)

    Eugene Stanley, H.

    We can superheat water above its boiling temperature and supercool it below its freezing temperature, down to approximately — 40°C, below which water inevitably crystallizes. In this deeply supercooled region, strange things happen: response functions and transport functions appear as if they might diverge to infinity at a temperature of about-45 °C. These experiments were pioneered by Angell and co-workers over the past 30 years [1-4]. Down in the glassy region of water, additional strange things happen, e.g., there is not just one glassy phase [1]. Rather, just as there is more than one polymorph of crystalline water, so also there appears to be more than one polyamorph of glassy water. The first clear indication of this was a discovery of Mishima in 1985: at low pressure there is one form, called low-density amorphous (LDA) ice [5], while at high pressure Mishima discovered a new form, called highdensity amorphous (HDA) ice [6]. The volume discontinuity separating these two phases is comparable to the volume discontinuity separating low-density and high-density polymorphs of crystalline ice, 25-35 percent [7, 8].

  12. Does water need a new Tg?

    NASA Astrophysics Data System (ADS)

    Johari, G. P.

    2002-05-01

    The basis for the conjecture that water's Tg may be 165±5 K [Velikov, Borick, and Angell, Science 294, 2335 (2001)] has been examined. It is shown that (i) differential scanning calorimetry (DSC) scans provided by Hallbrucker and Mayer [J. Phys. Chem. 91, 503 (1987)], and used as a basis for the conjecture, do not represent the heat capacity of the assumed, slow-cooled glassy water or of hyperquenched glassy water, and (ii) there is no fundamental requirement that the excess heat capacity show a peak at TTg. On heating, the enthalpy of glasses produced by hyperquenching or rapid cooling begins to decrease at a much lower T than that of the glasses obtained by slow cooling. Annealing increases this temperature toward Tg, and the enthalpy decrease continues at T above Tg. In the enthalpy relaxation region, the diffusion coefficient of the hyperquenched glassy state is higher than that of a slow-cooled glassy state at a given T, and a local minimum in the DSC scan does not appear at Twater's Tg may be ˜165 K. Several analyses confirm that the known sigmoid-shape endotherm of glassy water represents the glass-softening range with onset temperature of 136 K. The DSC scans of a glassy state similar to that of water have been simulated by using a nonlinear, nonexponential enthalpy relaxation formalism. These show that a peak in the difference scan of the simulated glass appears above its Tg of 136 K.

  13. Two Calorimetrically Distinct States of Liquid Water Below 150 Kelvin

    PubMed

    Johari; Hallbrucker; Mayer

    1996-07-01

    Vapor-deposited amorphous solid and hyperquenched glassy water were found to irreversibly transform, on compression at 77 kelvin, to a high-density amorphous solid. On heating at atmospheric pressure, this solid became viscous water (water B), with a reversible glass-liquid transition onset at 129 +/- 2 kelvin. A different form of viscous water (water A) was formed by heating the uncompressed vapor-deposited amorphous solid and hyperquenched liquid water. On thermal cycling up to 148 kelvin, water B remained kinetically and thermodynamically distinct from water A. The occurrence of these two states, which do not interconvert, helps explain both the configurational relaxation of water and stress-induced amorphization. PMID:8688057

  14. Pressure-induced transformations in glassy water: A computer simulation study using the TIP4P/2005 model

    NASA Astrophysics Data System (ADS)

    Wong, Jessina; Jahn, David A.; Giovambattista, Nicolas

    2015-08-01

    We study the pressure-induced transformations between low-density amorphous (LDA) and high-density amorphous (HDA) ice by performing out-of-equilibrium molecular dynamics (MD) simulations. We employ the TIP4P/2005 water model and show that this model reproduces qualitatively the LDA-HDA transformations observed experimentally. Specifically, the TIP4P/2005 model reproduces remarkably well the (i) structure (OO, OH, and HH radial distribution functions) and (ii) densities of LDA and HDA at P = 0.1 MPa and T = 80 K, as well as (iii) the qualitative behavior of ρ(P) during compression-induced LDA-to-HDA and decompression-induced HDA-to-LDA transformations. At the rates explored, the HDA-to-LDA transformation is less pronounced than in experiments. By studying the LDA-HDA transformations for a broad range of compression/decompression temperatures, we construct a "P-T phase diagram" for glassy water that is consistent with experiments and remarkably similar to that reported previously for ST2 water. This phase diagram is not inconsistent with the possibility of TIP4P/2005 water exhibiting a liquid-liquid phase transition at low temperatures. A comparison with previous MD simulation studies of SPC/E and ST2 water as well as experiments indicates that, overall, the TIP4P/2005 model performs better than the SPC/E and ST2 models. The effects of cooling and compression rates as well as aging on our MD simulations results are also discussed. The MD results are qualitatively robust under variations of cooling/compression rates (accessible in simulations) and are not affected by aging the hyperquenched glass for at least 1 μs. A byproduct of this work is the calculation of TIP4P/2005 water's diffusion coefficient D(T) at P = 0.1 MPa. It is found that, for T ≥ 210 K, D(T) ≈ (T - TMCT)-γ as predicted by mode coupling theory and in agreement with experiments. For TIP4P/2005 water, TMCT = 209 K and γ = 2.14, very close to the corresponding experimental values TMCT = 221 K

  15. How fast is water uptake on glassy and amorphous aerosol?

    NASA Astrophysics Data System (ADS)

    Bones, D. L.; Lienhard, D. M.; Krieger, U.; Reid, J. P.

    2011-12-01

    Atmospheric aerosol particles are typically complex mixtures of organic and inorganic species with correspondingly complex behaviour in their response to changes in humidity. Indeed, it has been recently recognised that many aerosols exist as highly viscous solutions or as amorphous glasses, rather than a crystalline state, over a wide range of relative humidities (Virtanen, et al. 2010). In this work, we investigate the formation of glassy or highly viscous phases in aqueous sugar aerosols such as sucrose and levoglucosan and aerosols of mixtures of sugars and inorganic compounds, reporting the timescale for the mass transfer of water between the particle and the gas phase with variation in water activity. Optical tweezers are used to trap single aerosol particles and examine the time-dependent response in their size to stepwise changes in RH, which result in the evaporation or condensation of water. The evolving particle size and homogeneity in composition are estimated from the wavelengths of specific resonance modes of the cavity enhanced Raman scattering spectra, deducing size changes with an accuracy of better than 1 nm. The experimental data is compared with a kinetic model of diffusional limited size change (Zobrist, et al. 2011), in which the diffusion of water within the particle bulk limits the rate of water transport between the gas and condensed phases. We report measurements in which ternary mixtures, with varying mole ratios of sucrose and sodium chloride, have allowed us to examine the water transport and response time in particle size over a wide range of bulk viscosities. Changes in size are dramatically hindered at low RH, with time scales approaching 10000s, for both increasing and decreasing RH regimes (Tong, et al. 2011). We also observe a marked relative shift in resonance modes, suggesting initial formation of a layer of water on the surface of the glassy particle and subsequent establishment of a steep concentration gradient within the

  16. Sorption of water by bidisperse mixtures of carbohydrates in glassy and rubbery states.

    PubMed

    Ubbink, Job; Giardiello, Maria-Isabelle; Limbach, Hans-Jörg

    2007-09-01

    Water sorption by bidisperse carbohydrate mixtures consisting of varying ratios of a narrow-molecular-weight distribution maltopolymer and the disaccharide maltose is investigated to establish a quantitative relation between the composition of the carbohydrate system and the water sorption isotherm. The sorption of water is approached from two limiting cases: the glassy state at low water content and the dilute aqueous carbohydrate solution. In the glassy state, the water content at a given water activity decreases with increasing maltose content of the matrix, whereas in the rubbery state it increases with increasing maltose content. The water sorption behavior in the glassy state is quantified using a variety of models, including the often-utilized but physically poorly founded Guggenheim-Anderson-de Boer model, several variants of the free-volume theory of sorption by glassy polymers, and a two-state sorption model introduced in the present paper. It is demonstrated that both the free-volume models and the two-state sorption model, which all encompass the Flory-Huggins theory for the rubbery-state sorption but which differ in their modeling of the glassy-state sorption, provide a physically consistent foundation for the analysis of water sorption by the carbohydrate matrixes. PMID:17691841

  17. Effect of water polyamorphism on the molecular vibrations of glycerol in its glassy aqueous solutions.

    PubMed

    Suzuki, Yoshiharu; Mishima, Osamu

    2016-07-14

    A glassy dilute glycerol-water solution undergoes a mutual polyamorphic transition relating to the transition between high- and low-density amorphous ices of solvent water. The polyamorphic transition behavior depends on the glycerol concentration, indicating that the glycerol affects the water polyamorphism. Here, we used the glassy dilute glycerol-water solution of the solute molar fraction of 0.07 and examined the effect of the polyamorphic change in solvent water on the molecular vibrations of glycerol via Raman spectroscopy. It is found that the molecular vibration of glycerol in high-density liquid like solvent water is different from that in the low-density liquid like solvent water and that the change in the molecular vibration of glycerol is synchronized with the polyamorphic transition of solvent water. The dynamical change of the solute molecule relates to the polyamorphic state of solvent water. This result suggests that the polyamorphic fluctuation of water structure emanated from the presumed liquid-liquid critical point plays an important role for the function of aqueous solution under an ambient condition such as the conformational stability of solute, the functional expression of solute, and so on. PMID:27421414

  18. Effect of water polyamorphism on the molecular vibrations of glycerol in its glassy aqueous solutions

    NASA Astrophysics Data System (ADS)

    Suzuki, Yoshiharu; Mishima, Osamu

    2016-07-01

    A glassy dilute glycerol-water solution undergoes a mutual polyamorphic transition relating to the transition between high- and low-density amorphous ices of solvent water. The polyamorphic transition behavior depends on the glycerol concentration, indicating that the glycerol affects the water polyamorphism. Here, we used the glassy dilute glycerol-water solution of the solute molar fraction of 0.07 and examined the effect of the polyamorphic change in solvent water on the molecular vibrations of glycerol via Raman spectroscopy. It is found that the molecular vibration of glycerol in high-density liquid like solvent water is different from that in the low-density liquid like solvent water and that the change in the molecular vibration of glycerol is synchronized with the polyamorphic transition of solvent water. The dynamical change of the solute molecule relates to the polyamorphic state of solvent water. This result suggests that the polyamorphic fluctuation of water structure emanated from the presumed liquid-liquid critical point plays an important role for the function of aqueous solution under an ambient condition such as the conformational stability of solute, the functional expression of solute, and so on.

  19. Comparing the mechanism of water condensation and evaporation in glassy aerosol

    PubMed Central

    Bones, David L.; Reid, Jonathan P.; Lienhard, Daniel M.; Krieger, Ulrich K.

    2012-01-01

    Atmospheric models generally assume that aerosol particles are in equilibrium with the surrounding gas phase. However, recent observations that secondary organic aerosols can exist in a glassy state have highlighted the need to more fully understand the kinetic limitations that may control water partitioning in ambient particles. Here, we explore the influence of slow water diffusion in the condensed aerosol phase on the rates of both condensation and evaporation, demonstrating that significant inhibition in mass transfer occurs for ultraviscous aerosol, not just for glassy aerosol. Using coarse mode (3–4 um radius) ternary sucrose/sodium chloride/aqueous droplets as a proxy for multicomponent ambient aerosol, we demonstrate that the timescale for particle equilibration correlates with bulk viscosity and can be ≫103 s. Extrapolation of these timescales to particle sizes in the accumulation mode (e.g., approximately 100 nm) by applying the Stokes-Einstein equation suggests that the kinetic limitations imposed on mass transfer of water by slow bulk phase diffusion must be more fully investigated for atmospheric aerosol. Measurements have been made on particles covering a range in dynamic viscosity from < 0.1 to > 1013 Pa s. We also retrieve the radial inhomogeneities apparent in particle composition during condensation and evaporation and contrast the dynamics of slow dissolution of a viscous core into a labile shell during condensation with the slow percolation of water during evaporation through a more homogeneous viscous particle bulk. PMID:22753520

  20. Contrasting the Evaporation and Condensation of Water from Glassy and Amorphous Aerosol Particles

    NASA Astrophysics Data System (ADS)

    Reid, J. P.; Bones, D. L.; Power, R.; Lienhard, D.; Krieger, U. K.

    2012-04-01

    The partitioning of water between the condensed and gas phases in atmospheric aerosol is usually assumed to occur instantaneously and to be regulated by solution thermodynamics. However, the persistence of high viscosity, glassy and amorphous aerosol to low relative humidity without crystallisation occurring is now widely recognised, suggesting that the timescale for water transport to or from the particle during condensation or evaporation may be significant. A kinetic limitation on water transport could have important implications for understanding hygroscopic growth measurements made on ambient particles, the ability of particles to act as ice nuclei or cloud condensation nuclei, the kinetics of chemical aging/heterogeneous chemistry, and the rate or condensation/evaporation of semi-volatile organic components. In this study we will report on measurements of the timescale of water transport to and from glassy aerosol and ultra-high viscosity solution droplets using aerosol optical tweezers to investigate the time-response of single particles to changes in relative humidity. As a benchmark system, mixed component aerosol particles containing sucrose and sodium chloride have been used; varying the mole fractions of the two solutes allows a wide range of solution viscosities to be studied. We will show that coarse particles can take many thousands of seconds to equilibrate in size and that the timescale correlates with the estimated bulk viscosity of the particle. We will also confirm that significant inhomogeneities in particle composition can be established during evaporation or condensation. Using the experimental data to benchmark a model for equilibration time, predictions can be made of the timescale for the equilibration of accumulation mode particles during water condensation or evaporation and these predictions will be described and their significance explored. Finally, the coalescence dynamics of highly viscous aerosol particles will be reported

  1. On the notion of ``1/f noise'' and data analysis for glassy water

    NASA Astrophysics Data System (ADS)

    Johari, G. P.

    2005-07-01

    It is argued that the measured dielectric loss is the sum of a background loss and a dipolar relaxation loss, and both should be considered in a dielectric spectrum analysis. The background loss can be determined by fitting a relaxation function to the spectral peak region. It is also shown that the dielectric loss tangent tanδ of glassy water, which has been rejected as "1/f noise" [A. Minoguchi, R. Richert, and C. A. Angell, Phys. Rev. Lett.93, 215703 (2004)], contains a large contribution from dipole relaxation loss, and its tanδ neither remains constant with change in f nor varies as 1/f. The incorrect attribution of water's tanδ of Minoguchi et al. puts into question the basis of their analysis.

  2. Comparing the mechanism of water condensation and evaporation in glassy aerosol.

    PubMed

    Bones, David L; Reid, Jonathan P; Lienhard, Daniel M; Krieger, Ulrich K

    2012-07-17

    Atmospheric models generally assume that aerosol particles are in equilibrium with the surrounding gas phase. However, recent observations that secondary organic aerosols can exist in a glassy state have highlighted the need to more fully understand the kinetic limitations that may control water partitioning in ambient particles. Here, we explore the influence of slow water diffusion in the condensed aerosol phase on the rates of both condensation and evaporation, demonstrating that significant inhibition in mass transfer occurs for ultraviscous aerosol, not just for glassy aerosol. Using coarse mode (3-4 um radius) ternary sucrose/sodium chloride/aqueous droplets as a proxy for multicomponent ambient aerosol, we demonstrate that the timescale for particle equilibration correlates with bulk viscosity and can be ≫10(3) s. Extrapolation of these timescales to particle sizes in the accumulation mode (e.g., approximately 100 nm) by applying the Stokes-Einstein equation suggests that the kinetic limitations imposed on mass transfer of water by slow bulk phase diffusion must be more fully investigated for atmospheric aerosol. Measurements have been made on particles covering a range in dynamic viscosity from < 0.1 to > 10(13) Pa s. We also retrieve the radial inhomogeneities apparent in particle composition during condensation and evaporation and contrast the dynamics of slow dissolution of a viscous core into a labile shell during condensation with the slow percolation of water during evaporation through a more homogeneous viscous particle bulk. PMID:22753520

  3. Hyperquenching and cold equilibration strategies for the study of liquid--liquid and protein folding transitions.

    PubMed

    Angell, C Austen; Wang, Li Min

    2003-09-01

    In this paper we consider the extension of the recent quantitative studies of hyperquenched glassformers to include (1). systems that exhibit first order liquid-liquid phase transitions, and (2). systems that contain molecules, which, during normal cooling, undergo internal structural changes above the glass temperature. The general aim of these studies is to trap-in a high enthalpy, high entropy, state of the system and then observe it evolving in time at low temperatures during a controlled annealing procedure. In this manner events that normally occur during change of temperature may be observed occurring during passage of time, at much lower temperatures. At such low temperatures the smearing effects of vibrations are greatly reduced. While the case of most interest in the second class is the refolding of thermally denatured protein molecules, any reconstructive molecular or chemical exchange process is a potential subject for investigation. Processes that occur in stages can be studied in greater detail, and any stage of interest can be frozen when desired, by drop of temperature, for more detailed spectroscopic examination. We review an electrospray method for hyperquenching liquids at approximately 10(5) K/s, and discuss some results of such experiments in order to illustrate a calorimetric approach to exploiting the hyperquenching-and- cold-equilibration strategy. To apply the idea to the study of proteins, the following protein solvent requirements must be met: (1). the solvents must not crystallize ice on cooling or heating, yet must not denature the proteins; (2). the solvents must support thermally denatured molecules without permitting aggregation. We describe two solvent systems, the first of which meets the first requirement, but the second only partially. The second solvent system apparently meets both. Preliminary results, only at the proof of concept stage, are reported for cold refolding of lysozyme, which, it seems, can be trapped in our solvent

  4. Compression-Induced Fusion of Glassy Core Polymer Micelles at the Air-Water Interface

    NASA Astrophysics Data System (ADS)

    Kim, Hyun Chang; Won, You-Yeon

    The surface mechanical and morphological properties of glassy core polymer micelles at the air-water interface were investigated. Asymmetric PS-PEG and PtBMA-PEG block copolymers with PEG weight fractions larger than 0.5 were formulated in the form of aqueous micelles and spread onto water. Compressed films of PS-PEG and PtBMA-PEG micelles reach high dynamic surface pressures. On the detailed level, however, PS-PEG and PtBMA-PEG micelles exhibit different surface pressure-area profiles. The PtBMA-PEG isotherm shows a transition to a plateau around a surface pressure of 24 mN/m, which is attributed to the PtBMA block as it forms a continuous film; this interpretation is supported by the fact that the surface pressure at the plateau transition is identical to the value of the spreading coefficient for PtBMA. This presents evidence that the core domains of PtBMA-PEG micelles melt and merge into a film when the micellar monolayer is laterally compressed. Such behavior was not observed with PS-PEG micelles. We suspect that under lateral compression, PtBMA-PEG micelles undergo fusion into a continuous film because PtBMA has the natural tendency to spread on the water surface, whereas PS-PEG micelles does not because the dewetting tendency of PS preventing formation of a uniform layer.

  5. Behavior of the Ru-bda water oxidation catalyst covalently anchored on glassy carbon electrodes

    DOE PAGESBeta

    Matheu, Roc; Francàs, Laia; Chernev, Petko; Ertem, Mehmed Z.; Batista, Victor; Haumann, Michael; Sala, Xavier; Llobet, Antoni

    2015-05-07

    Electrochemical reduction of the dizaonium complex, [RuII(bda)(NO)(N–N2)2]3+, 23+ (N–N22+ is 4-(pyridin-4-yl) benzenediazonium and bda2– is [2,2'-bipyridine]-6,6'-dicarboxylate), in acetone produces the covalent grafting of this molecular complex onto glassy carbon (GC) electrodes. Multiple cycling voltammetric experiments on the GC electrode generates hybrid materials labeled as GC-4, with the corresponding Ru-aqua complex anchored on the graphite surface. GC-4 has been characterized at pH = 7.0 by electrochemical techniques and X-ray absorption spectroscopy (XAS) and has been shown to act as an active catalyst for the oxidation of water to dioxygen. This new hybrid material has a lower catalytic performance than its counterpartmore » in homogeneous phase and progressively decomposes to form RuO2 at the electrode surface. The resulting metal oxide attached at the GC electrode surface, GC-RuO2, is a very fast and rugged heterogeneous water oxidation catalyst with TOFis of 300 s–1 and TONs >45000. The observed performance is comparable to the best electrocatalysts reported so far, at neutral pH.« less

  6. Behavior of the Ru-bda water oxidation catalyst covalently anchored on glassy carbon electrodes

    SciTech Connect

    Matheu, Roc; Francàs, Laia; Chernev, Petko; Ertem, Mehmed Z.; Batista, Victor; Haumann, Michael; Sala, Xavier; Llobet, Antoni

    2015-05-07

    Electrochemical reduction of the dizaonium complex, [RuII(bda)(NO)(N–N2)2]3+, 23+ (N–N22+ is 4-(pyridin-4-yl) benzenediazonium and bda2– is [2,2'-bipyridine]-6,6'-dicarboxylate), in acetone produces the covalent grafting of this molecular complex onto glassy carbon (GC) electrodes. Multiple cycling voltammetric experiments on the GC electrode generates hybrid materials labeled as GC-4, with the corresponding Ru-aqua complex anchored on the graphite surface. GC-4 has been characterized at pH = 7.0 by electrochemical techniques and X-ray absorption spectroscopy (XAS) and has been shown to act as an active catalyst for the oxidation of water to dioxygen. This new hybrid material has a lower catalytic performance than its counterpart in homogeneous phase and progressively decomposes to form RuO2 at the electrode surface. The resulting metal oxide attached at the GC electrode surface, GC-RuO2, is a very fast and rugged heterogeneous water oxidation catalyst with TOFis of 300 s–1 and TONs >45000. The observed performance is comparable to the best electrocatalysts reported so far, at neutral pH.

  7. Competition between water uptake and ice nucleation by glassy organic aerosol particles

    NASA Astrophysics Data System (ADS)

    Berkemeier, T.; Shiraiwa, M.; Pöschl, U.; Koop, T.

    2014-11-01

    Organic aerosol particles play a key role in climate by serving as nuclei for clouds and precipitation. Their sources and composition are highly variable, and their phase state ranges from liquid to solid under atmospheric conditions, affecting the pathway of activation to cloud droplets and ice crystals. Due to slow diffusion of water in the particle phase, organic particles may deviate in phase and morphology from their thermodynamic equilibrium state, hampering the prediction of their influence on cloud formation. We overcome this problem by combining a novel semi-empirical method for estimation of water diffusivity with a kinetic flux model that explicitly treats water diffusion. We estimate timescales for particle deliquescence as well as various ice nucleation pathways for a wide variety of organic substances, including secondary organic aerosol (SOA) from the oxidation of isoprene, α-pinene, naphthalene, and dodecane. The simulations show that, in typical atmospheric updrafts, glassy states and solid/liquid core-shell morphologies can persist for long enough that heterogeneous ice nucleation in the deposition and immersion mode can dominate over homogeneous ice nucleation. Such competition depends strongly on ambient temperature and relative humidity as well as humidification rate and particle size. Due to differences in glass transition temperature, hygroscopicity and atomic O / C ratio of the different SOA, naphthalene SOA particles have the highest potential to act as heterogeneous ice nuclei. Our findings demonstrate that kinetic limitations of water diffusion into organic aerosol particles are likely to be encountered under atmospheric conditions and can strongly affect ice nucleation pathways. For the incorporation of ice nucleation by organic aerosol particles into atmospheric models, our results demonstrate a demand for model formalisms that account for the effects of molecular diffusion and not only describe ice nucleation onsets as a function of

  8. Raman Spectroscopy of Isotopic Water Diffusion in Ultraviscous, Glassy, and Gel States in Aerosol by Use of Optical Tweezers.

    PubMed

    Davies, James F; Wilson, Kevin R

    2016-02-16

    The formation of ultraviscous, glassy, and amorphous gel states in aqueous aerosol following the loss of water results in nonequilibrium dynamics due to the extended time scales for diffusive mixing. Existing techniques for measuring water diffusion by isotopic exchange are limited by contact of samples with the substrate, and methods applied to infer diffusion coefficients from mass transport in levitated droplets requires analysis by complex coupled differential equations to derive diffusion coefficients. We present a new technique that combines contactless levitation with aerosol optical tweezers with isotopic exchange (D2O/H2O) to measure the water diffusion coefficient over a broad range (Dw ≈ 10(-12)-10(-17) m(2)·s(-1)) in viscous organic liquids (citric acid, sucrose, and shikimic acid) and inorganic gels (magnesium sulfate, MgSO4). For the organic liquids in binary and ternary mixtures, Dw depends on relative humidity and follows a simple compositional Vignes relationship. In MgSO4 droplets, water diffusivity decreases sharply with water activity and is consistent with predictions from percolation theory. These measurements show that, by combining micrometer-sized particle levitation (a contactless measurement with rapid mixing times) with an established probe of water diffusion, Dw can be simply and directly quantified for amorphous and glassy states that are inaccessible to existing methods. PMID:26751163

  9. Quantifying water diffusion in high-viscosity and glassy aqueous solutions using a Raman isotope tracer method

    NASA Astrophysics Data System (ADS)

    Price, H. C.; Murray, B. J.; Mattsson, J.; O'Sullivan, D.; Wilson, T. W.; Baustian, K. J.; Benning, L. G.

    2014-04-01

    Recent research suggests that under certain temperature and relative humidity conditions atmospheric aerosol may be present in the form of a glassy solid. In order to understand the impacts that this may have on aerosol-cloud interactions and atmospheric chemistry, knowledge of water diffusion within such aerosol particles is required. Here, a method is described in which Raman spectroscopy is used to observe D2O diffusion in high-viscosity aqueous solutions, enabling a quantitative assessment of water diffusion coefficients, Dwater, as a function of relative humidity. Results for sucrose solutions compare well with literature data at 23.5 ± 0.3 °C, and demonstrate that water diffusion is slow (Dwater ~5 × 10-17 m2 s-1), but not arrested, just below the glass transition at a water activity of 0.2. Room temperature water diffusion coefficients are also presented for aqueous levoglucosan and an aqueous mixture of raffinose, dicarboxylic acids and ammonium sulphate: at low humidity, diffusion is retarded but still occurs on millisecond to second timescales in atmospherically relevant-sized particles. The effect of gel formation on diffusion in magnesium sulfate solutions is shown to be markedly different from the gradual decrease in diffusion coefficients of highly viscous liquids. We show that using the Stokes-Einstein equation to determine diffusion timescales from viscosity leads to values which are more than 5 orders of magnitude too big, which emphasises the need to make measurements of diffusion coefficients. In addition, comparison of bounce fraction data for levoglucosan with measured diffusion data reveals that even when particles bounce the diffusion timescales for water are a fraction of a second for a 100 nm particle. This suggests a high bounce fraction does not necessarily indicate retarded water diffusion.

  10. Quantifying water diffusion in high-viscosity and glassy aqueous solutions using a Raman isotope tracer method

    NASA Astrophysics Data System (ADS)

    Price, H. C.; Murray, B. J.; Mattsson, J.; O'Sullivan, D.; Wilson, T. W.; Baustian, K. J.; Benning, L. G.

    2013-11-01

    Recent research suggests that under certain temperature and relative humidity conditions atmospheric aerosol may be present in the form of a glassy solid. In order to understand the impacts that this may have on aerosol-cloud interactions and atmospheric chemistry, knowledge of water diffusion within such aerosol particles is required. Here, a method is described in which Raman spectroscopy is used to observe D2O diffusion in high-viscosity aqueous solutions, enabling a quantitative assessment of water diffusion coefficients, Dwater, as a function of relative humidity. Results for sucrose solutions compare well with literature data at 23.5 ± 0.3 °C, and demonstrate that water diffusion is slow (Dwater~5 ×10-17m2s-1), but not arrested, just below the glass transition. Room temperature water diffusion coefficients are also presented for aqueous levoglucosan and an aqueous mixture of raffinose, dicarboxylic acids and ammonium sulphate: at low humidity, diffusion is retarded but still occurs on millisecond to second timescales in atmospherically relevant-sized particles. The effect of gel formation on diffusion in magnesium sulfate solutions is shown to be markedly different from the gradual decrease in diffusion coefficients of highly viscous liquids. We show that using the Stokes-Einstein equation to determine diffusion timescales from viscosity leads to values which are more than five orders of magnitude too big, which emphasises the need to make measurements of diffusion coefficients. In addition, comparison of bounce fraction data for levoglucosan with measured diffusion data reveals that even when particles bounce the equilibration timescales for water are a fraction of a second for a 100 nm particle. This suggests a high bounce fraction does not necessarily indicate retarded water diffusion.

  11. A simple electrochemical platform for detection of nitrobenzene in water samples using an alumina polished glassy carbon electrode.

    PubMed

    Thirumalraj, Balamurugan; Palanisamy, Selvakumar; Chen, Shen-Ming; Thangavelu, Kokulnathan; Periakaruppan, Prakash; Liu, Xiao-Heng

    2016-08-01

    In this work, we report a selective electrochemical sensing of nitrobenzene (NB) using an alumina (γ-Al2O3) polished glassy carbon electrode (GCE) for the first time. The scanning electron microscopy studies confirm the presence of alumina particles on the GCE surface. X-ray photoelectron spectroscopy studies reveal that the utilized alumina is γ-Al2O3. The alumina polished GCE shows an enhanced sensitivity and lower overpotential toward the reduction of NB compared to unpolished GCE. The differential pulse voltammetry response was used for the determination of NB and it shows that the reduction peak current of NB is linearly proportional to the concentrations of NB ranging from 0.5 to 145.5μM. The limit of detection is found to be 0.15μM based on 3σ. The fabricated electrode exhibits its appropriate selectivity towards NB in the presence of a range of nitro compounds and metal ions. The good practicality of the sensor in various water samples reveals that it can be a promising electrode material for practical applications. In addition, the proposed NB sensor is simple and cost effective one when compared with previously reported NB sensors in the literature. PMID:27163842

  12. Variabilities and uncertainties in characterising water transport kinetics in glassy and ultraviscous aerosol.

    PubMed

    Rickards, Andrew M J; Song, Young-Chul; Miles, Rachael E H; Preston, Thomas C; Reid, Jonathan P

    2015-04-21

    We present a comprehensive evaluation of the variabilities and uncertainties present in determining the kinetics of water transport in ultraviscous aerosol droplets, alongside new measurements of the water transport timescale in sucrose aerosol. Measurements are performed on individual droplets captured using aerosol optical tweezers and the change in particle size during water evaporation or condensation is inferred from shifts in the wavelength of the whispering gallery mode peaks at which spontaneous Raman scattering is enhanced. The characteristic relaxation timescale (τ) for condensation or evaporation of water from viscous droplets following a change in gas phase relative humidity can be described by the Kohlrausch-Williams-Watts function. To adequately characterise the water transport kinetics and determine τ, sufficient time must be allowed for the particle to progress towards the final state. However, instabilities in the environmental conditions can prevent an accurate characterisation of the kinetics over such long time frames. Comparison with established thermodynamic and diffusional water transport models suggests the determination of τ is insensitive to the choice of thermodynamic treatment. We report excellent agreement between experimental and simulated evaporation timescales, and investigate the scaling of τ with droplet radius. A clear increase in τ is observed for condensation with increase in drying (wait) time. This trend is qualitatively supported by model simulations. PMID:25786190

  13. Effects of plant water stress and temperature on glassy-winged sharpshooter feeding in relation to transmission of Xylella fastidiosa

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The glassy-winged sharpshooter (GWSS), Homalodisca vitripennis (Germar), is an economically important pest of grapevine, stone fruits, nursery trees, and ornamental plants in California because it transmits Xylella fastidiosa (Xf). Two related studies examined whether GWSS feeding behaviors that co...

  14. Predicting the diffusion coefficient of water vapor through glassy HPMC films at different environmental conditions using the free volume additivity approach.

    PubMed

    Laksmana, Fesia Lestari; Hartman Kok, Paul Jean Antoine; Vromans, Herman; Van der Voort Maarschalk, Kees

    2009-07-12

    Prediction of diffusion coefficient of polymer materials is important in the pharmaceutical research and becomes the aim of this paper. This paper bases the prediction method on the estimation of the polymer fractional free volume at different environmental conditions. Focussing on glassy polymers, the free volumes of polymer films were estimated using the model of Vrentas et al. [J.S. Vrentas, J.L. Duda, H.-C. Ling, Antiplasticization and volumetric behavior in glassy polymers, Macromolecules 21 (1988) 1470-1475]. The required data are the moisture sorption and glass transition temperature data, which were measured on various hydroxypropyl methylcellulose (used as a model material) free films at different water activities. The temperature and molecular weight particularly determine the free volume of the polymer, while the sorbed water can either decrease or increase the specific free volume of the polymer. At high water activity, the amount of water sorbed in the film increases to such level that the direct free volume addition by water becomes proportional to the contribution of the polymer itself. This confirms the importance of considering the environmental effect on the diffusivity of polymer during coating material selection. The presented approach enables the prediction of the diffusivity at any given relevant material variable and therefore has the potency to be used as a formulation development tool. PMID:19409985

  15. Determination of mutagenic amines in water and food samples by high pressure liquid chromatography with amperometric detection using a multiwall carbon nanotubes-glassy carbon electrode.

    PubMed

    Bueno, Ana María; Marín, Miguel Ángel; Contento, Ana María; Ríos, Ángel

    2016-02-01

    A chromatographic method, using amperometric detection, for the sensitive determination of six representative mutagenic amines was developed. A glassy carbon electrode (GCE), modified with multiwall carbon nanotubes (GCE-CNTs), was prepared and its response compared to a conventional glassy carbon electrode. The chromatographic method (HPLC-GCE-CNTs) allowed the separation and the determination of heterocyclic aromatic amines (HAAs) classified as mutagenic amines by the International Agency for Research of Cancer. The new electrode was systematically studied in terms of stability, sensitivity, and reproducibility. Statistical analysis of the obtained data demonstrated that the modified electrode provided better sensitivity than the conventional unmodified ones. Detection limits were in the 3.0 and 7.5 ng/mL range, whereas quantification limits ranged between 9.5 and 25.0 ng/mL were obtained. The applicability of the method was demonstrated by the determination of the amines in several types of samples (water and food samples). Recoveries indicate very good agreement between amounts added and those found for all HAAs (recoveries in the 92% and 105% range). PMID:26304357

  16. Sensitivity and selectivity determination of BPA in real water samples using PAMAM dendrimer and CoTe quantum dots modified glassy carbon electrode.

    PubMed

    Yin, Huanshun; Zhou, Yunlei; Ai, Shiyun; Chen, Quanpeng; Zhu, Xiangbin; Liu, Xianggang; Zhu, Lusheng

    2010-02-15

    Bisphenol A (BPA) is an environmental pollutant to disrupt endocrine system or cause cancer, thus the detection of BPA is very important. Herein, an amperometric sensor was fabricated based on immobilized CoTe quantum dots (CoTe QDs) and PAMAM dendrimer (PAMAM) onto glassy carbon electrode (GCE) surface. The cyclic voltammogram of BPA on the sensor exhibited a well-defined anodic peak at 0.490V in 0.1M pH 8.0 PBS. The determination conditions were optimized and the kinetic parameters were calculated. The linear range was 1.3 x 10(-8) to 9.89 x 10(-6)M with the correlation coefficient of 0.9999. The limit of detection was estimated to be 1 x 10(-9)M. The current reached the steady-state current within about 5s. Furthermore, the fabricated sensor was successfully applied to determine BPA in real water samples. PMID:19782469

  17. Glassy-winged sharpshooter feeding does not cause air embolisms in xylem of well-watered plants.

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Plant xylem vessels are under negative hydrostatic pressure (tension) as evapotranspiration of water from the leaf surface pulls the column of water in xylem upwards. When xylem fluid flux is under extreme tension, any puncture or breakage of the xylem vessel wall can cause formation of air embolis...

  18. The glassy wormlike chain

    NASA Astrophysics Data System (ADS)

    Kroy, Klaus; Glaser, Jens

    2007-11-01

    We introduce a new model for the dynamics of a wormlike chain (WLC) in an environment that gives rise to a rough free energy landscape, which we name the glassy WLC. It is obtained from the common WLC by an exponential stretching of the relaxation spectrum of its long-wavelength eigenmodes, controlled by a single parameter \\boldsymbol{\\cal E} . Predictions for pertinent observables such as the dynamic structure factor and the microrheological susceptibility exhibit the characteristics of soft glassy rheology and compare favourably with experimental data for reconstituted cytoskeletal networks and live cells. We speculate about the possible microscopic origin of the stretching, implications for the nonlinear rheology, and the potential physiological significance of our results.

  19. Dielectric relaxation time of bulk water at 136-140 K, background loss and crystallization effects

    NASA Astrophysics Data System (ADS)

    Johari, G. P.

    2005-04-01

    Dielectric relaxation time, τ, of ultraviscous bulk water has been determined by analyzing its loss tangent, tanδ, data, which had been measured on heating the vapor-deposited amorphous solid water and hyperquenched glassy water in our earlier studies. [Johari, Hallbrucker, and Mayer, J. Chem. Phys. 95, 2955 (1991); 97, 5851 (1992)]. As for glasses and liquids generally, the measured tanδ of water is the sum of a frequency-independent background loss and a frequency-dependent relaxational loss. A two-frequency method is provided for determining the background loss and used for obtaining the relaxational part of tanδ. After considering the structural relaxation and crystal-nuclei growth effects, τ for water has been determined. At 136±1K, it is 2.5±0.6s when a single relaxation time is (untenably) assumed, and 42±14s when a distribution of relaxation times, a characteristic of viscous liquids, is assumed, with Davidson-Cole distribution parameter of 0.75. Structural relaxation time of ˜70s for water at 136K, which was originally estimated from the DSC endotherm [Johari, Hallbrucker, and Mayer, Nature (London) 330, 552 (1987)], has been revised to ˜33s. Temperature dependence of τ could not be determined because ultraviscous water crystallizes too rapidly to cubic ice containing stacking faults and intergranular water. The study demonstrates that water is a liquid over the 136-155K range, thus removing the basis for a recent contention on its state.

  20. Protein/ionic liquid/glassy carbon sensors following analyte focusing by ionic liquid micelle collapse for simultaneous determination of water soluble vitamins in plasma matrices.

    PubMed

    Abd El-Hady, D; Albishri, H M

    2015-07-01

    Two novel sensors based on human serum albumin (HSA)-ionic liquid (IL) and bovine serum albumin (BSA)-ionic liquid (IL) composites modified glassy carbon electrode (GCE) were produced for simultaneous determination of water soluble vitamins B2, B6 and C in human plasma following analytes focusing by IL micelles collapse (AFILMC). For selective and efficient extraction, vitamins were dissolved in 3.0molL(-1) micellar solution of 1-octyl-3-methyl imidazolium bromide IL. The extracted vitamins were hydrodynamically injected by 25mbar for 20s into a running buffer of 12.5mmolL(-1) phosphate at pH 6.0 followed by electrochemical detection (ECD) on protein/1-octyl-3-methyl imidazolium hexafluorophosphate IL/GC sensors. The chemical stability of proposed sensors was achieved up to 7 days without any decomposition of PF6-based IL/protein and adsorption of interfering ions. In the current work, the sensitivity enhancement factor (SEF) up to 5000-fold was achieved using the AFILMC/ECD setup compared to conventional CE/UV. Under optimal conditions, linear calibration graphs were obtained from 0.5, 0.5 and 1.0 to 1500.0µgmL(-1) of vitamins B2, B6 and C, respectively. Detection limits of analytes were ranged from 180.0 to 520.0ngmL(-1). The proposed AFILMC/ECD setup was successfully applied to the assay of trace level quantification of vitamins in human plasma samples and also their binding constants with HSA and BSA were determined. The concurrent use of IL micelles for the proposed separation and detection processes exhibited some advantages, such as, a reduction of use toxic solvents, an efficient extraction and a direct injection of samples with a short-single run. Furthermore, IL micelles, having variable possibility of interactions, facilitated the successful achievements of AFILMC/ECD setup for the quantification of vitamins in plasma matrices. PMID:25882421

  1. Glassy correlations in nematic elastomers

    NASA Astrophysics Data System (ADS)

    Lu, Bing; Goldbart, Paul; Mao, Xiaoming

    2009-03-01

    We address the physical properties of an isotropic melt or solution of nematogenic polymers that is then cross-linked beyond the vulcanization point. To do this, we construct a replica Landau theory involving a coupled pair of order- parameter fields: one describing vulcanization, the other describing local nematic order. Thermal nematic fluctuations, present at the time of cross-linking, are trapped by cross- linking into the vulcanized network. The resulting glassy nematic fluctuations are analyzed in the Gaussian approximation in two regimes. When the localization length is shorter than the thermal nematic correlation length, the nematic correlations are well captured as glassy correlations. In the opposite regime, fluctuations in the positions of the localized polymers partially wash out the glassy nematic correlations.

  2. Glassy composition for hermetic seals

    DOEpatents

    Wilder, Jr., James A.

    1980-01-01

    The invention relates to a glassy composition adaptable for sealing to aluminum-based alloys to form a hermetically-sealed insulator body. The composition may either be employed as a glass or, after devitrifying heat treatment, as a glass-ceramic.

  3. Removal of a mixture tetracycline-tylosin from water based on anodic oxidation on a glassy carbon electrode coupled to activated sludge.

    PubMed

    Yahiaoui, Idris; Aissani-Benissad, Farida; Fourcade, Florence; Amrane, Abdeltif

    2015-01-01

    The purpose of this study was first to examine the electrochemical oxidation of two antibiotics, tetracycline (TC) and tylosin (Tylo), considered separately or in mixture, on a glassy carbon electrode in aqueous solutions; and then to assess the relevance of such electrochemical process as a pre-treatment prior to a biological treatment (activated sludge) for the removal of these antibiotics. The influence of the working potential and the initial concentration of TC and Tylo on the electrochemical pre-treatment process was also investigated. It was noticed that antibiotics degradation was favoured at high potential (2.4 V/ saturated calomel electrode (SCE)), achieving total degradation after 50 min for TC and 40 min for Tylo for 50 mg L(-1) initial concentration, with a higher mineralization efficiency in the case of TC. The biological oxygen demand in 5 days (BOD5)/Chemical oxygen demand (COD) ratio increased substantially, from 0.033 to 0.39 and from 0.038 to 0.50 for TC and Tylo, respectively. Regarding the mixture (TC and Tylo), the mineralization yield increased from 10.6% to 30.0% within 60 min of reaction time when the potential increased from 1.5 to 2.4 V/SCE and the BOD5/COD ratio increased substantially from 0.010 initially to 0.29 after 6 h of electrochemical pre-treatment. A biological treatment was, therefore, performed aerobically during 30 days, leading to an overall decrease of 72% of the dissolved organic carbon by means of the combined process. PMID:25650749

  4. How Glassy States Affect Brown Carbon Production?

    NASA Astrophysics Data System (ADS)

    Liu, P.; Li, Y.; Wang, Y.; Bateman, A. P.; Zhang, Y.; Gong, Z.; Gilles, M. K.; Martin, S. T.

    2015-12-01

    Secondary organic material (SOM) can become light-absorbing (i.e. brown carbon) via multiphase reactions with nitrogen-containing species such as ammonia and amines. The physical states of SOM, however, potentially slow the diffusion of reactant molecules in organic matrix under conditions that semisolids or solids prevail, thus inhibiting the browning reaction pathways. In this study, the physical states and the in-particle diffusivity were investigated by measuring the evaporation kinetics of both water and organics from aromatic-derived SOMs using a quartz-crystal-microbalance (QCM). The results indicate that the SOMs derived from aromatic precursors toluene and m-xylene became solid (glassy) and the in particle diffusion was significantly impeded for sufficiently low relative humidity ( < 20% RH) at 293 K. Optical properties and the AMS spectra were measured for toluene-derived SOM after ammonia exposure at varied RHs. The results suggest that the production of light-absorbing nitrogen-containing compounds from multiphase reactions with ammonia was kinetically limited in the glassy organic matrix, which otherwise produce brown carbon. The results of this study have significant implications for production and optical properties of brown carbon in urban atmospheres that ultimately influence the climate and tropospheric photochemistry.

  5. Oxidation Behavior of Glassy Alloys

    NASA Technical Reports Server (NTRS)

    Yurek, G.

    1985-01-01

    The oxidation behavior of high temperature glassy alloys produced by rapid solidification processing is investigated and the effects of processing and composition on oxidation behavior is studied. Glassy Ta-44.5at%Ir, Ta-40at%Ir-10at%B and Nb-45at%Ir oxidized rapidly at 700 to 800 C at an oxygen partial pressure of .001 atm. The alloys were embrittled during the oxidation process. No apparent oxidation or embrittlement of the Ta-Ir alloy occurred after oxidation for 4h at 500 C at an oxygen partial pressure of .001 atm. Embrittlement occurred, however, after 100h of exposure under the latter conditions. Alloy embrittlement is associated with the partial or full conversion of the metallic glass to a mixture of crystalline beta-Ta2O5 and metallic iridium. Hot compaction of glassy alloys of this type must be limited to relatively low temperatures (approx. 500 C) and short times at the low temperatures unless extremely low oxygen partial pressures can be achieved during the compaction process.

  6. Selective electrochemical detection of 2,4,6-trinitrotoluene (TNT) in water based on poly(styrene-co-acrylic acid) PSA/SiO2/Fe3O4/AuNPs/lignin-modified glassy carbon electrode.

    PubMed

    Mahmoud, Khaled A; Abdel-Wahab, Ahmed; Zourob, Mohammed

    2015-01-01

    A new versatile electrochemical sensor based on poly(styrene-co-acrylic acid) PSA/SiO2/Fe3O4/AuNPs/lignin (L-MMS) modified glassy carbon electrode (GCE) was developed for the selective detection of trace trinitrotoluene (TNT) from aqueous media with high sensitivity. The fabricated magnetic microspheres were characterized by transmission electron microscopy (TEM), energy-dispersive X-ray spectroscopy (EDS), and X-ray photoelectron spectroscopy (XPS). L-MMS films were cast on the GCE surface to fabricate the TNT sensing electrode. The limit of detection (LOD) of TNT determined by the amperometric i-t curve reached 35 pM. The lignin film and well packed Fe3O4/AuNPs facilitated the pre-concentration of trace TNT on the electrode surface resulting in a fast amperometric response of 3 seconds near the detection limit. The high sensitivity and excellent catalytic activity of the modified electrode could be attributed to the lignin layer and highly packed Fe3O4/AuNPs on the electrode surface. The total recovery of TNT from tapwater and seawater matrices was 98% and 96%, respectively. The electrode film was highly stable after five repeated adsorption/desorption cycles. The new electrochemical sensing scheme provides a highly selective, sensitive and versatile assay for the in-situ detection of TNT in complex water media. PMID:26540539

  7. Multifunctional Glassy Liquid Crystal for Photonics

    SciTech Connect

    Chen,S.H.

    2004-11-05

    As an emerging class of photonic materials, morphologically stable glassy liquid crystals, were developed following a versatile molecular design approach. Glassy cholesteric liquid crystals with elevated phase-transition temperatures and capability for selective-wavelength reflection and circular polarization were synthesized via determinstic synthesis strategies. Potential applications of glassy cholesteric liquid crystals include high-performance polarizers, optical notch filters and reflectors, and circularly polarized photoluminescence. A glassy nematic liquid crystal comprising a dithienylethene core was also synthesized for the demonstration of nondestructive rewritable optical memory and photonic switching in the sollid state.

  8. Fabrication of Bulk Glassy Alloy Foams by High Pressure Hydrogen

    NASA Astrophysics Data System (ADS)

    Wada, Takeshi; Inoue, Akihisa

    Porous Pd42.5Cu30Ni7.5P20 bulk glassy alloy rods with porosities of up to 70% were successfully prepared by high pressure hydrogen of 15 MPa. The melt of Pd42.5Cu30Ni7.5P20 alloy kept under high pressure hydrogen absorbs hydrogen and subsequent water quenching of the melt causes the homogeneous dispersion of hydrogen bubbles, which was resulted from the decrease of hydrogen solubility with decrease of pressure. Annealing the hydrogen bubble containing sample at a supercooled liquid state under vacuum, the bubbles are allowed to expand due to the decrease of viscosity of metallic glass matrix. Pores expansion continues until glassy matrix crystallizes or the equilibration among pressure of the pores, pressure of the atmosphere and surface tension is achieved. By utilizing these phenomena, pores up to 80 m in diameters are homogeneously distributed over the whole cross-sectional area of a fully glassy matrix. Under compressive deformation, the porous alloys with porosities exceeding 40% did not show macroscopic fracture in a wide compressive strain range up to 0.6 whereas the non-porous alloy fractures instantly after elastic limit of about 0.02. Porous bulk glassy alloys exhibit higher plateau stress, lower Young‧s modulus and higher energy absorption capacity compared with the conventional crystalline metal foams.

  9. Glassy features of crystal plasticity

    NASA Astrophysics Data System (ADS)

    Lehtinen, Arttu; Costantini, Giulio; Alava, Mikko J.; Zapperi, Stefano; Laurson, Lasse

    2016-08-01

    Crystal plasticity occurs by deformation bursts due to the avalanchelike motion of dislocations. Here we perform extensive numerical simulations of a three-dimensional dislocation dynamics model under quasistatic stress-controlled loading. Our results show that avalanches are power-law distributed and display peculiar stress and sample size dependence: The average avalanche size grows exponentially with the applied stress, and the amount of slip increases with the system size. These results suggest that intermittent deformation processes in crystalline materials exhibit an extended critical-like phase in analogy to glassy systems instead of originating from a nonequilibrium phase transition critical point.

  10. Large bulk soft magnetic [(Fe{sub 0.5}Co{sub 0.5}){sub 0.75}B{sub 0.20}Si{sub 0.05}]{sub 96}Nb{sub 4} glassy alloy prepared by B{sub 2}O{sub 3} flux melting and water quenching

    SciTech Connect

    Bitoh, T.; Makino, A.; Inoue, A.; Greer, A.L.

    2006-05-01

    The large bulk soft magnetic glassy [(Fe{sub 0.5}Co{sub 0.5}){sub 0.75}B{sub 0.20}Si{sub 0.05}]{sub 96}Nb{sub 4} alloy specimens with the diameters up to 7.7 mm have been prepared by water quenching the melt immersed in the molten flux of B{sub 2}O{sub 3}. The maximum diameter of the obtained specimens is approximately 1.5 times as large as the previous result for copper mold casting. The bulk specimen with 7.7 mm in diameter exhibits the saturation magnetization of 1.13 T, the coercivity lower than 20 A/m at room temperature, and the Curie temperature of 732 K. This bulk specimen is the thickest of any soft magnetic glassy alloys formed until now.

  11. Ending Aging in Super Glassy Polymer Membranes

    SciTech Connect

    Lau, CH; Nguyen, PT; Hill, MR; Thornton, AW; Konstas, K; Doherty, CM; Mulder, RJ; Bourgeois, L; Liu, ACY; Sprouster, DJ; Sullivan, JP; Bastow, TJ; Hill, AJ; Gin, DL; Noble, RD

    2014-04-16

    Aging in super glassy polymers such as poly(trimethylsilylpropyne) (PTMSP), poly(4-methyl-2-pentyne) (PMP), and polymers with intrinsic microporosity (PIM-1) reduces gas permeabilities and limits their application as gas-separation membranes. While super glassy polymers are initially very porous, and ultra-permeable, they quickly pack into a denser phase becoming less porous and permeable. This age-old problem has been solved by adding an ultraporous additive that maintains the low density, porous, initial stage of super glassy polymers through absorbing a portion of the polymer chains within its pores thereby holding the chains in their open position. This result is the first time that aging in super glassy polymers is inhibited whilst maintaining enhanced CO2 permeability for one year and improving CO2/N-2 selectivity. This approach could allow super glassy polymers to be revisited for commercial application in gas separations.

  12. Cooperative strings and glassy interfaces.

    PubMed

    Salez, Thomas; Salez, Justin; Dalnoki-Veress, Kari; Raphaël, Elie; Forrest, James A

    2015-07-01

    We introduce a minimal theory of glass formation based on the ideas of molecular crowding and resultant string-like cooperative rearrangement, and address the effects of free interfaces. In the bulk case, we obtain a scaling expression for the number of particles taking part in cooperative strings, and we recover the Adam-Gibbs description of glassy dynamics. Then, by including thermal dilatation, the Vogel-Fulcher-Tammann relation is derived. Moreover, the random and string-like characters of the cooperative rearrangement allow us to predict a temperature-dependent expression for the cooperative length ξ of bulk relaxation. Finally, we explore the influence of sample boundaries when the system size becomes comparable to ξ. The theory is in agreement with measurements of the glass-transition temperature of thin polymer films, and allows quantification of the temperature-dependent thickness hm of the interfacial mobile layer. PMID:26100908

  13. Cooperative strings and glassy interfaces

    PubMed Central

    Salez, Thomas; Salez, Justin; Dalnoki-Veress, Kari; Raphaël, Elie; Forrest, James A.

    2015-01-01

    We introduce a minimal theory of glass formation based on the ideas of molecular crowding and resultant string-like cooperative rearrangement, and address the effects of free interfaces. In the bulk case, we obtain a scaling expression for the number of particles taking part in cooperative strings, and we recover the Adam–Gibbs description of glassy dynamics. Then, by including thermal dilatation, the Vogel–Fulcher–Tammann relation is derived. Moreover, the random and string-like characters of the cooperative rearrangement allow us to predict a temperature-dependent expression for the cooperative length ξ of bulk relaxation. Finally, we explore the influence of sample boundaries when the system size becomes comparable to ξ. The theory is in agreement with measurements of the glass-transition temperature of thin polymer films, and allows quantification of the temperature-dependent thickness hm of the interfacial mobile layer. PMID:26100908

  14. Loss of halogens from crystallized and glassy silicic volcanic rocks

    USGS Publications Warehouse

    Noble, D.C.; Smith, V.C.; Peck, L.C.

    1967-01-01

    One hundred and sixty-four F and Cl analyses of silicic welded tuffs and lavas and glass separates are presented. Comparison of the F and Cl contents of crystallized rocks with those of nonhydrated glass and hydrated glassy rocks from the same rock units shows that most of the halogens originally present were lost on crystallization. An average of about half of the F and four-fifths of the Cl originally present was lost. Analyses of hydrated natural glasses and of glassy rocks indicate that in some cases significant amounts of halogens may be removed from or added to hydrated glass through prolonged contact with ground water. The data show that the original halogen contents of the groundmass of a silicic volcanic rock can be reliably determined only from nonhydrated glass. ?? 1967.

  15. Prediction of entropy and dynamic properties of water below the homogeneous nucleation temperature

    NASA Astrophysics Data System (ADS)

    Starr, Francis W.; Angell, C. Austen; Stanley, H. Eugene

    2003-05-01

    The behavior of thermodynamic and dynamic properties of liquid water at atmospheric pressure in the temperature range between the lower limit of supercooling (T H ≈ 235 K) and the onset of the glassy state at Tg has been the focus of much research, and many questions remain about the properties of water in this region. Since direct measurements on water in this temperature range remain largely infeasible, we use existing experimental measurements of the entropy, specific heat, and enthalpy outside this range to construct a possible form of the entropy in the “difficult-to-probe” region. Assuming that the entropy is well-defined in extreme metastable states, and that there is no intervening discontinuity at atmospheric pressure, we estimate the excess entropy Sex of the liquid over the crystal within relatively narrow limits. We find that our approximate form for Sex shows atypical behavior when compared with other liquids: using a thermodynamic categorization of “strong” and “fragile” liquids, water appears to be fragile on initial cooling below the melting temperature, and strong in the temperature region near the glass transition. This thermodynamic construction can be used, with appropriate reservations, to estimate the behavior of the dynamic properties of water by means of the Adam-Gibbs equation-which relates configurational entropy Sconf to dynamic behavior. Although the Adam-Gibbs equation uses Sconf rather than Sex as the control variable, the relation has been used successfully in a number of experimental studies with Sconf replaced by Sex. This is likely a result of a proportionality between Sconf and Sex, which we confirm for simulations of a model of water. Hence by using the constructed values of Sex, together with experimental data in the range where Sex is known, we estimate the temperature dependence of viscosity and diffusivity approaching the glass transition. Like the entropy plots, Arrhenius plots of viscosity or diffusion show an

  16. Molecular mobility in glassy dispersions.

    PubMed

    Mehta, Mehak; McKenna, Gregory B; Suryanarayanan, Raj

    2016-05-28

    Dielectric spectroscopy was used to characterize the structural relaxation in pharmaceutical dispersions containing nifedipine (NIF) and either poly(vinyl) pyrrolidone (PVP) or hydroxypropyl methylcellulose acetate succinate (HPMCAS). The shape of the dielectric response (permittivity versus log time) curve was observed to be independent of temperature. Thus, for the pure NIF as well as the dispersions, the validity of the time-temperature superposition principle was established. Furthermore, though the shape of the full dielectric response varied with polymer concentration, the regime related to the α- or structural relaxation was found to superimpose for the dispersions, though not with the response of the NIF itself. Hence, there is a limited time-temperature-concentration superposition for these systems as well. Therefore, in this polymer concentration range, calculation of long relaxation times in these glass-forming systems becomes possible. We found that strong drug-polymer hydrogen bonding interactions improved the physical stability (i.e., delayed crystallization) by reducing the molecular mobility. The strength of hydrogen bonding, structural relaxation time, and crystallization followed the order: NIF-PV P>NIF-HPMCAS>NIF. With an increase in polymer concentration, the relaxation times were longer indicating a decrease in molecular mobility. The temperature dependence of relaxation time, in other words fragility, was independent of polymer concentration. This is the first application of the superposition principle to characterize structural relaxation in glassy pharmaceutical dispersions. PMID:27250315

  17. Molecular mobility in glassy dispersions

    NASA Astrophysics Data System (ADS)

    Mehta, Mehak; McKenna, Gregory B.; Suryanarayanan, Raj

    2016-05-01

    Dielectric spectroscopy was used to characterize the structural relaxation in pharmaceutical dispersions containing nifedipine (NIF) and either poly(vinyl) pyrrolidone (PVP) or hydroxypropyl methylcellulose acetate succinate (HPMCAS). The shape of the dielectric response (permittivity versus log time) curve was observed to be independent of temperature. Thus, for the pure NIF as well as the dispersions, the validity of the time-temperature superposition principle was established. Furthermore, though the shape of the full dielectric response varied with polymer concentration, the regime related to the α- or structural relaxation was found to superimpose for the dispersions, though not with the response of the NIF itself. Hence, there is a limited time-temperature-concentration superposition for these systems as well. Therefore, in this polymer concentration range, calculation of long relaxation times in these glass-forming systems becomes possible. We found that strong drug-polymer hydrogen bonding interactions improved the physical stability (i.e., delayed crystallization) by reducing the molecular mobility. The strength of hydrogen bonding, structural relaxation time, and crystallization followed the order: NIF-PV P>NIF-HPMCAS>NIF. With an increase in polymer concentration, the relaxation times were longer indicating a decrease in molecular mobility. The temperature dependence of relaxation time, in other words fragility, was independent of polymer concentration. This is the first application of the superposition principle to characterize structural relaxation in glassy pharmaceutical dispersions.

  18. Crazing in Glassy Polymer Nanocomposites

    NASA Astrophysics Data System (ADS)

    Lee, Jong-Young; Zhang, Qingling; Emrick, Todd; Crosby, Alfred

    2006-03-01

    Crazing is a polymer deformation process in which dense arrays of nanoscale fibrils grow prior to the propagation of a crack. Here, we discuss experimental results on the impact of two nanostructured materials on the crazing process: 1) ordered glassy block copolymers and 2) homopolymer/nanoparticle composites. We not only find that an ordered lamellar microstructure leads a lower craze growth rate compared with polystyrene homopolymer, but also nanoscale, surface terraces significantly decrease the failure strain of these advanced materials. For homopolymer/nanoparticle composites, we discover significant alterations in the crazing process. Specifically, nanoparticles in the presence of a craze undergo three stages of rearrangement: 1) Alignment along the precraze (fluid-like region), 2) Expulsion from nanoscale craze fibrils, and 3) Assembly into clusters trapped between craze fibrils. Although nanoparticles have no effect on the initiation strain, fibril breakdown strain, and craze growth rate, the composite failure strain can be increased significantly by nearly 100% compared to neat homopolymer films. These results provide direct evidence for the physical mechanisms that control the mechanical properties of polymer nanocomposites.

  19. Active cage model of glassy dynamics.

    PubMed

    Fodor, Étienne; Hayakawa, Hisao; Visco, Paolo; van Wijland, Frédéric

    2016-07-01

    We build up a phenomenological picture in terms of the effective dynamics of a tracer confined in a cage experiencing random hops to capture some characteristics of glassy systems. This minimal description exhibits scale invariance properties for the small-displacement distribution that echo experimental observations. We predict the existence of exponential tails as a crossover between two Gaussian regimes. Moreover, we demonstrate that the onset of glassy behavior is controlled only by two dimensionless numbers: the number of hops occurring during the relaxation of the particle within a local cage and the ratio of the hopping length to the cage size. PMID:27575182

  20. Absorption Of Gases By Glassy Polymers

    NASA Technical Reports Server (NTRS)

    Fedors, Robert F.

    1990-01-01

    Report discusses solubility of gas in glassy polymer, both above and below glass-transition temperature (Tg). Thermodynamic arguments brought to bear on previously-developed mathematical models, result being new model that enables calculation of infinite-dilution partial molar volume of solvent in glass or liquid solvent from data on pressure, volume, and temperature of solute in equilibrium with solvent.

  1. On the cytoskeleton and soft glassy rheology.

    PubMed

    Mandadapu, Kranthi K; Govindjee, Sanjay; Mofrad, Mohammad R K

    2008-01-01

    The cytoskeleton is a complex structure within the cellular corpus that is responsible for the main structural properties and motilities of cells. A wide range of models have been utilized to understand cytoskeletal rheology and mechanics (see e.g. [Mofrad, M., Kamm, R., 2006. Cytoskeletal Mechanics: Models and Measurements. Cambridge University Press, Cambridge]). From this large collection of proposed models, the soft glassy rheological model (originally developed for inert soft glassy materials) has gained a certain traction in the literature due to the close resemblance of its predictions to certain mechanical data measured on cell cultures [Fabry, B., Maksym, G., Butler, J., Glogauer, M., Navajas, D., Fredberg, J., 2001. Scaling the microrheology of living cells. Physical Review Letters 87, 14102]. We first review classical linear rheological theory in a concise fashion followed by an examination of the soft glassy rheological theory. With this background we discuss the observed behavior of the cytoskeleton and the inherent limitations of classical rheological models for the cytoskeleton. This then leads into a discussion of the advantages and disadvantages presented to us by the soft glassy rheological model. We close with some comments of caution and recommendations on future avenues of exploration. PMID:18402964

  2. Movement of Glassy-Winged Sharpshooters in a Deficit Irrigated Citrus Orchard

    Technology Transfer Automated Retrieval System (TEKTRAN)

    A two-year study was conducted in a citrus orchard [Citrus sinensis (L.) Osbeck cv. ‘Valencia’] to determine the effects of plant water stress on population density and movement glassy-winged sharpshooter (GWSS), Homalodisca vitripennis (Germar). Experimental treatments included irrigation at 100% ...

  3. Plastic flow modeling in glassy polymers

    SciTech Connect

    Clements, Brad

    2010-12-13

    Glassy amorphous and semi-crystalline polymers exhibit strong rate, temperature, and pressure dependent polymeric yield. As a rule of thumb, in uniaxial compression experiments the yield stress increases with the loading rate and applied pressure, and decreases as the temperature increases. Moreover, by varying the loading state itself complex yield behavior can be observed. One example that illustrates this complexity is that most polymers in their glassy regimes (i.e., when the temperature is below their characteristic glass transition temperature) exhibit very pronounced yield in their uniaxial stress stress-strain response but very nebulous yield in their uniaxial strain response. In uniaxial compression, a prototypical glassy-polymer stress-strain curve has a stress plateau, often followed by softening, and upon further straining, a hardening response. Uniaxial compression experiments of this type are typically done from rates of 10{sup -5} s{sup -1} up to about 1 s{sup -1}. At still higher rates, say at several thousands per second as determined from Split Hopkinson Pressure Bar experiments, the yield can again be measured and is consistent with the above rule of thumb. One might expect that that these two sets of experiments should allow for a successful extrapolation to yet higher rates. A standard means to probe high rates (on the order of 105-107 S-I) is to use a uniaxial strain plate impact experiment. It is well known that in plate impact experiments on metals that the yield stress is manifested in a well-defined Hugoniot Elastic Limit (HEL). In contrast however, when plate impact experiments are done on glassy polymers, the HEL is arguably not observed, let alone observed at the stress estimated by extrapolating from the lower strain rate experiments. One might argue that polymer yield is still active but somehow masked by the experiment. After reviewing relevant experiments, we attempt to address this issue. We begin by first presenting our recently

  4. Zeolitization of glassy Topopah Spring tuff under hydrothermal conditions

    SciTech Connect

    Knauss, K.G.

    1987-01-01

    In support of the Nevada Nuclear Waste Storage Investigations Project experiments were conducted to study the effects of heat generated by a nuclear waste repository in densely welded, devitrified tuff on the underlying, compositionally-equivalent glassy tuff at Yucca Mtn. Solid wafers of glassy tuff were reacted with a dilute ground water for several months at 150{sup 0}C and 250{sup 0}C at 100 bars pressure in Dickson-type, gold-bag rocking autoclaves. The in-situ chemistry of the hydrothermal fluids was modeled and the chemical affinities for all possible mineral precipitation reactions were calculated using the EQ3/6 program. In the 250{sup 0}C experiment the calculations suggest that a zeolite mineral would be expected to form. Analyses of the run products showed that not only had the wafer been extensively corroded and the glass shards replaced by clinoptilolite, but pure clinoptilolite had precipitated directly from solution. In the 150{sup 0}C experiment, although clay minerals were thermodynamically favored to form in the first half of the experiment, by the end of the run a zeolite mineral was predicted to form. Analyses of the run products showed no well-formed secondary minerals (clays or zeolites) had formed. At the lower temperature the effects of precipitation kinetics may preclude the formation of the zeolite within the time span of this experiment. In general the observations are in relatively good agreement with the geochemical model calculations.

  5. The superconducting state parameters of glassy superconductors

    NASA Astrophysics Data System (ADS)

    Vora, Aditya M.

    2011-11-01

    We present theoretical investigations of the superconducting state parameters (SSPs), i.e. the electron-phonon coupling strength, λ, Coulomb pseudopotential, μ*, transition temperature, Tc, isotope effect exponent, α, and effective interaction strength, N0V, of glassy superconductors by employing Ashcroft's well know empty core model potential for the first time using five screening functions proposed by Hartree (H), Taylor, Ichimaru-Utsumi (IU), Farid et al and Sarkar et al. The Tc obtained from the H and IU screening functions is found to be in excellent agreement with available experimental data. Also, the present results confirm the superconducting phase in bulk metallic glass superconductors. A strong dependency of the SSPs of the glassy superconductors on the 'Z' valence is found.

  6. Glassy Spin Dynamics in Buckled Colloidal Crystal

    NASA Astrophysics Data System (ADS)

    Zhou, Di; Wang, Feng; Han, Yilong

    Geometric frustration arises when lattice structure prevents simultaneous minimization of local interaction energies. It leads to highly degenerate ground states and complex behaviors in frustrated magnetic materials. Here we experimentally studied buckled 1.5-layer colloidal NIPA microgel crystals confined between parallel plates. Spheres buckled up and down are analogous to antiferromagnetic Ising spins. These spins on the distorted triangular lattice exhibit glassy dynamics at low temperatures. In particular, a spin only has 13 nearest-neighbor configurations, which enables to reveal the correlation between structures and dynamical heterogeneity. Soft modes also localize at high-energy regions. Further, we compared the colloidal spin system with kinetic constrained models (KCMs) and observed dynamical facilitation behaviors including excitations lines in space-time. Similar structures and glassy dynamics are also observed in our simulation of Coulomb charges on a triangular lattice. The work was supported by Grant RGC-GRF601613.

  7. The viscoelastic behavior of notched glassy polymers

    NASA Technical Reports Server (NTRS)

    Crook, R. A.; Letton, Alan

    1993-01-01

    In the bulk, glassy polymers exhibit a nonlinear viscoelastic response during deformation. Stress or strain induced damage (i.e. crazing, microshear banding) results in the production of nonrecoverable work and observed nonlinearity. Stress or strain dependent shift factors have been used to mathematically model the mechanical behavior of these polymers. Glassy polymers that have been notched, may exhibit very different load displacement response compared to the same material under bulk deformation. If a sharp notch is introduced into the body then loaded, the load displacement trace may appear to be single-valued in the absence of viscoelasticity and crack growth. This suggests the volume of damaged material is small compared to the overall dimensions of the specimen. The ability to produce a single-valued load-load-line displacement trace through the use of the Correspondence Principle may prove to be useful for fracture of viscoelastic materials.

  8. Vapor Condensed and Supercooled Glassy Nanoclusters.

    PubMed

    Qi, Weikai; Bowles, Richard K

    2016-03-22

    We use molecular simulation to study the structural and dynamic properties of glassy nanoclusters formed both through the direct condensation of the vapor below the glass transition temperature, without the presence of a substrate, and via the slow supercooling of unsupported liquid nanodroplets. An analysis of local structure using Voronoi polyhedra shows that the energetic stability of the clusters is characterized by a large, increasing fraction of bicapped square antiprism motifs. We also show that nanoclusters with similar inherent structure energies are structurally similar, independent of their history, which suggests the supercooled clusters access the same low energy regions of the potential energy landscape as the vapor condensed clusters despite their different methods of formation. By measuring the intermediate scattering function at different radii from the cluster center, we find that the relaxation dynamics of the clusters are inhomogeneous, with the core becoming glassy above the glass transition temperature while the surface remains mobile at low temperatures. This helps the clusters sample the highly stable, low energy structures on the potential energy surface. Our work suggests the nanocluster systems are structurally more stable than the ultrastable glassy thin films, formed through vapor deposition onto a cold substrate, but the nanoclusters do not exhibit the superheating effects characteristic of the ultrastable glass states. PMID:26866858

  9. Wafer-level microstructuring of glassy carbon

    NASA Astrophysics Data System (ADS)

    Hans, Loïc. E.; Prater, Karin; Kilchoer, Cédric; Scharf, Toralf; Herzig, Hans Peter; Hermerschmidt, Andreas

    2014-03-01

    Glassy carbon is used nowadays for a variety of applications because of its mechanical strength, thermal stability and non-sticking adhesion properties. One application is glass molding that allows to realize high resolution diffractive optical elements on large areas and at affordable price appropriate for mass production. We study glassy carbon microstructuring for future precision compression molding of low and high glass-transition temperature. For applications in optics the uniformity, surface roughness, edge definition and lateral resolution are very important parameters for a stamp and the final product. We study different methods of microstructuring of glassy carbon by etching and milling. Reactive ion etching with different protection layers such as photoresists, aluminium and titanium hard masks have been performed and will be compare with Ion beam etching. We comment on the quality of the structure definition and give process details as well as drawbacks for the different methods. In our fabrications we were able to realize optically flat diffractive structures with slope angles of 80° at typical feature sizes of 5 micron and 700 nm depth qualified for high precision glass molding.

  10. Generation of fine hydromagmatic ash by growth and disintegration of glassy rinds

    USGS Publications Warehouse

    Mastin, L.G.

    2007-01-01

    The deposits of mafic hydromagmatic eruptions are more fine grained and variable in vesicularity than dry magmatic deposits. Blocky, equant shapes of many hydromagmatic clasts also contrast with droplet, thread, and bubble wall morphology of dry magmatic fragments. Small (glassy rinds on pyroclast surfaces as they deform within turbulent flows. This process, termed "turbulent shedding", may occur during the expansion phase of vapor explosions or during turbulent but nonexplosive mixing of magma with water, steam, or water sprays. The occurrence of turbulent shedding and the resulting fragment sizes depend on the timescale for rind growth and the timescale between disturbances that remove or disintegrate glassy rinds. Turbulent shedding is directly observable in some small littoral jets at Kilauea. Calculations suggest that, in the presence of liquid water or water sprays, glassy rinds having a thickness of microns to millimeters should form in milliseconds to seconds. This is similar to the timescale between turbulent velocity fluctuations that can shred lava globules and remove such rinds. The fraction of a deposit consisting of fine ash should increase with the duration of this process: Large-scale Surtseyan jets generate hundreds or thousands of shedding events; bubble bursts or tephra jets at Kilauea's coast may produce only a few.

  11. Glassy dislocation dynamics in colloidal dimer crystals

    NASA Astrophysics Data System (ADS)

    Gerbode, Sharon

    2012-02-01

    Dislocation mobility is central to both the mechanical response and the relaxation mechanisms of crystalline materials. Recent experiments have explored the role of novel particle anisotropies in affecting the rules of defect motion in crystals. ``Peanut-shaped'' colloidal dimer particles consisting of two connected spherical lobes form densely packed crystals in 2D. In these ``degenerate crystals,'' the particle lobes occupy triangular lattice sites while the particle axes are randomly oriented among the three crystalline directions. One consequence of the random orientations of the dimers is that dislocation glide is severely limited by certain particle arrangements in the degenerate crystals. Using optical tweezers to manipulate single lobe-sized spherical intruder particles, we locally deform the crystal, creating defects. During subsequent relaxation, the dislocations formed during the deformation leave the crystal grain, either via annihilation with other dislocations or by moving to a grain boundary. Interestingly, in large crystalline grains this dislocation relaxation occurs through a two-stage process reminiscent of slow relaxations in glassy systems, suggesting the novel concept that glassy phenomena may be introduced to certain kinds of colloidal crystals via simple anisotropic constituents.

  12. Approaching theoretical strength in glassy carbon nanolattices

    NASA Astrophysics Data System (ADS)

    Bauer, J.; Schroer, A.; Schwaiger, R.; Kraft, O.

    2016-04-01

    The strength of lightweight mechanical metamaterials, which aim to exploit material-strengthening size effects by their microscale lattice structure, has been limited by the resolution of three-dimensional lithography technologies and their restriction to mainly polymer resins. Here, we demonstrate that pyrolysis of polymeric microlattices can overcome these limitations and create ultra-strong glassy carbon nanolattices with single struts shorter than 1 μm and diameters as small as 200 nm. They represent the smallest lattice structures yet produced--achieved by an 80% shrinkage of the polymer during pyrolysis--and exhibit material strengths of up to 3 GPa, corresponding approximately to the theoretical strength of glassy carbon. The strength-to-density ratios of the nanolattices are six times higher than those of reported microlattices. With a honeycomb topology, effective strengths of 1.2 GPa at 0.6 g cm-3 are achieved. Diamond is the only bulk material with a notably higher strength-to-density ratio.

  13. Deformation and failure of glassy materials

    NASA Astrophysics Data System (ADS)

    Rottler, Joerg Gerhard

    Elastoplastic deformation of disordered solids and the formation of polymer crazes in amorphous polymer glasses are studied using large-scale molecular dynamics simulations. It is shown that the pressure-modified von Mises criterion accurately describes the maximum shear yield stress under general loading conditions. The pressure coefficient is insensitive to most model parameters, but is related to the bead geometry in analogy to friction coefficients. The yield stress decreases linearly with rising temperature and the strain rate dependence can be described by a power-law, or in a limited range, by a logarithm. The rate dependence does not vary with temperature, which is inconsistent with simple rate-state models of thermal activation such as the Eyring model. An analysis of the dynamics of the local stress distribution as well as modern phenomenological theories of rheology of glassy materials are discussed in light of these findings. We then present a comprehensive investigation of the deformation of glassy polymeric systems into a dense load-bearing network of fibrils and voids called a craze at large strains. This expansion takes place in the form of a drawing process, where the strain rate is strongly localized in a narrow interface region between dense polymer and craze. The expansion is controlled by some polymer chain segments between entanglements that are stretched taut during crazing. We also find that the distribution of tension in the craze develops an exponential force tail in close analogy to compressed jammed systems such as granular media. This highly anisotropic stress distribution and the localization of large forces on relatively few chains indicate that earlier models of the crazing process that treat the polymer as a viscous fluid with hydrodynamic interactions are incorrect. Simulations and simple scaling arguments are presented that describe craze breakdown through disentanglement or chain scission. Glassy polymers exhibit an unusually

  14. Ubiquitous ``glassy'' relaxation in catalytic reaction networks

    NASA Astrophysics Data System (ADS)

    Awazu, Akinori; Kaneko, Kunihiko

    2009-10-01

    Study of reversible catalytic reaction networks is important not only as an issue for chemical thermodynamics but also for protocells. From extensive numerical simulations and theoretical analysis, slow relaxation dynamics to sustain nonequlibrium states are commonly observed. These dynamics show two types of salient behaviors that are reminiscent of glassy behavior: slow relaxation along with the logarithmic time dependence of the correlation function and the emergence of plateaus in the relaxation-time course. The former behavior is explained by the eigenvalue distribution of a Jacobian matrix around the equilibrium state that depends on the distribution of kinetic coefficients of reactions. The latter behavior is associated with kinetic constraints rather than metastable states and is due to the absence of catalysts for chemicals in excess and the negative correlation between two chemical species. Examples are given and generality is discussed with relevance to bottleneck-type dynamics in biochemical reactions as well.

  15. Glassy dynamics of driven elastic manifolds

    SciTech Connect

    Vinokur, V.M.

    1996-12-31

    We study the low-temperature dynamics of an elastic manifold driven through a random medium. For driving forces well below the zero- temperature depinning force, the manifold advances via thermally activated hops over the energy barriers separating favorable metastable states. We develop a scaling theory of the thermally activated dynamics (creep) and find a nonlinear glassy response for the driven manifold, {upsilon}{approximately}exp(-const{times}F{sup - {mu}}). We consider an exactly solvable 1-D model for random driven dynamics which exhibits a creep-like velocity-force characteristic. We discuss a microscopic mechanism for the creep motion and show that the distribution of waiting times for the hopping processes scales as a power law. This power-law distribution naturally yields an exponential response for the creep of the manifold.

  16. Active fluidization in dense glassy systems.

    PubMed

    Mandal, Rituparno; Bhuyan, Pranab Jyoti; Rao, Madan; Dasgupta, Chandan

    2016-07-20

    Dense soft glasses show strong collective caging behavior at sufficiently low temperatures. Using molecular dynamics simulations of a model glass former, we show that the incorporation of activity or self-propulsion, f0, can induce cage breaking and fluidization, resulting in the disappearance of the glassy phase beyond a critical f0. The diffusion coefficient crosses over from being strongly to weakly temperature dependent as f0 is increased. In addition, we demonstrate that activity induces a crossover from a fragile to a strong glass and a tendency of active particles to cluster. Our results are of direct relevance to the collective dynamics of dense active colloidal glasses and to recent experiments on tagged particle diffusion in living cells. PMID:27380935

  17. Shear banding in soft glassy materials.

    PubMed

    Fielding, S M

    2014-10-01

    Many soft materials, including microgels, dense colloidal emulsions, star polymers, dense packings of multilamellar vesicles, and textured morphologies of liquid crystals, share the basic 'glassy' features of structural disorder and metastability. These in turn give rise to several notable features in the low frequency shear rheology (deformation and flow properties) of these materials: in particular, the existence of a yield stress below which the material behaves like a solid, and above which it flows like a liquid. In the last decade, intense experimental activity has also revealed that these materials often display a phenomenon known as shear banding, in which the flow profile across the shear cell exhibits macroscopic bands of different viscosity. Two distinct classes of yield stress fluid have been identified: those in which the shear bands apparently persist permanently (for as long as the flow remains applied), and those in which banding arises only transiently during a process in which a steady flowing state is established out of an initial rest state (for example, in a shear startup or step stress experiment). Despite being technically transient, such bands may in practice persist for a very long time and so be mistaken for the true steady state response of the material in experimental practice. After surveying the motivating experimental data, we describe recent progress in addressing it theoretically, using the soft glassy rheology model and a simple fluidity model. We also briefly place these theoretical approaches in the context of others in the literature, including elasto-plastic models, shear transformation zone theories, and molecular dynamics simulations. We discuss finally some challenges that remain open to theory and experiment alike. PMID:25303030

  18. Anodic electrosynthesis of some peroxy compounds on glassy carbon electrodes

    SciTech Connect

    Khomutov, N.E.; Zakhodyakina, N.A.; Svirida, L.V.; Nesvat, N.V.

    1987-11-10

    The authors present the results of a study of the anodic electrosynthesis of hydrogen peroxide and its derivatives on glassy carbon in solutions of sodium carbonate and sodium carbonate with sodium borate. We studied the kinetics of anodic processes on glassy carbon with the aid of polarization measurements and a method for determining the concentrations of active oxygen in the anolyte and the current efficiency. The current efficiencies with respect to active oxygen obtained on glassy carbon in the mixed solution of sodium borate and sodium carbonate are close to the current efficiencies which are observed on platinum anodes in the industrial electrosynthesis of perborates.

  19. Mathematical modeling of glassy-winged sharpshooter population.

    PubMed

    Yoon, Jeong-Mi; Hrynkiv, Volodymyr; Morano, Lisa; Nguyen, Anh Tuan; Wilder, Sara; Mitchell, Forrest

    2014-06-01

    Pierce's disease (PD) is a fatal disease of grapevines which results from an infection by the plant pathogen Xyllela fastidiosa. This bacterium grows in the xylem (water-conducting) vessels of the plant blocking movement of water. PD can kill vines in one year and poses a serious threat to both the California and the expanding Texas wine industries. Bacteria are vectored from one vine to the next by a number of xylem feeding insect species. Of these, the Glassy-winged Sharpshooter (GWSS) is considered to be the primary xylem feeding insect in Texas vineyards. An extensive database of the xylem-feeding population frequencies was collected by USDA-APHIS for Texas vineyards over multiple years. This project focused on a subset of data, GWSS frequencies within 25 vineyards in Edwards Plateau located in central Texas. The proposed model investigates the natural population dynamics and the decline in GWSS, likely the result of pest management campaigns on the insects within the region. The model is a delay Gompertz differential equation with harvesting and immigration terms, and we use the data to estimate the model parameters. PMID:24506556

  20. Metagenomics of Glassy-Winged Sharpshooter, Homalodisca vitripennis (Hemiptera: Cicadellidae)

    Technology Transfer Automated Retrieval System (TEKTRAN)

    A Metagenomics approach was used to identify unknown organisms which live in association with the glassy-winged sharpshooter, Homalodisca vitripennis (Hemiptera: Cicadellidae). Metagenomics combines molecular biology and genetics to identify, and characterize genetic material from unique biological ...

  1. Glassy dislocation dynamics in 2D colloidal dimer crystals.

    PubMed

    Gerbode, Sharon J; Agarwal, Umang; Ong, Desmond C; Liddell, Chekesha M; Escobedo, Fernando; Cohen, Itai

    2010-08-13

    Although glassy relaxation is typically associated with disorder, here we report on a new type of glassy dynamics relating to dislocations within 2D crystals of colloidal dimers. Previous studies have demonstrated that dislocation motion in dimer crystals is restricted by certain particle orientations. Here, we drag an optically trapped particle through such dimer crystals, creating dislocations. We find a two-stage relaxation response where initially dislocations glide until encountering particles that cage their motion. Subsequent relaxation occurs logarithmically slowly through a second process where dislocations hop between caged configurations. Finally, in simulations of sheared dimer crystals, the dislocation mean squared displacement displays a caging plateau typical of glassy dynamics. Together, these results reveal a novel glassy system within a colloidal crystal. PMID:20868079

  2. Ductile mode electrochemical oxidation assisted micromachining for glassy carbon

    NASA Astrophysics Data System (ADS)

    Nam, Eunseok; Lee, Chan-Young; Jun, Martin B. G.; Min, Byung-Kwon

    2015-04-01

    Recently, a new mechanical machining process using electrochemical oxidation was reported. Electrochemical oxidation assisted micromachining was applied to the machining of glassy carbon. The material removal process of the electrochemical oxidation assisted micromachining consists of repeated cycles of oxidation followed by removal of the oxide layer. In this paper, we experimentally investigate and compare the critical chip thickness for ductile mode cutting in mechanical machining and electrochemical oxidation assisted micromachining of glassy carbon. The theoretical critical chip thickness is calculated for mechanical machining of glassy carbon and experimentally verified. The effect of electrochemical oxidation on the critical chip thickness for ductile mode micromachining is also studied for glassy carbon. It is found that the critical chip thickness is increased for the electrochemical oxidation assisted micromachining.

  3. A structural approach to relaxation in glassy liquids

    NASA Astrophysics Data System (ADS)

    Schoenholz, S. S.; Cubuk, E. D.; Sussman, D. M.; Kaxiras, E.; Liu, A. J.

    2016-05-01

    In contrast with crystallization, there is no noticeable structural change at the glass transition. Characteristic features of glassy dynamics that appear below an onset temperature, T0 (refs ,,), are qualitatively captured by mean field theory, which assumes uniform local structure. Studies of more realistic systems have found only weak correlations between structure and dynamics. This raises the question: is structure important to glassy dynamics in three dimensions? We answer this question affirmatively, using machine learning to identify a new field, `softness' which characterizes local structure and is strongly correlated with dynamics. We find that the onset of glassy dynamics at T0 corresponds to the onset of correlations between softness (that is, structure) and dynamics. Moreover, we construct a simple model of relaxation that agrees well with our simulation results, showing that a theory of the evolution of softness in time would constitute a theory of glassy dynamics.

  4. No inherent glassiness in a Penrose tiling quasicrystal

    SciTech Connect

    Strandburg, K.J.; Dressel, P.R.

    1988-11-01

    Consideration of the structure of the Penrose pattern has led to speculation that a system with a Penrose tiling ground state might be subject to inherent glassy behavior. Monte Carol simulations show, using a simple model of the energetics, that there is no inherent glassiness in the Penrose tiling. Thermodynamic quantities measured are completely reversible, displaying no observable hysterisis, and the system may be easily cooled from a highly disordered configuration into its lowest energy state. 11 refs., 7 figs.

  5. Lithium ion diffusion through glassy carbon plate

    SciTech Connect

    Inaba, M.; Nohmi, S.; Funabiki, A.; Abe, T.; Ogumi, Z.

    1998-07-01

    The electrochemical permeation method was applied to the determination of the diffusion coefficient of Li{sup +} ion (D{sub Li{sup +}}) in a glassy carbon (GC) plate. The cell was composed of two compartments, which were separated by the GC plate. Li{sup +} ions were inserted electrochemically from one face, and extracted from the other. The flux of the permeated Li{sup +} ions was monitored as an oxidation current at the latter face. The diffusion coefficient was determined by fitting the transient current curve with a theoretical one derived from Fick's law. When the potential was stepped between two potentials in the range of 0 to 0.5 V, transient curves were well fitted with the theoretical one, which gave D{sub Li{sup +}} values on the order of 10{sup {minus}8} cm{sup {minus}2} s{sup {minus}1}. In contrast, when the potential was stepped between two potentials across 0.5 V, significant deviation was observed. The deviation indicated the presence of trap sites as well as diffusion sites for Li{sup +} ions, the former of which is the origin of the irreversible capacity of GC.

  6. Structural Properties of Defects in Glassy Liquids.

    PubMed

    Cubuk, Ekin D; Schoenholz, Samuel S; Kaxiras, Efthimios; Liu, Andrea J

    2016-07-01

    At zero temperature a disordered solid corresponds to a local minimum in the energy landscape. As the temperature is raised or the system is driven with a mechanical load, the system explores different minima via dynamical events in which particles rearrange their relative positions. We have shown recently that the dynamics of particle rearrangements are strongly correlated with a structural quantity associated with each particle, "softness", which we can identify using supervised machine learning. Particles of a given softness have a well-defined energy scale that governs local rearrangements; because of this property, softness greatly simplifies our understanding of glassy dynamics. Here we investigate the correlation of softness with other commonly used structural quantities, such as coordination number and local potential energy. We show that although softness strongly correlates with these properties, its predictive power for rearrangement dynamics is much higher. We introduce a useful metric for quantifying the quality of structural quantities as predictors of dynamics. We hope that, in the future, authors introducing new structural measures of dynamics will compare their proposals quantitatively to softness using this metric. We also show how softness correlations give insight into rearrangements. Finally, we explore the physical meaning of softness using unsupervised dimensionality reduction and reduced curve-fitting models, and show that softness can be recast in a form that is amenable to analytical treatment. PMID:27092716

  7. Dispersal and Movement of the Glassy-winged Sharpshooter and Associated Natural Enemies in a Continuous, Deficit-irrigated Agricultural Landscape

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Host-plant water status is thought to influence dispersal of the glassy-winged sharpshooter (GWSS). Preference of adult GWSS for citrus plants maintained under different water deficit regimes was studied under laboratory and field conditions. In laboratory studies, settling and oviposition prefere...

  8. Shear banding in soft glassy materials

    NASA Astrophysics Data System (ADS)

    Fielding, S. M.

    2014-10-01

    Many soft materials, including microgels, dense colloidal emulsions, star polymers, dense packings of multilamellar vesicles, and textured morphologies of liquid crystals, share the basic ‘glassy’ features of structural disorder and metastability. These in turn give rise to several notable features in the low frequency shear rheology (deformation and flow properties) of these materials: in particular, the existence of a yield stress below which the material behaves like a solid, and above which it flows like a liquid. In the last decade, intense experimental activity has also revealed that these materials often display a phenomenon known as shear banding, in which the flow profile across the shear cell exhibits macroscopic bands of different viscosity. Two distinct classes of yield stress fluid have been identified: those in which the shear bands apparently persist permanently (for as long as the flow remains applied), and those in which banding arises only transiently during a process in which a steady flowing state is established out of an initial rest state (for example, in a shear startup or step stress experiment). Despite being technically transient, such bands may in practice persist for a very long time and so be mistaken for the true steady state response of the material in experimental practice. After surveying the motivating experimental data, we describe recent progress in addressing it theoretically, using the soft glassy rheology model and a simple fluidity model. We also briefly place these theoretical approaches in the context of others in the literature, including elasto-plastic models, shear transformation zone theories, and molecular dynamics simulations. We discuss finally some challenges that remain open to theory and experiment alike.

  9. Dynamical Heterogeneity of the Glassy State

    NASA Astrophysics Data System (ADS)

    Wisitsorasak, Apiwat

    The understanding and the complete description of the glass transition are impeded by the complexity of nature of the glass. Parts of this complexity come from the emergence of long-lived inherent structures of a liquid at a temperature below which the activated reconfiguration events play a dominant role. Molecules in a glass change their locations through the activated process at a rate which varies throughout the glass owing to these local and aperiodic structures. Motions in one location also cause or relieve constrains, thereby altering the rate of transitions of neighboring regions. The key to understanding this problem is the interplay between the activated events that generate mobility and the transport of mobility. In the following we explore fluctuating mobility generation and transport in glasses to understand the dynamics of the glassy state within the framework of the random first order transition theory of glass. Fluctuating mobility generation and transport in the glass that arise from there being a distribution of local stability and thus effective temperature are treated by numerically solving stochastic continuum equations for mobility and fictive temperature fields. Fluctuating spatiotemporal structures in aging and rejuvenating glasses lead to dynamical heterogeneity in glasses with characteristics that are distinct from those found in the equilibrium liquid. We illustrate in this thesis how the heterogeneity in glasses gives rises of a non-Gaussian distribution of activation free energies, the stretching exponent, and the growth of characteristic lengths. These are studied along with the four-point dynamic correlation function. Asymmetric thermodynamic responses upon heating and cooling are also predicted to be the results of the heterogeneity and the out-of-equilibrium behavior of glasses below the glass transition temperature. Moreover the dynamical heterogeneity can lead to a growth front of mobility in rejuvenating glasses that emanates

  10. Optical speckles of blood proteins embedded in porous glassy substrate

    NASA Astrophysics Data System (ADS)

    Holden, T.; Dehipawala, S.; Kokkinos, D.; Berisha, A.; Cheung, E.; Nguyen, A.; Golebiewska, U.; Schneider, P.; Tremberger, G., Jr.; Lieberman, D.; Cheung, T.

    2012-03-01

    Blood protein molecules could be embedded in porous glassy substrate with 10-nm pores. The embedding principle is based on blood cell dehydration with the destruction of the cell membrane, and reconstitution and centrifuge could yield a suitable solution for doping into a porous glassy medium. The doped glassy substrate speckle pattern under laser illumination could be used to characterize the protein size distribution. Calibration with known protein embedded samples would result in an optical procedure for the characterization of a blood sample. Samples embedded with larger kilo-Dalton protein molecule show more variation in the speckle patterns, consistent with protein folding interaction inside a pore cavity. A regression model has been used to correlate the protein molecule sizes with speckle sizes. The use of diffusion mean free path information to study protein folding in the embedding process is briefly discussed.

  11. Solubility of gases and liquids in glassy polymers.

    PubMed

    De Angelis, Maria Grazia; Sarti, Giulio C

    2011-01-01

    This review discusses a macroscopic thermodynamic procedure to calculate the solubility of gases, vapors, and liquids in glassy polymers that is based on the general procedure provided by the nonequilibrium thermodynamics for glassy polymers (NET-GP) method. Several examples are presented using various nonequilibrium (NE) models including lattice fluid (NELF), statistical associating fluid theory (NE-SAFT), and perturbed hard sphere chain (NE-PHSC). Particular applications illustrate the calculation of infinite-dilution solubility coefficients in different glassy polymers and the prediction of solubility isotherms for different gases and vapors in pure polymers as well as in polymer blends. The determination of model parameters is discussed, and the predictive abilities of the models are illustrated. Attention is also given to the solubility of gas mixtures and solubility isotherms in nanocomposite mixed matrices. The fractional free volume determined from solubility data can be used to correlate solute diffusivities in mixed matrices. PMID:22432612

  12. The Erevan howardite: Petrology of glassy clasts and mineral chemistry

    NASA Technical Reports Server (NTRS)

    Nazarov, M. A.; Ariskin, A. A.

    1993-01-01

    The Erevan howardite is a polymict regolith breccia containing xenoliths of carbonaceous chondrites. In this work, we studied glassy clasts, which could be considered as primary quenched melts, and mineral chemistry of the breccia. The study reveals that the Erevan howardite consists of common rocks of the HED suite. However, unique glassy clasts, which are present in some eucritic melts, were identified. The mineral chemistry and the simulation of crystallization of the melts suggest that the compositions of the melts reflect those of some primary lithologies of EPB.

  13. Behavior of nuclear waste elements during hydrothermal alteration of glassy rhyolite in an active geothermal system: Yellowstone National Park, Wyoming

    SciTech Connect

    Sturchio, N.C.; Seitz, M.G.

    1984-12-31

    The behavior of a group of nuclear waste elements (U, Th, Sr, Zr, Sb, Cs, Ba, and Sm) during hydrothermal alteration of glassy rhyolite is investigated through detailed geochemical analyses of whole rocks, glass and mineral separates, and thermal waters. Significant mobility of U, Sr, Sb, Cs, and Ba is found, and the role of sorption processes in their observed behavior is identified. Th, Zr, and Sm are relatively immobile, except on a microscopic scale. 9 references, 2 figures, 2 tables.

  14. Aryl Diazonium Chemistry for the Surface Functionalization of Glassy Biosensors.

    PubMed

    Zheng, Wei; van den Hurk, Remko; Cao, Yong; Du, Rongbing; Sun, Xuejun; Wang, Yiyu; McDermott, Mark T; Evoy, Stephane

    2016-03-01

    Nanostring resonator and fiber-optics-based biosensors are of interest as they offer high sensitivity, real-time measurements and the ability to integrate with electronics. However, these devices are somewhat impaired by issues related to surface modification. Both nanostring resonators and photonic sensors employ glassy materials, which are incompatible with electrochemistry. A surface chemistry approach providing strong and stable adhesion to glassy surfaces is thus required. In this work, a diazonium salt induced aryl film grafting process is employed to modify a novel SiCN glassy material. Sandwich rabbit IgG binding assays are performed on the diazonium treated SiCN surfaces. Fluorescently labelled anti-rabbit IgG and anti-rabbit IgG conjugated gold nanoparticles were used as markers to demonstrate the absorption of anti-rabbit IgG and therefore verify the successful grafting of the aryl film. The results of the experiments support the effectiveness of diazonium chemistry for the surface functionalization of SiCN surfaces. This method is applicable to other types of glassy materials and potentially can be expanded to various nanomechanical and optical biosensors. PMID:26985910

  15. The nonequilibrium glassy dynamics of self-propelled particles.

    PubMed

    Flenner, Elijah; Szamel, Grzegorz; Berthier, Ludovic

    2016-09-14

    We study the glassy dynamics taking place in dense assemblies of athermal active particles that are driven solely by a nonequilibrium self-propulsion mechanism. Active forces are modeled as an Ornstein-Uhlenbeck stochastic process, characterized by a persistence time and an effective temperature, and particles interact via a Lennard-Jones potential that yields well-studied glassy behavior in the Brownian limit, which is obtained as the persistence time vanishes. By increasing the persistence time, the system departs more strongly from thermal equilibrium and we provide a comprehensive numerical analysis of the structure and dynamics of the resulting active fluid. Finite persistence times profoundly affect the static structure of the fluid and give rise to nonequilibrium velocity correlations that are absent in thermal systems. Despite these nonequilibrium features, for any value of the persistence time we observe a nonequilibrium glass transition as the effective temperature is decreased. Surprisingly, increasing departure from thermal equilibrium is found to promote (rather than suppress) the glassy dynamics. Overall, our results suggest that with increasing persistence time, microscopic properties of the active fluid change quantitatively, but the general features of the nonequilibrium glassy dynamics observed with decreasing the effective temperature remain qualitatively similar to those of thermal glass-formers. PMID:27499055

  16. Aryl Diazonium Chemistry for the Surface Functionalization of Glassy Biosensors

    PubMed Central

    Zheng, Wei; van den Hurk, Remko; Cao, Yong; Du, Rongbing; Sun, Xuejun; Wang, Yiyu; McDermott, Mark T.; Evoy, Stephane

    2016-01-01

    Nanostring resonator and fiber-optics-based biosensors are of interest as they offer high sensitivity, real-time measurements and the ability to integrate with electronics. However, these devices are somewhat impaired by issues related to surface modification. Both nanostring resonators and photonic sensors employ glassy materials, which are incompatible with electrochemistry. A surface chemistry approach providing strong and stable adhesion to glassy surfaces is thus required. In this work, a diazonium salt induced aryl film grafting process is employed to modify a novel SiCN glassy material. Sandwich rabbit IgG binding assays are performed on the diazonium treated SiCN surfaces. Fluorescently labelled anti-rabbit IgG and anti-rabbit IgG conjugated gold nanoparticles were used as markers to demonstrate the absorption of anti-rabbit IgG and therefore verify the successful grafting of the aryl film. The results of the experiments support the effectiveness of diazonium chemistry for the surface functionalization of SiCN surfaces. This method is applicable to other types of glassy materials and potentially can be expanded to various nanomechanical and optical biosensors. PMID:26985910

  17. MODELING GLASSY-WINGED SHARPSHOOTER PHENOLOGY AND PIERCE'S DISEASE INCIDENCE

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Insect, plant, and bacterial growth are all regulated by environmental factors, such as temperature. Consequently, climate plays an important role in the: 1) ability of glassy winged sharpshooter (GWSS) to survive the winter, 2) development of GWSS populations throughout the year, and 3) propensity...

  18. A method to quantify glassy-winged sharpshooter egg maturation

    Technology Transfer Automated Retrieval System (TEKTRAN)

    To identify factors affecting glassy-winged sharpshooter egg production, a method to accurately estimate the number of mature eggs produced during a short-term assay is needed. Egg production is typically quantified by determining the number of eggs deposited during the assay plus the number of matu...

  19. Immunological detection of glassy-winged sharpshooter saliva in grapevine

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Glassy-winged sharpshooter (GWSS), Homalodisca vitripennis, is a major vector for transmission of Xylella fastidiosa (Xf), the causative agent of Pierce’s Disease in grapevine. During the feeding process of stylet penetration and xylem fluid ingestion, GWSS inject saliva into the plant. Inoculation...

  20. A comparison of specific surface area and crystallization kinetics in compact and porous amorphous solid water

    NASA Astrophysics Data System (ADS)

    Herrero, V. J.; Mate, B.; Roriguez-Lazcano, Y.; Galvez, O.; Moreno, M. A.; Escribano, R. M.

    2011-12-01

    In astronomical ices, both compact and porous morphologies can be expected depending on the particular ice history [1]. These different morphologies might be relevant for the interpretation of astronomical observations as demonstrated in recent works [2], where the characteristic ν4 band of NH4+ at 6.85 μm, used in tentative identifications of this ion in astronomical observations, was shown to broaden and virtually disappear, when embedded in compact ice samples. In this work we present a more detailed characterization of the compact ices used in ref. [2], which are produced in the laboratory through the sudden freezing of water droplets on a cold substrate, a procedure similar to that reported by Loerting et al. [3] for the generation of hyperquenched (HQ) glassy water. The present study is based on infrared (IR) vibrational spectroscopy measurements of the solids. The compactness, specific surface area (SSA), and crystallization kinetics of the HQ samples is compared to that of vapour deposited (VD) ices. SSA values are estimated from the isothermal adsorption of CH4 and CO2 at 40 and 90 K. The rates of crystallization are determined at several temperatures up to 150 K by monitoring the position and width of the OD stretching band of isolated HDO molecules in ice samples with a 4% HDO content (see ref. [4] for a previous application of the method). From these experiments we derive the conclusions that follow. The much higher porosity of the VD samples is immediately evidenced by the IR absorption peak of uncoordinated OH dangling bonds, which is practically absent in the HQ ices. The SSA values for the HQ ices are about one order of magnitude lower than those for VD ices, and likewise, the rates of crystallization, are also found to be lower in HQ than in VD ices. These results, and their likely astrophysical implications, will be discussed at the conference. This work has been funded by the Spanish Ministry of Science under Grants FIS2007-61686 and FIS2010

  1. Electrochemical behavior of triflusal, aspirin and their metabolites at glassy carbon and boron doped diamond electrodes.

    PubMed

    Enache, Teodor Adrian; Fatibello-Filho, Orlando; Oliveira-Brett, Ana Maria

    2010-08-01

    The electrochemical behavior of triflusal (TRF) and aspirin (ASA), before and after hydrolysis in water and in alkaline medium using two different electrode surfaces, glassy carbon and boron doped diamond, was study by differential pulse voltammetry over a wide pH range. The hydrolysis products are 2-(hydroxyl)-4-(trifluoromethyl)-benzoic acid (HTB) for triflusal and salicylic acid (SA) for aspirin, which in vivo represent their main metabolites. The hydrolysis processes were also followed by spectrophotometry. The UV results showed complete hydrolysis after one hour for TRF and after two hours for ASA in alkaline solution. The glassy carbon electrode enables only indirect determination of TRF and ASA through the electrochemical detection of their hydrolysis products HTB and SA, respectively. The oxidation processes of HTB and SA are pH dependent and involve different numbers of electrons and protons. Moreover, the difference between the oxidation peak potential of SA and HTB was equal to 100 mV in the studied pH range from 1 to 8 due to the CF3 of the aromatic ring of HTB molecule. Due to its wider oxidation potential range, the boron doped diamond electrode was used to study the direct oxidation of TRF and ASA, as well as of their respective metabolites HTB and SA. PMID:20402644

  2. 2H NMR studies of supercooled and glassy aspirin

    NASA Astrophysics Data System (ADS)

    Nath, R.; Nowaczyk, A.; Geil, B.; Bohmer, R.

    2007-11-01

    Acetyl salicylic acid, deuterated at the methyl group, was investigated using 2H-NMR in its supercooled and glassy states. Just above the glass transition temperature the molecular reorientations were studied using stimulated-echo spectroscopy and demonstrated a large degree of similarity with other glass formers. Deep in the glassy phase the NMR spectra look similar to those reported for the crystal [A. Detken, P. Focke, H. Zimmermann, U. Haeberlen, Z. Olejniczak, Z. T. Lalowicz, Z. Naturforsch. A 50 (1995) 95] and below 20 K they are indicative for rotational tunneling with a relatively large tunneling frequency. Measurements of the spin-lattice relaxation times for temperatures below 150 K reveal a broad distribution of correlation times in the glass. The dominant energy barrier characterizing the slow-down of the methyl group is significantly smaller than the well defined barrier in the crystal.

  3. Glassy correlations and thermal fluctuations in nematic elastomers

    NASA Astrophysics Data System (ADS)

    Lu, Bing; Xing, Xiangjun; Ye, Fangfu; Goldbart, Paul

    2010-03-01

    By means of the vulcanization theory framework we address the properties of nematic elastomers prepared in the isotropic liquid state and subsequently randomly cross-linked beyond the gelation point. We base our analysis on a model replica Landau free energy, in which the vulcanization order parameter is coupled to the order parameter describing the local degree of nematic ordering, retaining fluctuation terms to the Gaussian level. We explore how the cross-linking renormalizes the thermal correlations of the local nematic order, and also results in frozen-in, glassy nematic correlations. We examine these thermal and glassy correlations for two different preparation histories of the system: in the first, the cross-linking is done at temperatures close to the isotropic-nematic transition; in the other, the cross-linking is done at higher temperatures, but the system is subsequently cooled to near this transition temperature.

  4. Understanding soft glassy materials using an energy landscape approach.

    PubMed

    Hwang, Hyun Joo; Riggleman, Robert A; Crocker, John C

    2016-09-01

    Many seemingly different soft materials-such as soap foams, mayonnaise, toothpaste and living cells-display strikingly similar viscoelastic behaviour. A fundamental physical understanding of such soft glassy rheology and how it can manifest in such diverse materials, however, remains unknown. Here, by using a model soap foam consisting of compressible spherical bubbles, whose sizes slowly evolve and whose collective motion is simply dictated by energy minimization, we study the foam's dynamics as it corresponds to downhill motion on an energy landscape function spanning a high-dimensional configuration space. We find that these downhill paths, when viewed in this configuration space, are, surprisingly, fractal. The complex behaviour of our model, including power-law rheology and non-diffusive bubble motion and avalanches, stems directly from the fractal dimension and energy function of these paths. Our results suggest that ubiquitous soft glassy rheology may be a consequence of emergent fractal geometry in the energy landscapes of many complex fluids. PMID:27322823

  5. Nanoparticle Alignment and Repulsion During Failure of Glassy Polymer Nanocomposites

    NASA Astrophysics Data System (ADS)

    Crosby, Alfred; Lee, Jong-Young; Zhang, Qingling; Emrick, Todd

    2007-03-01

    We investigate crazing and failure in a model nanocomposite of surface modified nanoparticles (cadmium selenide, diameter is 5 nm) blended into polystyrene. We demonstrate that nanoparticles undergo three stages of rearrangement during craze formation and propagation in glassy polymer nanocomposites: 1) Alignment along the precraze, 2) Expulsion from craze fibrils, and 3) Assembly into clusters entrapped between craze fibrils. At an optimal volume fraction of nanoparticles, the failure strain of the nanocomposite is increased by nearly 100% relative to unfilled polystyrene. This optimal volume fraction is related to the balance of two mechanisms: 1) the decrease in cross-tie fibril density for craze structures, and 2) the decrease in the probability of craze widening at higher tensile strain by decreasing the number of polymer entanglements at small interparticle lengths. These results offer a clear and detailed understanding of failure mechanism of glassy polymer-nanoparticle composites, and provide predictions for the future design of nanoparticle-based materials.

  6. Localization and Glassy Dynamics in the Immune System

    NASA Astrophysics Data System (ADS)

    Sun, Jun; Earl, David J.; Deem, Michael W.

    We discuss use of the generalized NK model to examine evolutionary dynamics within the immune system. We describe how randomness and diversity play key roles in the immune response and how their effects are captured by this hierarchical spin glass model. We discuss analytical aspects of the model as well as practical applications to design of the annual influenza vaccine. We discuss the subtle role that the glassy evolutionary dynamics plays in suppressing autoimmune disease.

  7. The Nature of the Glassy Phase in 4He Crystals

    NASA Astrophysics Data System (ADS)

    Antsygina, T. N.; Poltavskaya, M. I.; Chishko, K. A.

    2015-08-01

    A model of a close-packed polytype with a random stacking fault structure is used to interpret the anomalies of the thermodynamic properties of the disordered (glassy) phase in solid HCP 4He in the so-called supersolid state. The temperature dependence of the phonon pressure is calculated theoretically, and compared to experimental data. A quantitative agreement between the theory and the experiment is achieved.

  8. Molecular mechanisms of deformation and failure in glassy materials

    NASA Astrophysics Data System (ADS)

    Rottler, Joerg

    2004-03-01

    Understanding the molecular origins of macroscopic mechanical properties is a fundamental scientific challenge. Fracture of both amorphous and crystalline materials involves many length scales reaching from the continuum to atomic level processes near a crack tip. Using molecular simulations of simple models for amorphous glassy materials, we first study elastoplastic deformation and discuss the nature of the shear yield stress and its dependence on loading conditions, strain rate and temperature. We then focus on the deformation of glassy polymeric systems into crazes at large strains. In the craze, polymers ( 0.5 nm diameter) are bundled into an intricate network of 10 nm diameter fibrils that extends 10 micrometers on either side of a mm crack tip. Analysis of local geometry and stresses provide insight into the real-space nature of the entanglements that control craze formation as well as melt dynamics. Crazes are also shown to share many features with jammed systems such as granular media and foams, but are unique in jamming under a tensile load. This allows explanations for the exponential force distribution in jammed systems to be tested. The force distribution strongly influences the ultimate breakdown of the craze fibrils either through disentanglement or chain scission. We conclude by quantifying the contribution of crazing to the unusually large fracture energy of glassy polymers.

  9. Yield Stress Enhancement in Glassy-Polyethylene Block Copolymers

    NASA Astrophysics Data System (ADS)

    Mulhearn, William; Register, Richard

    Polyethylene (PE) has the highest annual production volume of all synthetic polymers worldwide, and is valuable across many applications due to its low cost, toughness, processability, and chemical resistance. However, PE is not well suited to certain applications due to its modest yield stress and Young's modulus (approximately 30 MPa and 1 GPa, respectively for linear, high-density PE). Irreversible deformation of PE results from dislocation of crystal stems and eventual crystal fragmentation under applied stress. The liquid-like amorphous fraction provides no useful mechanical support to the crystal fold surface in a PE homopolymer, so the only method to enhance the force required for crystal slip, and hence the yield stress, is crystal thickening via thermal treatment. An alternative route towards modifying the mechanical properties of PE involves copolymerization of a minority high-glass transition temperature block into a majority-PE block copolymer. In this work, we investigate a system of glassy/linear-PE block copolymers prepared via ring-opening metathesis polymerization of cyclopentene and substituted norbornene monomers followed by hydrogenation. We demonstrate that a large change in mechanical properties can be achieved with the addition of a short glassy block (e.g. a doubling of the yield stress and Young's modulus versus PE homopolymer with the addition of 25 percent glassy block). Furthermore, owing to the low interaction energy between PE and the substituted polynorbornene blocks employed, these high-yield PE block copolymers can exhibit single-phase melts for ease of processability.

  10. Three-dimensional jamming and flows of soft glassy materials.

    PubMed

    Ovarlez, G; Barral, Q; Coussot, P

    2010-02-01

    Various disordered dense systems, such as foams, gels, emulsions and colloidal suspensions, undergo a jamming transition from a liquid state (they flow) to a solid state below a yield stress. Their structure, which has been thoroughly studied with powerful means of three-dimensional characterization, shows some analogy with that of glasses, which led to them being named soft glassy materials. However, despite its importance for geophysical and industrial applications, their rheological behaviour, and its microscopic origin, is still poorly known, in particular because of its nonlinear nature. Here we show from two original experiments that a simple three-dimensional continuum description of the behaviour of soft glassy materials can be built. We first show that when a flow is imposed in some direction there is no yield resistance to a secondary flow: these systems are always unjammed simultaneously in all directions of space. The three-dimensional jamming criterion seems to be the plasticity criterion encountered in most solids. We also find that they behave as simple liquids in the direction orthogonal to that of the main flow; their viscosity is inversely proportional to the main flow shear rate, as a signature of shear-induced structural relaxation, in close similarity to the structural relaxations driven by temperature and density in other glassy systems. PMID:20062046

  11. Magnetoresistance, electrical conductivity, and Hall effect of glassy carbon

    SciTech Connect

    Baker, D.F.

    1983-02-01

    These properties of glassy carbon heat treated for three hours between 1200 and 2700/sup 0/C were measured from 3 to 300/sup 0/K in magnetic fields up to 5 tesla. The magnetoresistance was generally negative and saturated with reciprocal temperature, but still increased as a function of magnetic field. The maximum negative magnetoresistance measured was 2.2% for 2700/sup 0/C material. Several models based on the negative magnetoresistance being proportional to the square of the magnetic moment were attempted; the best fit was obtained for the simplest model combining Curie and Pauli paramagnetism for heat treatments above 1600/sup 0/C. Positive magnetoresistance was found only in less than 1600/sup 0/C treated glassy carbon. The electrical conductivity, of the order of 200 (ohm-cm)/sup -1/ at room temperature, can be empirically written as sigma = A + Bexp(-CT/sup -1/4) - DT/sup -1/2. The Hall coefficient was independent of magnetic field, insensitive to temperature, but was a strong function of heat treatment temperature, crossing over from negative to positive at about 1700/sup 0/C and ranging from -0.048 to 0.126 cm/sup 3//coul. The idea of one-dimensional filaments in glassy carbon suggested by the electrical conductivity is compatible with the present consensus view of the microstructure.

  12. Quantifying glassy and crystalline basalt partitioning in the oceanic crust

    NASA Astrophysics Data System (ADS)

    Moore, Rachael; Ménez, Bénédicte

    2016-04-01

    The upper layers of the oceanic crust are predominately basaltic rock, some of which hosts microbial life. Current studies of microbial life within the ocean crust mainly focus on the sedimentary rock fraction, or those organisms found within glassy basalts while the potential habitability of crystalline basalts are poorly explored. Recently, there has been recognition that microbial life develops within fractures and grain boundaries of crystalline basalts, therefore estimations of total biomass within the oceanic crust may be largely under evaluated. A deeper understanding of the bulk composition and fractionation of rocks within the oceanic crust is required before more accurate estimations of biomass can be made. To augment our understanding of glassy and crystalline basalts within the oceanic crust we created two end-member models describing basalt fractionation: a pillow basalt with massive, or sheet, flows crust and a pillow basalt with sheeted dike crust. Using known measurements of massive flow thickness, dike thickness, chilled margin thickness, pillow lava size, and pillow lava glass thickness, we have calculated the percentage of glassy versus crystalline basalts within the oceanic crust for each model. These models aid our understanding of textural fractionation within the oceanic crust, and can be applied with bioenergetics models to better constrain deep biomass estimates.

  13. Exploration for facultative endosymbionts of glassy-wingedsharpshooter (Hemiptera: Cicadellidae)

    SciTech Connect

    Montllor-Curley, C.; Brodie, E.L.; Lechner, M.G.; Purcell, A.H.

    2006-07-01

    Homalodisca vitripennis (Germar) (Hemiptera: Cicadellidae),glassy-winged sharpshooter, was collected in California and severalstates in the southeastern United States in 2002 and 2003 and analyzedfor endosymbiotic bacteria. Hemolymph, eggs, and bacteriomes wereexamined for the presence of bacteria by polymerase chain reaction. Asubset of hemolymph and egg samples had their 16S rRNA gene ampliconscloned and sequenced or analyzed by restriction digest patterns ofsamples compared with known bacterial DNA. Baumannia cicadellinicola, oneof the primary symbionts of glassy-winged sharpshooter, was found in themajority of hemolymph samples, although it has been considered until nowto reside primarily inside the specialized host bacteriocytes. Wolbachiasp., a common secondary symbiont in many insect taxa investigated todate, was the second most frequently detected bacterium in hemolymphsamples. In addition, we detected bacteria that were most closely related(by 16S rRNA gene sequence) to Pseudomonas, Stenotrophomonas, andAcinetobacter in hemolymph samples of one and/or two glassy-wingedsharpshooters, but their origin is uncertain.

  14. Fast algorithms for glassy materials: methods and explorations

    NASA Astrophysics Data System (ADS)

    Middleton, A. Alan

    2014-03-01

    Glassy materials with frozen disorder, including random magnets such as spin glasses and interfaces in disordered materials, exhibit striking non-equilibrium behavior such as the ability to store a history of external parameters (memory). Precisely due to their glassy nature, direct simulation of models of these materials is very slow. In some fortunate cases, however, algorithms exist that exactly compute thermodynamic quantities. Such cases include spin glasses in two dimensions and interfaces and random field magnets in arbitrary dimensions at zero temperature. Using algorithms built using ideas developed by computer scientists and mathematicians, one can even directly sample equilibrium configurations in very large systems, as if one picked the configurations out of a ``hat'' of all configurations weighted by their Boltzmann factors. This talk will provide some of the background for these methods and discuss the connections between physics and computer science, as used by a number of groups. Recent applications of these methods to investigating phase transitions in glassy materials and to answering qualitative questions about the free energy landscape and memory effects will be discussed. This work was supported in part by NSF grant DMR-1006731. Creighton Thomas and David Huse also contributed to much of the work to be presented.

  15. Investigation of glassy state molecular motions in thermoset polymers

    NASA Astrophysics Data System (ADS)

    Tu, Jianwei

    This dissertation presents the investigation of the glassy state molecular motions in isomeric thermoset epoxies by means of solid-state deuterium (2H) NMR spectroscopy technique. The network structure of crosslinked epoxies was altered through monomer isomerism; specifically, diglycidyl ether of bisphenol A (DGEBA) was cured with isomeric amine curatives, i.e., the meta-substituted diaminodiphenylsulfone (33DDS) and para-substituted diaminodiphenylsulfone (44DDS). The use of structural isomerism provided a path way for altering macroscopic material properties while maintaining identical chemical composition within the crosslinked networks. The effects of structural isomerism on the glassy state molecular motions were studied using solid-state 2H NMR spectroscopy, which offers unrivaled power to monitor site-specific molecular motions. Three distinctive molecular groups on each isomeric network, i.e., the phenylene rings in the bisphenol A structure (BPA), the phenylene rings in the diaminodiphenylsulfone structure (DDS), and the hydroxypropoyl ether group (HPE) have been selectively deuterated for a comprehensive study of the structure-dynamics- property relationships in thermoset epoxies. Quadrupolar echo experiments and line shape simulations were employed as the main research approach to gain both qualitative and quantitative motional information of the epoxy networks in the glassy state. Quantitative information on the geometry and rate of the molecular motions allows the elucidation of the relationship between molecular motions and macro physical properties and the role of these motions in the mechanical relaxation. Specifically, it is revealed that both the BPA and HPE moieties in the isomeric networks have almost identical behaviors in the deep glassy state, which indicates that the molecular motions in the glassy state are localized, and the correlation length of the motions does not exceed the length of the DGEBA repeat unit. BPA ring motions contribute

  16. An electrochemically aminated glassy carbon electrode for simultaneous determination of hydroquinone and catechol.

    PubMed

    Wang, Xiuyun; Xi, Min; Guo, Mengmeng; Sheng, Fangmeng; Xiao, Guang; Wu, Shuo; Uchiyama, Shunichi; Matsuura, Hiroaki

    2016-02-01

    In this contribution, a very simple and reliable strategy based on the easy modification of a glassy carbon electrode (GCE) by pre-electrolyzing GCE in ammonium carbamate aqueous solution was employed for the simultaneous determination of hydroquinone (HQ) and catechol (CC). Compared with bare GCE, the incorporation of nitrogen into the GCE surface structure improved the electrocatalytic properties of GCE towards the electro-oxidation of HQ and CC. The nitrogen-introduced GCE (N-GCE) was evaluated for the simultaneous detection of HQ and CC and the linear ranges for HQ and CC were both from 5 to 260 μM. Their detection limits were both evaluated to be 0.2 μM (S/N = 3). The present method was applied for the determination of HQ and CC in real river water samples with recoveries of 95.0-102.1%. In addition, a possible detection mechanism of HQ and CC was discussed. PMID:26613194

  17. Crystallization of the glassy grain boundary phase in silicon nitride ceramics

    NASA Technical Reports Server (NTRS)

    Drummond, Charles H., III

    1991-01-01

    The role was studied of the intergranular glassy phase in silicon nitride as-processed with yttria as a sintering aid. The microstructure, crystallization, and viscosity of the glassy phase were areas studied. Crystallization of the intergranular glassy phase to more refractory crystalline phases should improve the high temperature mechanical properties of the silicon nitride. The addition of a nucleating agent will increase the rate of crystallization. The measurement of the viscosity of the glassy phase will permit the estimation of the high temperature deformation of the silicon nitride.

  18. Evidence for the absence of enzymatic reactions in the glassy state. A case study of xanthophyll cycle pigments in the desiccation-tolerant moss Syntrichia ruralis

    PubMed Central

    Fernández-Marín, Beatriz; Kranner, Ilse; Sebastián, María San; Artetxe, Unai; Laza, José Manuel; Vilas, José Luis; Pritchard, Hugh W.; Nadajaran, Jayanthi; Míguez, Fátima; Becerril, José María; García-Plazaola, José Ignacio

    2013-01-01

    Desiccation-tolerant plants are able to withstand dehydration and resume normal metabolic functions upon rehydration. These plants can be dehydrated until their cytoplasm enters a ‘glassy state’ in which molecular mobility is severely reduced. In desiccation-tolerant seeds, longevity can be enhanced by drying and lowering storage temperature. In these conditions, they still deteriorate slowly, but it is not known if deteriorative processes include enzyme activity. The storage stability of photosynthetic organisms is less studied, and no reports are available on the glassy state in photosynthetic tissues. Here, the desiccation-tolerant moss Syntrichia ruralis was dehydrated at either 75% or <5% relative humidity, resulting in slow (SD) or rapid desiccation (RD), respectively, and different residual water content of the desiccated tissues. The molecular mobility within dry mosses was assessed through dynamic mechanical thermal analysis, showing that at room temperature only rapidly desiccated samples entered the glassy state, whereas slowly desiccated samples were in a ‘rubbery’ state. Violaxanthin cycle activity, accumulation of plastoglobules, and reorganization of thylakoids were observed upon SD, but not upon RD. Violaxanthin cycle activity critically depends on the activity of violaxanthin de-epoxidase (VDE). Hence, it is proposed that enzymatic activity occurred in the rubbery state (after SD), and that in the glassy state (after RD) no VDE activity was possible. Furthermore, evidence is provided that zeaxanthin has some role in recovery apparently independent of its role in non-photochemical quenching of chlorophyll fluorescence. PMID:23761488

  19. Asphaltene-laden interfaces form soft glassy layers in contraction experiments: a mechanism for coalescence blocking.

    PubMed

    Pauchard, Vincent; Rane, Jayant P; Banerjee, Sanjoy

    2014-11-01

    In previous studies, the adsorption kinetics of asphaltenes at the water-oil interface were interpreted utilizing a Langmuir equation of state (EOS) based on droplet expansion experiments.1-3 Long-term adsorption kinetics followed random sequential adsorption (RSA) theory predictions, asymptotically reaching ∼85% limiting surface coverage, which is similar to limiting random 2D close packing of disks. To extend this work beyond this slow adsorption process, we performed rapid contractions and contraction-expansions of asphaltene-laden interfaces using the pendant drop experiment to emulate a Langmuir trough. This simulates the rapid increase in interfacial asphaltene concentration that occurs during coalescence events. For the contraction of droplets aged in asphaltene solutions, deviation from the EOS consistently occurs at a surface pressure value ∼21 mN/m corresponding to a surface coverage ∼80%. At this point droplets lose the shape required for validity of the Laplace-Young equation, indicating solidlike surface behavior. On further contraction wrinkles appear, which disappear when the droplet is held at constant volume. Surface pressure also decreases down to an equilibrium value near that measured for slow adsorption experiments. This behavior appears to be due to a transition to a glassy interface on contraction past the packing limit, followed by relaxation toward equilibrium by desorption at constant volume. This hypothesis is supported by cycling experiments around the close-packed limit where the transition to and from a solidlike state appears to be both fast and reversible, with little hysteresis. Also, the soft glass rheology model of Sollich is shown to capture previously reported shear behavior during adsorption. The results suggest that the mechanism by which asphaltenes stabilize water-in-oil emulsions is by blocking coalescence due to rapid formation of a glassy interface, in turn caused by interfacial asphaltenes rapidly increasing in

  20. Some Recent Developments in Structure and Glassy Behavior of Proteins

    NASA Astrophysics Data System (ADS)

    Hu, Chin-Kun

    2012-02-01

    We have used ARVO developed by us to find that the ratio of volume and surface area of proteins in Protein Data Bank distributed in a very narrow region [1]. Such result is useful for the determination of protein 3D structures. It has been widely known that a spin glass model can be used to understand the slow relaxation behavior of a glass at low temperatures [2]. We have used molecular dynamics and simple models of polymer chains to study relaxation and aggregation of proteins under various conditions and found that polymer chains with neighboring monomers connected by rigid bonds can relax very slowly and show glassy behavior [3]. We have also found that native collagen fibrils show glassy behavior at room temperatures [4]. The results of [3] and [4] about the glassy behavior of polymers or proteins are useful for understanding the mechanism for a biological system to maintain in a non-equilibrium state, including the ancient seed [5], which can maintain in a non-equilibrium state for a very long time. (1) M.-C. Wu, M. S. Li, W.-J. Ma, M. Kouza, and C.-K. Hu, EPL, in press (2011); (2) C. Dasgupta, S.-K. Ma, and C.-K. Hu. Phys. Rev. B 20, 3837-3849 (1979); (3) W.-J. Ma and C.-K. Hu, J. Phys. Soc. Japan 79, 024005, 024006, 054001, and 104002 (2010), C.-K. Hu and W.-J. Ma, Prog. Theor. Phys. Supp. 184, 369 (2010); S. G. Gevorkian, A. E. Allahverdyan, D. S. Gevorgyan and C.-K. Hu, EPL 95, 23001 (2011); S. Sallon, et al. Science 320, 1464 (2008).

  1. Positronics of radiation-induced effects in chalcogenide glassy semiconductors

    SciTech Connect

    Shpotyuk, O.; Kozyukhin, S. A.; Shpotyuk, M.; Ingram, A.; Szatanik, R.

    2015-03-15

    Using As{sub 2}S{sub 3} and AsS{sub 2} glasses as an example, the principal possibility of using positron annihilation spectroscopy methods for studying the evolution of the free volume of hollow nanoobjects in chalcogenide glassy semiconductors exposed to radiation is shown. The results obtained by measurements of the positron annihilation lifetime and Doppler broadening of the annihilation line in reverse chronological order are in full agreement with the optical spectroscopy data in the region of the fundamental absorption edge, being adequately described within coordination defect-formation and physical-aging models.

  2. Anomalous glassy relaxation near the isotropic-nematic phase transition

    NASA Astrophysics Data System (ADS)

    Jose, Prasanth P.; Chakrabarti, Dwaipayan; Bagchi, Biman

    2005-03-01

    Dynamical heterogeneity in a system of Gay-Berne ellipsoids near its isotropic-nematic (I-N) transition, and also in an equimolar mixture of Lennard-Jones spheres and Gay-Berne ellipsoids in deeply supercooled regime, is probed by the time evolution of non-Gaussian parameters (NGP). The appearance of a dominant second peak in the rotational NGP near the I-N transition signals the growth of pseudonematic domains. Surprisingly, such a second peak is instead observed in the translational NGP for the glassy binary mixture. Localization of orientational motion near the I-N transition is found to be responsible for the observed anomalous orientational relaxation.

  3. Linear Response Theory for Hard and Soft Glassy Materials

    SciTech Connect

    Langer, J.; Bouchbinder, Eran

    2011-01-01

    Despite qualitative differences in their underlying physics, both hard and soft glassy materials exhibit almost identical linear rheological behaviors. We show that these nearly universal properties emerge naturally in a shear-transformation-zone (STZ) theory of amorphous plasticity, extended to include a broad distribution of internal thermal-activation barriers. The principal features of this barrier distribution are predicted by nonequilibrium, effective-temperature thermodynamics. Our theoretical loss modulus G{double_prime}({omega}) has a peak at the {alpha} relaxation rate, and a power law decay of the form {omega}{sup -{zeta}} for higher frequencies, in quantitative agreement with experimental data.

  4. Nonequilibrium thermodynamics of the soft glassy rheology model.

    PubMed

    Fuereder, Ingo; Ilg, Patrick

    2013-10-01

    The soft glassy rheology (SGR) model is a mesoscopic framework which proved to be very successful in describing flow and deformation of various amorphous materials phenomenologically (e.g., pastes, slurries, foams, etc.). In this paper, we cast SGR in a general, model-independent framework for nonequilibrium thermodynamics called general equation for the nonequilibrium reversible-irreversible coupling. This leads to a formulation of SGR which clarifies how it can properly be coupled to hydrodynamic fields, resulting in a thermodynamically consistent, local, continuum version of SGR. Additionally, we find that compliance with thermodynamics imposes the existence of a modification to the stress tensor as predicted by SGR. PMID:24229142

  5. Evidence for a glassy state in strongly driven carbon

    SciTech Connect

    Brown, C. R. D.; Gericke, D. O.; Cammarata, M.; Cho, B. I.; Gwangju Inst. of Science and Technology, Gwangju; Inst. for Basic Science, Gwangju ; Döppner, T.; Engelhorn, K.; Förster, E.; Fortmann, C.; Fritz, D.; Galtier, E.; Glenzer, S. H.; Harmand, M.; Heimann, P.; Kugland, N. L.; Lamb, D. Q.; Lee, H. J.; Lee, R. W.; Lemke, H.; Makita, M.; Moinard, A.; Murphy, C. D.; Nagler, B.; Neumayer, P.; Plagemann, K. -U.; Redmer, R.; Riley, D.; Rosmej, F. B.; Sperling, P.; Toleikis, S.; Vinko, S. M.; Vorberger, J.; White, S.; White, T. G.; Wünsch, K.; Zastrau, U.; Zhu, D.; Tschentscher, T.; Gregori, G.

    2014-06-09

    Here, we report results of an experiment creating a transient, highly correlated carbon state using a combination of optical and x-ray lasers. Scattered x-rays reveal a highly ordered state with an electrostatic energy significantly exceeding the thermal energy of the ions. Strong Coulomb forces are predicted to induce nucleation into a crystalline ion structure within a few picoseconds. However, we observe no evidence of such phase transition after several tens of picoseconds but strong indications for an over-correlated fluid state. The experiment suggests a much slower nucleation and points to an intermediate glassy state where the ions are frozen close to their original positions in the fluid.

  6. Behavior of nuclear waste elements during hydrothermal alteration of glassy rhyolite in an active geothermal system: Yellowstone National Park, Wyoming

    SciTech Connect

    Sturchio, N.C.; Seitz, M.G.

    1984-12-31

    The behavior of a group of nuclear waste elements (U, Th, Sr, Zr, Sb, Cs, Ba, and Sm) during hydrothermal alteration of glassy rhyolite is investigated through geochemical analyses of whole rocks, glass and mineral separates, and thermal waters. Significant enrichments of U, Sr, Sb, Cs, and Ba are found in altered rock relative to unaltered rock. Excess Sr, Cs, and Ba are concentrated in zeolites in altered rock. Excess U is associated with titanomagnetite surfaces. Th, Zr, and Sm are relatively immobile during alteration, and are strongly concentrated in celadonite. 19 refs., 2 figs., 2 tabs.

  7. Electrical studies on silver based fast ion conducting glassy materials

    SciTech Connect

    Rao, B. Appa Kumar, E. Ramesh Kumari, K. Rajani Bhikshamaiah, G.

    2014-04-24

    Among all the available fast ion conductors, silver based glasses exhibit high conductivity. Further, glasses containing silver iodide enhances fast ion conducting behavior at room temperature. Glasses of various compositions of silver based fast ion conductors in the AgI−Ag{sub 2}O−[(1−x)B{sub 2}O{sub 3}−xTeO{sub 2}] (x=0 to1 mol% in steps of 0.2) glassy system have been prepared by melt quenching method. The glassy nature of the compounds has been confirmed by X-ray diffraction. The electrical conductivity (AC) measurements have been carried out in the frequency range of 1 KHz–3MHz by Impedance Analyzer in the temperature range 303–423K. The DC conductivity measurements were also carried out in the temperature range 300–523K. From both AC and DC conductivity studies, it is found that the conductivity increases and activation energy decreases with increasing the concentration of TeO{sub 2} as well as with temperature. The conductivity of the present glass system is found to be of the order of 10{sup −2} S/cm at room temperature. The ionic transport number of these glasses is found to be 0.999 indicating that these glasses can be used as electrolyte in batteries.

  8. Electrical studies on silver based fast ion conducting glassy materials

    NASA Astrophysics Data System (ADS)

    Rao, B. Appa; Kumar, E. Ramesh; Kumari, K. Rajani; Bhikshamaiah, G.

    2014-04-01

    Among all the available fast ion conductors, silver based glasses exhibit high conductivity. Further, glasses containing silver iodide enhances fast ion conducting behavior at room temperature. Glasses of various compositions of silver based fast ion conductors in the AgI-Ag2O-[(1-x)B2O3-xTeO2] (x=0 to1 mol% in steps of 0.2) glassy system have been prepared by melt quenching method. The glassy nature of the compounds has been confirmed by X-ray diffraction. The electrical conductivity (AC) measurements have been carried out in the frequency range of 1 KHz-3MHz by Impedance Analyzer in the temperature range 303-423K. The DC conductivity measurements were also carried out in the temperature range 300-523K. From both AC and DC conductivity studies, it is found that the conductivity increases and activation energy decreases with increasing the concentration of TeO2 as well as with temperature. The conductivity of the present glass system is found to be of the order of 10-2 S/cm at room temperature. The ionic transport number of these glasses is found to be 0.999 indicating that these glasses can be used as electrolyte in batteries.

  9. Deformation in Thin Glassy Polymer Films from Surface towards Interior

    NASA Astrophysics Data System (ADS)

    Chowdhury, Mithun; de Silva, Johann P.; Cross, Graham L. W.

    Polymer thin glassy films occupy an important place in last two decades of condensed matter research, concerning its surprising surface mobility and spatially dependent structural relaxation. However, ranges of cleverly designed indirect measurements on confined polymer glassy films already probed its mechanical properties; it is still a challenging task to directly probe such small confined volume through conventional mechanical testing. We have designed confined layer compression testing with a precisely designed and aligned flat probe during nanoindentation, which was further accompanied with atomic force microscopy. Due to natural confinement from the surrounding material, we show that a state of `uniaxial strain' is created beneath the probe under small axial strains. By this methodology we are able to directly probe uniaxial flows under both anelastic and plastic conditions while doing controlled creep studies at different positions in the film starting from surface towards interior. Depending on the extent of deformation, we found ranges of effects, such as densification, anelastic yield, and plastic yield. Enhanced creep rate upon deformation supports the idea of `deformation induced mobility'. Work performed at Trinity College Dublin.

  10. Confined glassy dynamics at grain boundaries in colloidal crystals

    PubMed Central

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

    2011-01-01

    Grain boundary (GB) microstructure and dynamics dictate the macroscopic properties of polycrystalline materials. Although GBs have been investigated extensively in conventional materials, it is only recently that molecular dynamics simulations have shown that GBs exhibit features similar to those of glass-forming liquids. However, current simulation techniques to probe GBs are limited to temperatures and driving forces much higher than those typically encountered in atomic experiments. Further, the short spatial and temporal scales in atomic systems preclude direct experimental access to GB dynamics. Here, we have used confocal microscopy to investigate the dynamics of high misorientation angle GBs in a three-dimensional colloidal polycrystal, with single-particle resolution, in the zero-driving force limit. We show quantitatively that glassy behavior is inherent to GBs as exemplified by the slowing down of particle dynamics due to transient cages formed by their nearest neighbors, non-Gaussian probability distribution of particle displacements and string-like cooperative rearrangements of particles. Remarkably, geometric confinement of the GB region by adjacent crystallites decreases with the misorientation angle and results in an increase in the size of cooperatively rearranging regions and hence the fragility of the glassy GBs. PMID:21705662

  11. Approaching theoretical strength in glassy carbon nanolattices.

    PubMed

    Bauer, J; Schroer, A; Schwaiger, R; Kraft, O

    2016-04-01

    The strength of lightweight mechanical metamaterials, which aim to exploit material-strengthening size effects by their microscale lattice structure, has been limited by the resolution of three-dimensional lithography technologies and their restriction to mainly polymer resins. Here, we demonstrate that pyrolysis of polymeric microlattices can overcome these limitations and create ultra-strong glassy carbon nanolattices with single struts shorter than 1 μm and diameters as small as 200 nm. They represent the smallest lattice structures yet produced--achieved by an 80% shrinkage of the polymer during pyrolysis--and exhibit material strengths of up to 3 GPa, corresponding approximately to the theoretical strength of glassy carbon. The strength-to-density ratios of the nanolattices are six times higher than those of reported microlattices. With a honeycomb topology, effective strengths of 1.2 GPa at 0.6 g cm(-3) are achieved. Diamond is the only bulk material with a notably higher strength-to-density ratio. PMID:26828314

  12. TOPICAL REVIEW: Fracture in glassy polymers: a molecular modeling perspective

    NASA Astrophysics Data System (ADS)

    Rottler, Jörg

    2009-11-01

    Over the past 25 years, molecular modeling and simulations have provided important insights into the physics of deformation and fracture of glassy polymers. This review presents an overview of key results discussed in the context of experimentally observed polymer behavior. Both atomistic and coarse-grained polymer models have been used in different deformation protocols to study elastic properties, shear yielding, creep, physical aging, strain hardening and crazing. Simulations reproduce most of the macroscopic features of plasticity in polymer glasses such as stress-strain relations and creep response, and reveal information about the underlying atomistic processes. Trends of the shear yield stress with loading conditions, temperature and strain rate, and the atomistic dynamics under load have been systematically explored. Most polymers undergo physical aging, which leads to a history-dependent mechanical response. Simulations of strain hardening and crazing demonstrate the nature of polymer entanglements in the glassy state and the role of local plasticity and provide insight into the origin of fracture toughness of amorphous polymers.

  13. Fracture in glassy polymers: a molecular modeling perspective.

    PubMed

    Rottler, Jörg

    2009-11-18

    Over the past 25 years, molecular modeling and simulations have provided important insights into the physics of deformation and fracture of glassy polymers. This review presents an overview of key results discussed in the context of experimentally observed polymer behavior. Both atomistic and coarse-grained polymer models have been used in different deformation protocols to study elastic properties, shear yielding, creep, physical aging, strain hardening and crazing. Simulations reproduce most of the macroscopic features of plasticity in polymer glasses such as stress-strain relations and creep response, and reveal information about the underlying atomistic processes. Trends of the shear yield stress with loading conditions, temperature and strain rate, and the atomistic dynamics under load have been systematically explored. Most polymers undergo physical aging, which leads to a history-dependent mechanical response. Simulations of strain hardening and crazing demonstrate the nature of polymer entanglements in the glassy state and the role of local plasticity and provide insight into the origin of fracture toughness of amorphous polymers. PMID:21715863

  14. Modeling VOC Sorption and Transport in Glassy Polymeric Membranes

    NASA Astrophysics Data System (ADS)

    De Angelis, Maria Grazia; Olivieri, Luca; Sarti, G. C.

    2010-06-01

    In this work we evaluated the sorption, diffusion and permeation of a series of volatile organic compounds (VOCs) (acetone, n-butane, n-pentane, n-hexane, ethanol, methanol, chloroform and toluene) into glassy polymers of increasing fractional free volume (FFV): Polycarbonate (PC), Amorphous Teflon AF1600 and AF2400, poly-trimethylsilyl norbornene (PTMSN) and poly[1-(trimethylsilyl)-1-propyne] (PTMSP). Based on some experimental data of sorption and diffusion, and on theoretical and empirical models for the solubility and diffusion coefficients, the permeability for vapor/N2 mixtures was evaluated. These parameters are useful for the membrane separation processes and for other applications such as chemical sensors. The ideal separation factors of glassy polymeric membranes versus mixtures of VOCs and N2 were estimated at various pressures and compositions and at 25° C. The selectivity vs. permeability maps for the mixtures considered were plotted, showing that some of these materials show potentially the same selective ability of rubbery polymeric films. In particular it is shown that, the higher the FFV, the better the vapor/gas selectivity.

  15. Use of glassy carbon as a working electrode in controlled potential coulometry.

    PubMed

    Plock, C E; Vasquez, J

    1969-11-01

    Glassy carbon has been used as the working electrode in controlled potential coulometry. The results of coulometric investigations of chromium, copper, iron, uranium and neptunium are compared with results obtained with platinum or mercury working electrodes. The accuracy of results with the glassy carbon electrode compares favourably with the results obtainable with the other electrodes, but the precision is poorer. PMID:18960665

  16. Effects of glassy-winged sharpshooter feeding, size, and lipid content on egg maturation

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The glassy-winged sharpshooter (Homalodisca vitripennis) is synovigenic and must feed during the adult stage to produce eggs. While glassy-winged sharpshooter egg production is related to adult feeding, rates of egg production are variable. In this study, effects of lipid allocation to eggs and fema...

  17. Glassy-winged sharpshooter excreta production and egg maturation on grapevines

    Technology Transfer Automated Retrieval System (TEKTRAN)

    To better understand glassy-winged sharpshooter movement and reproduction in vineyards, studies evaluating glassy-winged sharpshooter feeding (as measured by excreta production) and egg maturation on grapevines were conducted. In 2010, studies compared excreta production and egg maturation of femal...

  18. Silicon-tin oxynitride glassy composition and use as anode for lithium-ion battery

    DOEpatents

    Neudecker, Bernd J.; Bates, John B.

    2001-01-01

    Disclosed are silicon-tin oxynitride glassy compositions which are especially useful in the construction of anode material for thin-film electrochemical devices including rechargeable lithium-ion batteries, electrochromic mirrors, electrochromic windows, and actuators. Additional applications of silicon-tin oxynitride glassy compositions include optical fibers and optical waveguides.

  19. Evaluation of grapevine as a host for the glassy-winged sharpshooter

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Grapevine was evaluated as a feeding and oviposition host for the glassy-winged sharpshooter. Two sets of experiments were conducted. The first set compared performance and preference of glassy-winged sharpshooter females for grapevine (cv. Chardonnay) versus cowpea (Vigna unguiculata cultivar black...

  20. Heterogeneous nucleation of ice particles on glassy aerosols modifies TTL cirrus

    NASA Astrophysics Data System (ADS)

    Wilson, T. W.; Murray, B. J.; Dobbie, S.; Al-Jumur, S. M.; Cui, Z.; Wagner, R.; Moehler, O.; Schnaiter, M.; Benz, S.; Niemand, M.; Saathoff, H.; Skrotzki, J.; Ebert, V.; Wagner, S.; Karcher, B.

    2010-12-01

    Experiments at the AIDA chamber, Karlsruhe Institute of Technology, have shown that glassy aqueous citric acid aerosol can nucleate ice at temperatures relevant to the tropical tropopause layer (TTL)(1). Modelling suggests this new route to the formation of TTL cirrus can provide an explanation for the very low ice particle number density observed in cirrus clouds in this region and may lead to high in-cloud supersaturations(1). Nucleation of ice on glassy aerosol is consistent with the absence of traditional ice nuclei in sampled TTL cirrus residue(2). In addition, we will present new data from experiments performed in July 2010 at the AIDA chamber using glassy aerosols composed of other atmospherically relevant compounds (levoglucosan, raffinose) and an internal mixture of five dicarboxylic acids and ammonium sulphate (raffinose/M5AS)(3). All four systems tested nucleate ice when in a glassy state. This indicates that heterogeneous ice nucleation is a general property of glassy aerosols and that natural aerosols which are composed of similar molecules will also nucleate ice if glassy. Glassy aqueous levoglucosan and raffinose/M5AS aerosol nucleated ice at temperatures similar to those found for glassy aqueous citric acid aerosol (<202 K). Whereas raffinose, which forms a glass at much higher temperatures, nucleated ice heterogeneously at up to ~220 K. This activity at higher temperatures suggests that ice nucleation by glassy aerosol may also play a role in the formation of warmer ice clouds. (1)B. J. Murray et al., Heterogeneous nucleation of ice particles on glassy aerosols under cirrus conditions, Nature Geosci, 2010, 3, 233-237. (2)K. D. Froyd et al., Aerosols that form subvisible cirrus at the tropical tropopause, Atmos. Chem. Phys., 2010, 10, 209-218. (3)B. Zobrist et al., Do atmospheric aerosols form glasses?, Atmos. Chem. Phys., 2008, 8, 5221-5244.

  1. Surface treatment of Glassy Polymeric Carbon artifacts for medical applications

    SciTech Connect

    Rodrigues, M. G.; Zimmerman, R. L.; Rezende, M. C.

    1999-06-10

    Glassy Polymeric Carbon (GPC) has been used for mechanical cardiac valves. GCP valves are chemically biocompatible and durable, but less thromboresistant than biological valves. Enhanced thromboresistance of mechanical cardiac components with porous surface has been demonstrated. The endothelialized tissue blood-contacting surface adheres to the porous prosthetic component and decreases the formation of thrombus. Our experience has shown that the porosity of GPC can be increased and controlled by MeV ion bombardment. We report here that the surface roughness of heat-treated GPC bombarded with C, O, Si and Au is also enhanced. The surface roughness of the ion-bombarded samples is on a smaller scale than those roughened by sand blasting (measurements made with Perthomete S and P). The roughness decreases slightly after heat treatment, in linear proportion to the shrinkage of the test piece. Possible beneficial effects of the imbedded ions on tissue adherence and thromboresistance must be determined by in vivo animal experiments.

  2. Manufacturing of glassy thin shell for adaptive optics: results achieved

    NASA Astrophysics Data System (ADS)

    Poutriquet, F.; Rinchet, A.; Carel, J.-L.; Leplan, H.; Ruch, E.; Geyl, R.; Marque, G.

    2012-07-01

    Glassy thin shells are key components for the development of adaptive optics and are part of future & innovative projects such as ELT. However, manufacturing thin shells is a real challenge. Even though optical requirements for the front face - or optical face - are relaxed compared to conventional passive mirrors, requirements concerning thickness uniformity are difficult to achieve. In addition, process has to be completely re-defined as thin mirror generates new manufacturing issues. In particular, scratches and digs requirement is more difficult as this could weaken the shell, handling is also an important issue due to the fragility of the mirror. Sagem, through REOSC program, has recently manufactured different types of thin shells in the frame of European projects: E-ELT M4 prototypes and VLT Deformable Secondary Mirror (VLT DSM).

  3. Anomalous glassy relaxation near the isotropic-nematic phase transition.

    PubMed

    Jose, Prasanth P; Chakrabarti, Dwaipayan; Bagchi, Biman

    2005-03-01

    Dynamical heterogeneity in a system of Gay-Berne ellipsoids near its isotropic-nematic (I-N) transition, and also in an equimolar mixture of Lennard-Jones spheres and Gay-Berne ellipsoids in deeply supercooled regime, is probed by the time evolution of non-Gaussian parameters (NGP). The appearance of a dominant second peak in the rotational NGP near the I-N transition signals the growth of pseudonematic domains. Surprisingly, such a second peak is instead observed in the translational NGP for the glassy binary mixture. Localization of orientational motion near the I-N transition is found to be responsible for the observed anomalous orientational relaxation. PMID:15903399

  4. Determination of Fracture Patterns in Glass and Glassy Polymers.

    PubMed

    Baca, Allison C; Thornton, John I; Tulleners, Frederic A

    2016-01-01

    The study of fractures of glass, glassy-type materials, and plastic has long been of interest to the forensic community. The focus of this interest has been the use of glass and polymer fractures to associate items of evidence under the assumption that each fracture is different. Generally, it is well-accepted that deviations exist; however, the emphasis has been on classifying and predicting fracture rather than determining that each fracture is different. This study documented the controlled fracture patterns of 60 glass panes, 60 glass bottles, and 60 plastic tail light lens covers using both dynamic impact and static pressure methods under closely controlled conditions. Each pattern was intercompared, and based on the limited specimens tested in this study, the results illustrate that the fracture patterns are different. Further repetitive studies, under controlled conditions, will be needed to provide more statistical significance to the theory that each fracture forms a nonreproducible fracture pattern. PMID:26524485

  5. Evidence for a glassy state in strongly driven carbon

    DOE PAGESBeta

    Brown, C. R. D.; Gericke, D. O.; Cammarata, M.; Cho, B. I.; Döppner, T.; Engelhorn, K.; Förster, E.; Fortmann, C.; Fritz, D.; Galtier, E.; et al

    2014-06-09

    Here, we report results of an experiment creating a transient, highly correlated carbon state using a combination of optical and x-ray lasers. Scattered x-rays reveal a highly ordered state with an electrostatic energy significantly exceeding the thermal energy of the ions. Strong Coulomb forces are predicted to induce nucleation into a crystalline ion structure within a few picoseconds. However, we observe no evidence of such phase transition after several tens of picoseconds but strong indications for an over-correlated fluid state. The experiment suggests a much slower nucleation and points to an intermediate glassy state where the ions are frozen closemore » to their original positions in the fluid.« less

  6. Evidence for a glassy state in strongly driven carbon.

    PubMed

    Brown, C R D; Gericke, D O; Cammarata, M; Cho, B I; Döppner, T; Engelhorn, K; Förster, E; Fortmann, C; Fritz, D; Galtier, E; Glenzer, S H; Harmand, M; Heimann, P; Kugland, N L; Lamb, D Q; Lee, H J; Lee, R W; Lemke, H; Makita, M; Moinard, A; Murphy, C D; Nagler, B; Neumayer, P; Plagemann, K-U; Redmer, R; Riley, D; Rosmej, F B; Sperling, P; Toleikis, S; Vinko, S M; Vorberger, J; White, S; White, T G; Wünsch, K; Zastrau, U; Zhu, D; Tschentscher, T; Gregori, G

    2014-01-01

    Here, we report results of an experiment creating a transient, highly correlated carbon state using a combination of optical and x-ray lasers. Scattered x-rays reveal a highly ordered state with an electrostatic energy significantly exceeding the thermal energy of the ions. Strong Coulomb forces are predicted to induce nucleation into a crystalline ion structure within a few picoseconds. However, we observe no evidence of such phase transition after several tens of picoseconds but strong indications for an over-correlated fluid state. The experiment suggests a much slower nucleation and points to an intermediate glassy state where the ions are frozen close to their original positions in the fluid. PMID:24909903

  7. Evidence for a glassy state in strongly driven carbon

    PubMed Central

    Brown, C. R. D.; Gericke, D. O.; Cammarata, M.; Cho, B. I.; Döppner, T.; Engelhorn, K.; Förster, E.; Fortmann, C.; Fritz, D.; Galtier, E.; Glenzer, S. H.; Harmand, M.; Heimann, P.; Kugland, N. L.; Lamb, D. Q.; Lee, H. J.; Lee, R. W.; Lemke, H.; Makita, M.; Moinard, A.; Murphy, C. D.; Nagler, B.; Neumayer, P.; Plagemann, K.-U.; Redmer, R.; Riley, D.; Rosmej, F. B.; Sperling, P.; Toleikis, S.; Vinko, S. M.; Vorberger, J.; White, S.; White, T. G.; Wünsch, K.; Zastrau, U.; Zhu, D.; Tschentscher, T.; Gregori, G.

    2014-01-01

    Here, we report results of an experiment creating a transient, highly correlated carbon state using a combination of optical and x-ray lasers. Scattered x-rays reveal a highly ordered state with an electrostatic energy significantly exceeding the thermal energy of the ions. Strong Coulomb forces are predicted to induce nucleation into a crystalline ion structure within a few picoseconds. However, we observe no evidence of such phase transition after several tens of picoseconds but strong indications for an over-correlated fluid state. The experiment suggests a much slower nucleation and points to an intermediate glassy state where the ions are frozen close to their original positions in the fluid. PMID:24909903

  8. Poly(4-vinylpyridine)-coated glassy carbon flow detectors

    SciTech Connect

    Wang, J.; Golden, T.; Tuzhi, P.

    1987-03-01

    The performance of a thin-layer flow detector with a glassy carbon electrode coated with a film of protonated poly(4-vinylpyridine) is described. Substantial improvement in the selectivity of amperometric detection for liquid chromatography and flow injection systems is observed as a result of excluding cationic species from the surface. The detector response was evaluated with respect to flow rate, solute concentration, coating scheme, film-to-film reproducibility, and other variables. Despite the increase in diffusional resistance, low detection limits of ca. 0.04 and 0.10 ng of ascorbic acid and uric acid, respectively, are maintained. Protection from organic surfactants can be coupled to the charge exclusion effect by using a bilayer coating, with a cellulose acetate film atop the poly(4-vinylpyridine) layer. Applicability to urine sample is demonstrated.

  9. Polymorphism in glassy silicon: Inherited from liquid-liquid phase transition in supercooled liquid

    NASA Astrophysics Data System (ADS)

    Zhang, Shiliang; Wang, Li-Min; Zhang, Xinyu; Qi, Li; Zhang, Suhong; Ma, Mingzhen; Liu, Riping

    2015-02-01

    Combining molecular dynamics (MD) simulation and Voronoi polyhedral analyses, we discussed the microstructure evolution in liquid and glassy silicon during cooling by focusing on the fraction of various clusters. Liquid-liquid phase transition (LLPT) is detected in supercooled liquid silicon However, freezing the high-density liquid (HDL) to the glassy state is not achieved as the quenching rate goes up to 1014 K/s. The polyamorphism in glassy silicon is found to be mainly associated with low-density liquid (LDL).

  10. Polymorphism in glassy silicon: Inherited from liquid-liquid phase transition in supercooled liquid

    PubMed Central

    Zhang, Shiliang; Wang, Li-Min; Zhang, Xinyu; Qi, Li; Zhang, Suhong; Ma, Mingzhen; Liu, Riping

    2015-01-01

    Combining molecular dynamics (MD) simulation and Voronoi polyhedral analyses, we discussed the microstructure evolution in liquid and glassy silicon during cooling by focusing on the fraction of various clusters. Liquid-liquid phase transition (LLPT) is detected in supercooled liquid silicon However, freezing the high-density liquid (HDL) to the glassy state is not achieved as the quenching rate goes up to 1014 K/s. The polyamorphism in glassy silicon is found to be mainly associated with low-density liquid (LDL). PMID:25716054

  11. Au nanoparticles and graphene quantum dots co-modified glassy carbon electrode for catechol sensing

    NASA Astrophysics Data System (ADS)

    Zhao, Xuan; He, Dawei; Wang, Yongsheng; Hu, Yin; Fu, Chen

    2016-03-01

    In this letter, the gold nanoparticles and graphene quantum dots were applied to the modification of glassy carbon electrode for the detection of catechol. The synergist cooperation between gold nanoparticles and graphene quantum dots can increase specific surface area and enhance electronic and catalytic properties of glassy carbon electrode. The detection limit of catechol is 0.869 μmol/L, demonstrating the superior detection efficiency of the gold nanoparticles and graphene quantum dots co-modified glassy carbon electrode as a new sensing platform.

  12. Boron doped diamond and glassy carbon electrodes comparative study of the oxidation behaviour of cysteine and methionine.

    PubMed

    Enache, T A; Oliveira-Brett, A M

    2011-04-01

    The electrochemical oxidation behaviour at boron doped diamond and glassy carbon electrodes of the sulphur-containing amino acids cysteine and methionine, using cyclic and differential pulse voltammetry over a wide pH range, was compared. The oxidation reactions of these amino acids are irreversible, diffusion-controlled pH dependent processes, and occur in a complex cascade mechanism. The amino acid cysteine undergoes similar three consecutive oxidation reactions at both electrodes. The first step involves the oxidation of the sulfhydryl group with radical formation, that undergoes nucleophilic attack by water to give an intermediate species that is oxidized in the second step to cysteic acid. The oxidation of the sulfhydryl group leads to a disulfide bridge between two similar cysteine moieties forming cysteine. The subsequent oxidation of cystine occurs at a higher potential, due to the strong disulfide bridge covalent bond. The electro-oxidation of methionine at a glassy carbon electrode occurs in two steps, corresponding to the formation of sulfoxide and sulfone, involving the adsorption and protonation/deprotonation of the thiol group, followed by electrochemical oxidation. Methionine undergoes a one-step oxidation reaction at boron doped diamond electrodes due to the negligible adsorption, and the oxidation also leads to the formation of methionine sulfone. PMID:21377428

  13. Jump in the electrical conductivity of shock-compressed glassy carbon

    NASA Astrophysics Data System (ADS)

    Molodets, A. M.; Golyshev, A. A.; Emel'yanov, A. N.; Shul'ga, Yu. M.; Fortov, V. E.

    2014-04-01

    The effect of high dynamic pressures on the electrical conductivity of the amorphous conducting carbon phase (glassy carbon) has been studied. The electrical conductivity of glassy carbon samples has been measured under the condition of shock compression and subsequent release wave. The history of the shock loading of glassy carbon has been calculated with the developed semiempirical equations of state. It has been shown the electrical conductivity of glassy carbon samples in the compression phase at a pressure of 45(5) GPa decreases abruptly by two orders of magnitude. In the relief phase, partially reversible change in the electrical conductivity of an amorphous carbon sample occurs. The recorded effect has been treated as a result of a partially reversible physicochemical transformation of shock-compressed amorphous carbon.

  14. Sub-nanoscale nanoimprint fabrication of atomically stepped glassy substrates of silicate glass and acryl polymer

    NASA Astrophysics Data System (ADS)

    Yoshimoto, Mamoru

    2015-11-01

    In the nanoimprint process, the resolution limit of patterning has attracted much attention from both scientific and industrial aspects. In this article, we briefly review the main achievements of our research group on sub-nanoscale nanoimprint fabrication of atomically patterned glassy substrates of oxide glass and polymer. By applying the sapphire (α-Al2O3 single crystal) wafers with self-organized nanopatterns of atomic steps as thermal nanoimprinting molds, we successfully transferred their nanoscale patterns onto the surfaces of glassy substrates such as soda-lime silicate glasses and poly(methyl methacrylate) polymers. The surfaces of nanoimprinted glassy materials exhibited regularly arrayed atomic stairs with 0.2-0.3 nm step height, which were in good agreement with the sub-nanopatterns of sapphire molds. These atomically stepped morphologies on the glassy substrates were found to be stable for about 1 year.

  15. Robust organic lasers comprising glassy-cholesteric pentafluorene doped with a red-emitting oligofluorene

    NASA Astrophysics Data System (ADS)

    Wei, Simon K. H.; Chen, Shaw H.; Dolgaleva, Ksenia; Lukishova, Svetlana G.; Boyd, Robert W.

    2009-01-01

    Doped with a red-emitting oligofluorene, fluid and glassy cholesteric liquid crystal (CLC) films are characterized by similar lasing thresholds and efficiencies. With picosecond excitations the output from a glassy CLC laser is temporally stable, but that from a fluid CLC laser decays with time. The difference in stability is attributable to external perturbations on supramolecular structure in the fluid but not the solid state, such as heating through optical pumping, light-induced pitch dilation, and laser-induced flow.

  16. Structural and thermodynamic aspects of plasticization and antiplasticization in glassy encapsulation and biostabilization matrices.

    PubMed

    Ubbink, Job

    2016-05-01

    The structural and thermodynamic properties of glassy carbohydrate matrices for the encapsulation and biostabilization of sensitive bioactive compounds, such as pharmaceutically active proteins and oxidation-sensitive compounds, are reviewed in the context of the plasticization and antiplasticization of glassy carbohydrates of intermediate and high molecular weight by low molecular weight diluents. Plasticization and antiplasticization may be monitored either by dynamic measures or by structural and thermodynamic features of the glassy matrices. Specifically, it is demonstrated that the decrease in size of the molecular free volume holes with increasing diluent content, as determined by positron annihilation lifetime spectroscopy (PALS), is related to the antiplasticization of glassy carbohydrate matrices, resulting in increased barrier properties of the glassy matrix. As far as could be ascertained from the available data, the regimes as identified by PALS map on those detected by neutron scattering and dielectric spectroscopy for glassy matrices consisting of trehalose and the diluent glycerol. The review is concluded by a survey of the published results on the stability of bioactive compounds encapsulated in carbohydrate glasses and an overview of outstanding questions. PMID:26748258

  17. Surface micro-structuring of glassy carbon for precision glass molding of diffractive optical elements

    NASA Astrophysics Data System (ADS)

    Prater, Karin; Dukwen, Julia; Scharf, Toralf; Herzig, Hans Peter; Hermerschmidt, Andreas

    2014-09-01

    Glassy carbon is used nowadays for a variety of applications because of its mechanical strength, thermal stability and non-sticking adhesion properties. This makes it also a suitable candidate as mold material for precision compression molding of low and high glass-transition temperature materials. To fabricate molds for diffractive optics a highresolution structuring technique is needed. We introduce a process that allows the micro-structuring of glassy carbon by reactive ion etching. Key parameters such as uniformity, surface roughness, edge definition and lateral resolution are discussed. They are the most relevant parameters for a stamp in optical applications. The use of titanium as a hard mask makes it possible to achieve a reasonable selectivity of 4:1, which has so far been one of the main problems in microstructuring of glassy carbon. We investigate the titanium surface structure with its 5-10 nm thick layer of TiO2 grains and its influence on the shape of the hard mask. In our fabrication procedure we were able to realize optically flat diffractive structures with slope angles of more than 80° at typical feature sizes of 5 μm and at 700 nm depth. The fabricated glassy carbon molds were applied to thermal imprinting onto different glasses. Glassy carbon molds with 1 mm thickness were tested with binary optical structures. Our experiments show the suitability of glassy carbon as molds for cost efficient mass production with a high quality.

  18. Glassy Dynamics versus Thermodynamics: The Case of 2-Adamantanone.

    PubMed

    Szewczyk, D; Jeżowski, A; Vdovichenko, G A; Krivchikov, A I; Bermejo, F J; Tamarit, J Ll; Pardo, L C; Taylor, J W

    2015-07-01

    The heat capacity and thermal conductivity of the monoclinic and the fully ordered orthorhombic phases of 2-adamantanone (C10H14O) have been measured for temperatures between 2 and 150 K. The heat capacities for both phases are shown to be strikingly close regardless of the site disorder present in the monoclinic crystal which arises from the occupancy of three nonequivalent sites for the oxygen atom. The heat capacity curves are also well accounted for by an evaluation carried out within the harmonic approximation in terms of the g(ω) vibrational frequency distributions measured by means of inelastic neutron scattering. Such spectral functions show however a significant excess of low frequency modes for the crystal showing statistical disorder. In contrast, large differences are found for the thermal conductivity which contrary to what could be expected, shows the substitutionally disordered crystal to exhibit better heat transport properties than the fully ordered orthorhombic phase. Such an anomalous behavior is understood from examination of the crystalline structure of the orthorhombic phase which leads to very strong scattering of heat-carrying phonons due to grain boundary effects able to yield a largely reduced value of the conductivity as well as to a plateau-like feature at intermediate temperatures which contrasts with a bell-shaped maximum shown by data pertaining the disordered crystal. The relevance of the present findings within the context of glassy dynamics of the orientational glass state is finally discussed. PMID:26073682

  19. Electrochemical determination of mesotrione at organoclay modified glassy carbon electrodes.

    PubMed

    Kamga Wagheu, Josephine; Forano, Claude; Besse-Hoggan, Pascale; Tonle, Ignas K; Ngameni, Emmanuel; Mousty, Christine

    2013-01-15

    A natural Cameroonian smectite-type clay (SaNa) was exchanged with cationic surfactants, namely cetyltrimethylammonium (CTA) and didodecyldimethyl ammonium (DDA) modifying its physico-chemical properties. The resulting organoclays that have higher adsorption capacity for mesotrione than the pristine SaNa clay, have been used as modifiers of glassy carbon electrode for the electrochemical detection of this herbicide by square wave voltammetry. The stripping performances of SaNa, SaCTA and SaDDA modified electrodes were therefore evaluated and the experimental parameters were optimized. SaDDA gives the best results in deoxygenated acetate buffer solution (pH 6.0) after 2 min accumulation under open circuit conditions. Under optimal conditions, the reduction current is proportional to mesotrione concentration in the range from 0.25 to 2.5 μM with a detection limit of 0.26 μM. The fabricated electrode was also applied for the commercial formulation CALLISTO, used in European maize market. PMID:23200396

  20. Frequency-dependent conductivity in bismuth-vanadate glassy semiconductors

    NASA Astrophysics Data System (ADS)

    Ghosh, Aswini

    1990-01-01

    The first measurements are reported for the frequency-dependent (ac) conductivity (real as well as imaginary parts) for various compositions of the bismuth-vanadate glassy semiconductors in the frequency range 102-105 Hz and in the temperature range 77-420 K. The behavior of the ac conductivity is broadly similar to what has been observed previously in many other types of amorphous semiconductors, namely, nearly linear frequency dependence and weak temperature dependence. The experimental results are analyzed with reference to various theoretical models based on quantum-mechanical tunneling and classical hopping over barriers. The analysis shows that the temperature dependence of the ac conductivity is consistent with the simple quantum-mechanical tunneling model at low temperatures; however, this model completely fails to predict the observed temperature dependence of the frequency exponent. The overlapping-large-polaron tunneling model can explain the temperature dependence of the frequency exponent at low temperatures. Fitting of this model to the low-temperature data yields a reasonable value of the wave-function decay constant. However, this model predicts the temperature dependence of the ac conductivity much higher than what actual data showed. The correlated barrier hopping model is consistent with the temperature dependence of both the ac conductivity and its frequency exponent. This model provides reasonable values of the maximum barrier heights but higher values of characteristic relaxation times.

  1. Real-time nonequilibrium dynamics of quantum glassy systems

    NASA Astrophysics Data System (ADS)

    Cugliandolo, Leticia F.; Lozano, Gustavo

    1999-01-01

    We develop a systematic analytic approach to aging effects in quantum disordered systems in contact with an environment. Within the closed-time path-integral formalism we include dissipation by coupling the system to a set of independent harmonic oscillators that mimic a quantum thermal bath. After integrating over the bath variables and averaging over disorder we obtain an effective action that determines the real-time dynamics of the system. The classical limit yields the Martin-Siggia-Rose generating functional associated to a colored noise. We apply this general formalism to a prototype model related to the p spin glass. We show that the model has a dynamic phase transition separating the paramagnetic from the spin-glass phase and that quantum fluctuations depress the transition temperature until a quantum critical point is reached. We show that the dynamics in the paramagnetic phase is stationary but presents an interesting crossover from a region controlled by the classical critical point to another one controlled by the quantum critical point. The most characteristic property of the dynamics in a glassy phase, namely, aging, survives the quantum fluctuations. In the subcritical region the quantum fluctuation-dissipation theorem is modified in a way that is consistent with the notion of effective temperatures introduced for the classical case. We discuss these results in connection with recent experiments in dipolar quantum spin glasses and the relevance of the effective temperatures with respect to the understanding of the low-temperature dynamics.

  2. Structural origin of low temperature glassy relaxation in magnetic nanoparticles

    NASA Astrophysics Data System (ADS)

    Laha, Suvra; Regmi, Rajesh; Lawes, Gavin

    2013-03-01

    Magnetic nanoparticles often exhibit glass-like relaxation features at low temperatures. Here we discuss the effects of doping boron, cobalt, gadolinium and lanthanum on the low temperature magnetic properties of Fe3O4 nanoparticles. We investigated the structure of the nanoparticles using both X-ray diffraction and Raman studies, and find evidence for secondary phase formation in certain samples. We acquired Transmission Electron Microscopic images to give direct information on the morphology and microstructure of these doped nanoparticles. We measured the ac out-of-phase susceptibility (χ//) vs temperature (T) to parameterize the low temperature glassy magnetic relaxation. All samples show low temperature magnetic relaxation, but the amplitude of the signal increases dramatically for certain dopants. We attribute these low temperature frequency-dependent magnetic relaxation features to structural defects, which are enhanced in some of the doped Fe3O4 nanoparticles. These studies also confirm that the low temperature relaxation in nanoparticles arises from single particle effects and are not associated with interparticle interactions.

  3. Growth, microstructure, and failure of crazes in glassy polymers

    NASA Astrophysics Data System (ADS)

    Rottler, Jörg; Robbins, Mark O.

    2003-07-01

    We report on an extensive study of craze formation in glassy polymers. Molecular dynamics simulations of a coarse-grained bead-spring model were employed to investigate the molecular level processes during craze nucleation, widening, and breakdown for a wide range of temperature, polymer chain length N, entanglement length Ne, and strength of adhesive interactions between polymer chains. Craze widening proceeds via a fibril-drawing process at constant drawing stress. The extension ratio is determined by the entanglement length, and the characteristic length of stretched chain segments in the polymer craze is Ne/3. In the craze, tension is mostly carried by the covalent backbone bonds, and the force distribution develops an exponential tail at large tensile forces. The failure mode of crazes changes from disentanglement to scission for N/Ne˜10, and breakdown through scission is governed by large stress fluctuations. The simulations also reveal inconsistencies with previous theoretical models of craze widening, which were based on continuum level hydrodynamics.

  4. Gamma ray attenuation in a developed borate glassy system

    NASA Astrophysics Data System (ADS)

    Saeed, Aly; El shazly, R. M.; Elbashar, Y. H.; Abou El-azm, A. M.; El-Okr, M. M.; Comsan, M. N. H.; Osman, A. M.; Abdal-monem, A. M.; El-Sersy, A. R.

    2014-09-01

    Measurements and calculations of gamma ray attenuation coefficients in glass barriers of xBaO-5ZnO-5MgO-14Na2O--1Li2O-(75-x)B2O3, previously prepared by the melt-quenching technique [1], were performed for γ-ray of energies 121.8, 244.7, 344.14, 661.66, 778.7, 974, 1086.7, 1173.24, 1332.5, and 1407.9 keV; which emitted from 152Eu, 137Cs, and 60Co radioactive gamma ray sources. The transmitted γ-rays were detected by 3″×3″ and 5″×5″ NaI (Tl) scintillation γ-ray spectrometers, and a highly calibrated survey meter. The mass attenuation coefficients of γ-rays (σ(E) were deduced from the attenuation curves, while the WinXCom computer program (version 3.1) was used to calculate the mass attenuation coefficients of γ-rays for such energies at different barium concentrations of a glassy system. A good agreement between both experimental and theoretical results was achieved as well as results obtained by other workers in similar field.

  5. CO2 reduction catalyzed by mercaptopteridine on glassy carbon.

    PubMed

    Xiang, Dongmei; Magana, Donny; Dyer, R Brian

    2014-10-01

    The catalytic reduction of CO2 is of great current interest because of its role in climate change and the energy cycle. We report a pterin electrocatalyst, 6,7-dimethyl-4-hydroxy-2-mercaptopteridine (PTE), that catalyzes the reduction of CO2 and formic acid on a glassy carbon electrode. Pterins are natural cofactors for a wide range of enzymes, functioning as redox mediators and C1 carriers, but they have not been exploited as electrocatalysts. Bulk electrolysis of a saturated CO2 solution in the presence of the PTE catalyst produces methanol, as confirmed by gas chromatography and (13)C NMR spectroscopy, with a Faradaic efficiency of 10-23%. FTIR spectroelectrochemistry detected a progression of two-electron reduction products during bulk electrolysis, including formate, aqueous formaldehyde, and methanol. A transient intermediate was also detected by FTIR and tentatively assigned as a PTE carbamate. The results demonstrate that PTE catalyzes the reduction of CO2 at low overpotential and without the involvement of any metal. PMID:25259884

  6. Terbium induced glassy magnetism in La,Ca-based cobaltites

    SciTech Connect

    Maryško, M. Hejtmánek, J.; Jirák, Z.; Kaman, O.; Knížek, K.

    2014-05-07

    The La{sub 0.8–x}Tb{sub x}Ca{sub 0.2}CoO{sub 3} cobaltites of orthoperovskite Pbnm structure were investigated by the X-ray and neutron diffraction, specific heat, and magnetization measurements. The terbium doping has two important effects, it increases the size disorder on perovskite A-sites and influences the magnetic properties due to large Ising-type moments (∼8.9 Bohr magnetons per Tb). The compounds show a bulk magnetic moment below T{sub C} = 82 K, 53 K, and 30 K for x = 0.1, 0.2, and 0.3, respectively. The neutron diffraction evidences a long-range ferromagnetic arrangement of cobalt moments, combined below ∼20 K with ordering of terbium moments in a canted arrangement. A homogeneous magnetic phase is proved for the x = 0.1 sample, while x = 0.2 and 0.3 are in an intrinsically non-homogeneous magnetic state with long-range ordering only comprising 55% and 30% of the sample volumes. The ac susceptibility experiments prove a glassy character of the terbium doped samples and provide arguments for the short-range ordering above T{sub C} and wide distribution of relaxation times.

  7. Mechanics of particulate composites with glassy polymer binders in compression

    PubMed Central

    Jordan, J. L.; Spowart, J. E.; Kendall, M. J.; Woodworth, B.; Siviour, C. R.

    2014-01-01

    Whether used as structural components in design or matrix materials for composites, the mechanical properties of polymers are increasingly important. The compressive response of extruded polymethyl methacrylate (PMMA) rod with aligned polymer chains and Al–Ni–PMMA particulate composites are investigated across a range of strain rates and temperatures. The particulate composites were prepared using an injection-moulding technique resulting in highly anisotropic microstructures. The mechanics of these materials are discussed in the light of theories of deformation for glassy polymers. The experimental data from this study are compared with PMMA results from the literature as well as epoxy-based composites with identical particulates. The PMMA exhibited the expected strain rate and temperature dependence and brittle failure was observed at the highest strain rates and lowest temperatures. The Al–Ni–PMMA composites were found to have similar stress–strain response to the PMMA with reduced strain softening after yield. Increasing volume fraction of particulates in the composite resulted in decreased strength. PMID:24711495

  8. Surface temperatures and glassy state investigations in tribology, part 1

    NASA Technical Reports Server (NTRS)

    Winer, W. O.; Sanborn, D. M.

    1978-01-01

    The research in this report is divided into two categories: (1) lubricant rheological behavior, and (2) thermal behavior of a simulated elastohydrodynamic contact. The studies of the lubricant rheological behavior consists of high pressure, low shear rate viscosity measurements, viscoelastic transition measurements, by volume dilatometry, dielectric transitions at atmospheric pressure and light scattering transitions. Lubricant shear stress-strain behavior in the amorphous glassy state was measured on several fluids. It appears clear from these investigations that many lubricants undergo viscoplastic transitions in typical EHD contacts and that the lubricant has a limiting maximum shear stress it can support which in turn will determine the traction in the contact except in cases of very low slide-roll ratio. Surface temperature measurements were made for a naphthenic mineral oil and a polyphenyl ether. The maximum surface temperature in these experiments was approximately symmetrical about the zero slide-roll ration except for absolute values of slide-roll ratio greater than about 0.9. Additional surface temperature measurements were made in contacts with rough surfaces where the composite surface roughness was approximately equal to the EHD film thickness. A regression analysis was done to obtain a predictive equation for surface temperatures as a function of pressure, sliding speed, and surface roughness. A correction factor for surface roughness effects to the typical flash temperature analysis was found.

  9. Dielectric studies of molecular motions in glassy and liquid nicotine

    NASA Astrophysics Data System (ADS)

    Kaminski, K.; Paluch, M.; Ziolo, J.; Ngai, K. L.

    2006-06-01

    The dielectric permittivity and loss spectra of glassy and liquid states of nicotine have been measured over the frequency range 10-2-109 Hz. The relaxation spectra are similar to common small molecular glass-forming substances, showing the structural α-relaxation and its precursor, the Johari-Goldstein β-relaxation. The α-relaxation is well described by the Fourier transform of the Kohlrausch-Williams-Watts stretched exponential function with an approximately constant stretch exponent that is equal to 0.70 as the glass transition temperature is approached. The dielectric α-relaxation time measured over 11 orders of magnitude cannot be described by a single Vogel-Fulcher-Tamman-Hesse equation. The most probable Johari-Goldstein β-relaxation time determined from the dielectric spectra is in good agreement with the primitive relaxation time of the coupling model calculated from parameters of the structural α-relaxation. The shape of the dielectric spectra of nicotine is compared with that of other glass-formers having about the same stretch exponent, and they are shown to be nearly isomorphic. The results indicate that the molecular dynamics of nicotine conform to the general pattern found in other glass-formers, and the presence of the universal Johari-Goldstein secondary relaxation, which plays a role in the crystallization of amorphous pharmaceuticals.

  10. Evolution of Entanglements During Crazing of Glassy Polymers

    NASA Astrophysics Data System (ADS)

    Ge, Ting; Robbins, Mark O.; Hoy, Robert; Anogiannakis, Stefanos; Tzoumanekas, Christos; Theodorou, Doros

    2011-03-01

    Craze formation increases the fracture energy of glassy polymers by orders of magnitude. The polymer volume expands by an extension ratio which is assumed to be determined by the entanglement network. We test this assumption with molecular simulations that use the Contour Reduction Topological Analysis (CReTA) algorithm to follow topological constraints (TCs) associated with the entanglement network. The TCs are identified with contacts between chains after applying CReTA. Within systematic errors, crazing does not change the number of TCs or the distribution of chemical distances between them. Moreover, about 75% of the contacts remain between the same chains at nearly the same location. The 25% of contacts that change do not reflect a comparable loss of entanglements. Instead, small displacements within the tube change which chains contact after CReTA. This interpretation is tested by adding fixed crosslinks to a sparse entanglement network and crazing preoriented samples. This material is based upon work supported by NSF Grant DMR 108474.

  11. Entanglements and the Mechanical Properties of Glassy Polymers

    NASA Astrophysics Data System (ADS)

    Robbins, Mark

    2011-03-01

    The response of glassy polymers to shear or tensile strain is strongly influenced by the entanglement network that is inherited from the melt. Molecular dynamics simulations are used to probe the microscopic origins of stress-strain curves and their connection to entanglements. The latter are identified in real space by examining topological constraints along the primitive path. The first part of the talk will consider the process of craze formation, where the entanglement density is correlated to the volume increase during crazing. Simulations show that entanglements are preserved during crazing, but the craze density does not correspond to pulling chains taut between entanglements. The second part of the talk will examine the effect of entanglements on strain hardening under uniaxial strain. The stress is directly associated with the degree of orientational order along the strain axis, and nearly independent of order along perpendicular directions. Studies with mixtures of short and long chains show that the degree of order is independent of the surrounding chains. The final part of the talk will examine the strength of welds formed by diffusion across polymer interfaces. The shear stress follows the bulk response until chains are pulled taut on the scale of the length of segments that have diffused across the interface. When this length is several times the entanglement length, the maximum shear stress saturates at the bulk value and chains fail through scission. Similar trends are found for the fracture energy in tensile loading. This material is based upon work supported by NSF Grant DMR 108474.

  12. Application of low-temperature glassy carbon films in solid-phase microextraction.

    PubMed

    Giardina, M; Olesik, S V

    2001-12-15

    Low-temperature glassy carbon (LTGC) films were investigated as a sorbent coating for solid-phase microextraction because of its uniquely selective adsorptive characteristics. The selectivity of these coatings is primarily controlled by shape characteristics of the solute molecule and the final processing temperature used to form the LTGC, demonstrating unique adsorptive characteristics compared to commercial phases. The LTGC films were prepared by first coating porous silica particles with a diethylnyl oligomer precursor and then heat curing at temperatures between 300 and 1000 degrees C to form the LTGC. Then, using a sol-gel process, the LTGC-coated silica particles were immobilized onto stainless steel fibers and subsequently used for headspace and liquid extractions followed by GC-FID analysis. The selectivity of the LTGC is demonstrated by the extraction of a variety of aromatic hydrocarbons as well as the taste and odor contaminants geosmin, 2-methylisoborneol, and 2,4,6-trichloroanisole commonly found in water supplies. The data show that the LTGC coating has the highest affinity for molecules with the greatest cross-sectional surface area and polarizability and that this selective mechanism increases as a function of LTGC processing temperature. PMID:11791552

  13. Bucky-gel coated glassy carbon electrodes, for voltammetric detection of femtomolar leveled lead ions.

    PubMed

    Wan, Qijin; Yu, Fen; Zhu, Lina; Wang, Xiaoxia; Yang, Nianjun

    2010-10-15

    Femtomolar (fM) leveled lead ions were electrochemically detected using a bucky-gel coated glassy carbon electrode and differential pulse anodic stripping voltammetry. The bucky-gel was composed of dithizone, ionic liquid (1-butyl-3-methylimidazolium hexafluorophosphate), and multi-walled carbon nanotubes (MWCNTs). The fabrication of the bucky-gel coated electrode was optimized. The modified electrode was characterized with voltammetry, electrochemical impedance spectroscopy, and chronoamperometry. After the accumulation of lead ions into the bucky-gel modified electrode at -1.2V vs. saturated calomel electrode (SCE) for 5 min in a pH 4.4 sodium acetate-acetate acid buffer solution, differential pulse anodic stripping voltammograms of the accumulated lead show an anodic wave at -0.58 V. The anodic peak current is detectable for lead ions in the concentration range from 1.0 μM down to 500 fM. The detection limit is calculated to be 100 fM. The proposed method was successfully applied for the detection of lead ions in lake water. PMID:20875583

  14. Impact of SO 2 poisoning of platinum nanoparticles modified glassy carbon electrode on oxygen reduction

    NASA Astrophysics Data System (ADS)

    Awad, M. I.; Saleh, M. M.; Ohsaka, T.

    An extraordinary recovery characteristic of Pt-nanoparticles from SO 2 poisoning is introduced in this study. Platinum nanoparticles (nano-Pt) modified glassy carbon electrode (nano-Pt/GC) has been compared with polycrystalline platinum (poly-Pt) electrode towards SO 2 poisoning. Two procedures of recovery of the poisoned electrodes were achieved by cycling the potential in the narrow potential range (NPR, 0-0.8 V vs. Ag/AgCl/KCl (sat.)) and wide potential range (WPR, -0.2 to 1.3 V). The extent of recovery was marked using oxygen reduction reaction (ORR) as a probing reaction. SO 2 poisoning of the electrodes changed the mechanism of the oxygen reduction from the direct reduction to water to the stepwise reduction involving the formation of H 2O 2 as an intermediate, as indicated by the rotating ring-disk voltammetry. Using the WPR recovery procedure, it was found that two potential cycles were enough to recover 100% of the activity of the ORR on the nano-Pt/GC electrode. At the poly-Pt electrode, however, four potential cycles of the WPR caused only 79% in the current recovery, while the peak potential of the ORR was 130 mV negatively shifted as compared with the fresh poly-Pt electrode. Interestingly, the NPR procedure at the nano-Pt/GC electrode was even more efficient in the recovery than the WPR procedure at the poly-Pt electrode.

  15. Development of the glassy state of benzophenone and effect of heating rate from the glassy state on solidification

    SciTech Connect

    Thoma, P.E.; Boehm, J.J.

    1997-12-31

    Benzophenone supercools to a glass when cooled to {minus}100 C. In fact, it is difficult to freeze benzophenone on cooling. In this investigation, the effect of cooling rate and the minimum cooling rate to obtain benzophenone as a glass is determined. From the glassy state, the influence of heating rate on the solidification temperature of benzophenone is determined. When heated at 3 C/min., solidification starts at about {minus}29 C. Upon additional heating, melting usually starts at about +24 C, which is 23 C lower than the solid equilibrium structure melting temperature of 47 C. Occasionally the solid that forms at about {minus}29 C undergoes a solid state phase transformation at about +22 C, when heated at 3 C/min. If this solid state phase transformation occurs, then the solid benzophenone starts to melt at 47 C. When solid benzophenone with the equilibrium structure is cooled to {minus}100 C, no solid state phase transformation occurs. It appears that the structure that solidified at {minus}29 C is metastable.

  16. Immobilization of DNA at Glassy Ccarbon Electrodes: A Critical Study of Adsorbed Layer

    PubMed Central

    Pedano, M. L.; Rivas, G. A.

    2005-01-01

    In this work we present a critical study of the nucleic acid layer immobilized at glassy carbon electrodes. Different studies were performed in order to assess the nature of the interaction between DNA and the electrode surface. The adsorption and electrooxidation of DNA demonstrated to be highly dependent on the surface and nature of the glassy carbon electrode. The DNA layer immobilized at a freshly polished glassy carbon electrode was very stable even after applying highly negative potentials. The electron transfer of potassium ferricyanide, catechol and dopamine at glassy carbon surfaces modified with thin (obtained by adsorption under controlled potential conditions) and thick (obtained by casting the glassy carbon surface with highly concentrated DNA solutions) DNA layers was slower than that at the bare glassy carbon electrode, although this effect was dependent on the thickness of the layer and was not charge selective. Raman experiments showed an important decrease of the vibrational modes assigned to the nucleobases residues, suggesting a strong interaction of these residues with the electrode surface. The hybridization of oligo(dG)21 and oligo(dC)21 was evaluated from the guanine oxidation signal and the reduction of the redox indicator Co(phen)33+. In both cases the chronopotentiometric response indicated that the compromise of the bases in the interaction of DNA with the electrode surface is too strong, preventing further hybridization. In summary, glassy carbon is a useful electrode material to detect DNA in a direct and very sensitive way, but not to be used for the preparation of biorecognition layers by direct adsorption of the probe sequence on the electrode surface for detecting the hybridization event.

  17. How important are glassy SOA ice nuclei for the formation of cirrus clouds?

    NASA Astrophysics Data System (ADS)

    Zhou, C.; Penner, J. E.; Lin, G.; Liu, X.; Wang, M.

    2014-12-01

    Extremely low ice numbers (i.e. 5 - 100 / L) have been observed in the tropical troposphere layer (TTL) in a variety of field campaigns. Various mechanisms have been proposed to explain these low numbers, including the effect of glassy secondary organic aerosol acting as heterogeneous ice nuclei (IN). In this study, we explored these effects using the CAM5.3 model. SOA fields were provided by an offline version of the University of Michigan-IMPACT model, which has a detailed process-based mechanism that describes aerosol microphysics and SOA formation through both gas phase and multiphase reactions. The transition criterion of SOA to glassy heterogeneous IN follows the parameterization developed by Wang et al. 2012. With this parameterization, glassy SOA IN form mainly when the temperature (T) is lower than 210K. In the default CAM5.3 set-up in which only the fraction of Aitken mode sulfate aerosols with diameter larger than 100nm participate in the ice nucleation (Liu and Penner 2005 parameterization), glassy SOA IN are shown to decrease the ice number (Ni) by suppressing some of the homogeneous freezing at low temperatures thereby leading to an improved representation of the relationship between Ni and T compared to the observations summarized by Kramer et al. 2009. However, when we allow the total number of the Aitken mode sulfate particles to participate in homogeneous freezing, glassy SOA IN have only a small impact on the relationship between Ni and T. If the subgrid updraft velocity is decreased to 0.1 m/s (compared to 0.2 m/s in the default set-up), there is a large decrease of Ni, since homogeneous freezing is more easily suppressed by glassy SOA IN at these updrafts. We also present the effects of glassy SOA IN using an alternative ice nucleation scheme (Barahona and Nenes, 2009).

  18. Modeling mechanophore activation within a crosslinked glassy matrix

    NASA Astrophysics Data System (ADS)

    Silberstein, Meredith N.; Min, Kyoungmin; Cremar, Lee D.; Degen, Cassandra M.; Martinez, Todd J.; Aluru, Narayana R.; White, Scott R.; Sottos, Nancy R.

    2013-07-01

    Mechanically induced reactivity is a promising means for designing self-reporting materials. Mechanically sensitive chemical groups called mechanophores are covalently linked into polymers in order to trigger specific chemical reactions upon mechanical loading. These mechanophores can be linked either within the backbone or as crosslinks between backbone segments. Mechanophore response is sensitive to both the matrix properties and placement within the matrix, providing two avenues for material design. A model framework is developed to describe reactivity of mechanophores located as crosslinks in a glassy polymer matrix. Simulations are conducted at the molecular and macromolecular scales in order to develop macroscale constitutive relations. The model is developed specifically for the case of spiropyran (SP) in lightly crosslinked polymethylmethacrylate (PMMA). This optically trackable mechanophore (fluorescent when activated) allows the model to be assessed in terms of observed experimental behavior. The force modified potential energy surface (FMPES) framework is used in conjunction with ab initio steered molecular dynamics (MD) simulations of SP to determine the mechanophore kinetics. MD simulations of the crosslinked PMMA structure under shear deformation are used to determine the relationship between macroscale stress and local force on the crosslinks. A continuum model implemented in a finite element framework synthesizes these mechanochemical relations with the mechanical behavior. The continuum model with parameters taken directly from the FMPES and MD analyses under predicts stress-driven activation relative to experimental data. The continuum model, with the physically motivated modification of force fluctuations, provides an accurate prediction for monotonic loading across three decades of strain rate and creep loading, suggesting that the fundamental physics are captured.

  19. Electrochemical oxidation of butein at glassy carbon electrodes.

    PubMed

    Tesio, Alvaro Yamil; Robledo, Sebastián Noel; Fernández, Héctor; Zon, María Alicia

    2013-06-01

    The electrochemical oxidation of flavonoid butein is studied at glassy carbon electrodes in phosphate and citrate buffer solutions of different pH values, and 1M perchloric acid aqueous solutions by cyclic and square wave voltammetries. The oxidation peak corresponds to the 2e(-), 2H(+) oxidation of the 3,4-dihydroxy group in B ring of butein, given the corresponding quinone species. The overall electrode process shows a quasi-reversible behavior and an adsorption/diffusion mixed control at high butein bulk concentrations. At low butein concentrations, the electrode process shows mainly an adsorption control. Butein surface concentration values were obtained from the charge associated with the adsorbed butein oxidation peaks, which are in agreement with those values expected for the formation of a monolayer of adsorbate in the concentration range from 1 to 5μM. Square wave voltammetry was used to perform a full thermodynamic and kinetics characterization of the butein surface redox couple. Therefore, from the combination of the "quasi-reversible maximum" and the "splitting of the net square wave voltammetric peak" methods, values of (0.386±0.003) V, (0.46±0.04), and 2.7×10(2)s(-1) were calculated for the formal potential, the anodic transfer coefficient, and the formal rate constant, respectively, of the butein overall surface redox process in pH4.00 citrate buffer solutions. These results will be then used to study the interaction of butein, and other flavonoids with the deoxyribonucleic acid, in order to better understand the potential therapeutic applications of these compounds. PMID:23434740

  20. Charge Transport and Glassy Dynamics in Ionic Liquids

    SciTech Connect

    Sangoro, Joshua R; Kremer, Friedrich

    2012-01-01

    Ionic liquids (ILs) exhibit unique features such as low melting points, low vapor pressures, wide liquidus temperature ranges, high thermal stability, high ionic conductivity, and wide electrochemical windows. As a result, they show promise for use in variety of applications: as reaction media, in batteries and supercapacitors, in solar and fuel cells, for electrochemical deposition of metals and semiconductors, for protein extraction and crystallization, and many others. Because of the ease with which they can be supercooled, ionic liquids offer new opportunities to investigate long-standing questions regarding the nature of the dynamic glass transition and its possible link to charge transport. Despite the significant steps achieved from experimental and theoretical studies, no generally accepted quantitative theory of dynamic glass transition to date has been capable of reproducing all the experimentally observed features. In this Account, we discuss recent studies of the interplay between charge transport and glassy dynamics in ionic liquids as investigated by a combination of several experimental techniques including broadband dielectric spectroscopy, pulsed field gradient nuclear magnetic resonance, dynamic mechanical spectroscopy, and differential scanning calorimetry. Based on EinsteinSmoluchowski relations, we use dielectric spectra of ionic liquids to determine diffusion coefficients in quantitative agreement with independent pulsed field gradient nuclear magnetic resonance measurements, but spanning a broader range of more than 10 orders of magnitude. This approach provides a novel opportunity to determine the electrical mobility and effective number density of charge carriers as well as their types of thermal activation from the measured dc conductivity separately. We also unravel the origin of the remarkable universality of charge transport in different classes of glass-forming ionic liquids.

  1. Charge transport and glassy dynamics in ionic liquids.

    PubMed

    Sangoro, Joshua R; Kremer, Friedrich

    2012-04-17

    Ionic liquids (ILs) exhibit unique features such as low melting points, low vapor pressures, wide liquidus temperature ranges, high thermal stability, high ionic conductivity, and wide electrochemical windows. As a result, they show promise for use in variety of applications: as reaction media, in batteries and supercapacitors, in solar and fuel cells, for electrochemical deposition of metals and semiconductors, for protein extraction and crystallization, and many others. Because of the ease with which they can be supercooled, ionic liquids offer new opportunities to investigate long-standing questions regarding the nature of the dynamic glass transition and its possible link to charge transport. Despite the significant steps achieved from experimental and theoretical studies, no generally accepted quantitative theory of dynamic glass transition to date has been capable of reproducing all the experimentally observed features. In this Account, we discuss recent studies of the interplay between charge transport and glassy dynamics in ionic liquids as investigated by a combination of several experimental techniques including broadband dielectric spectroscopy, pulsed field gradient nuclear magnetic resonance, dynamic mechanical spectroscopy, and differential scanning calorimetry. Based on Einstein-Smoluchowski relations, we use dielectric spectra of ionic liquids to determine diffusion coefficients in quantitative agreement with independent pulsed field gradient nuclear magnetic resonance measurements, but spanning a broader range of more than 10 orders of magnitude. This approach provides a novel opportunity to determine the electrical mobility and effective number density of charge carriers as well as their types of thermal activation from the measured dc conductivity separately. We also unravel the origin of the remarkable universality of charge transport in different classes of glass-forming ionic liquids. PMID:22082024

  2. Relaxation dynamics and crystallization study of sildenafil in the liquid and glassy states.

    PubMed

    Kolodziejczyk, K; Paluch, M; Grzybowska, K; Grzybowski, A; Wojnarowska, Z; Hawelek, L; Ziolo, J D

    2013-06-01

    In this paper, the physical stability and molecular dynamics of amorphous sildenafil are investigated in both the liquid and glassy states. We have established that the amorphous sildenafil is resistant to recrystallization at temperatures below the glass transition temperature Tg during the experimental period of its storage (i.e., above 6 months), however, it easily undergoes cold crystallization at T > Tg. To determine the crystallization mechanism, the isothermal and non-isothermal studies of the cold crystallization kinetics of the drug are performed by using the broadband dielectric spectroscopy (BDS) and the differential scanning calorimetry (DSC), respectively. The cold crystallization mechanism has been found to be similar in both the isothermal and non-isothermal cases. This mechanism has been analyzed from the point of view of the molecular mobility of sildenafil investigated in the supercooled liquid and glassy states by using the BDS measurements in the wide temperature range. This analysis has been enriched with a new approach based on a recently reported measure of dynamic heterogeneity given by a four-point dynamic susceptibility function. No tendency to recrystallization of glassy sildenafil at T < Tg is also discussed in relation to molecular dynamics of sildenafil in the glassy state. The relatively small molecular mobility reflected in one secondary relaxation as well as the predicted large time scale of structural relaxation of glassy sildenafil suggests that amorphous sildenafil should not recrystallize during its long-term storage at room temperature. PMID:23594226

  3. Understanding the Physical Aging Behavior of Glassy Polystyrene Layers in Close Contact with Rubbery Domains

    NASA Astrophysics Data System (ADS)

    Roth, Connie; Rauscher, Phil; Pye, Justin; Baglay, Roman

    2014-03-01

    Recent advances in synthesis strategies and processing methods have led to new nanostructured polymer blend and block-copolymer materials containing domain sizes less than 100 nm with glassy and rubbery domains in close proximity. Given the outsized role interfacial perturbations have played in causing large changes in the glass transition temperature Tg and physical aging of ultrathin single-layer films, we are interested in studying how the presence of glassy-rubbery interfaces between neighboring polymer domains may alter the local stability and physical aging of confined glassy layers. Using a polystyrene (PS) / poly(n-butyl methacrylate) (PnBMA) weakly immiscible system with 7 nm interfacial width, we demonstrate how ellipsometry can be used to isolate the physical aging rate of thin PS layers atop rubbery PnBMA layers. Despite a 25-30 K reduction in the average Tg of 84 nm thick PS layers atop PnBMA as measured by fluorescence, we observe no change in the PS aging rate relative to bulk. These results are in contrast with previous works on single-layer polymer films that have found the local aging rate to often be correlated with local Tg changes. This appears not to be the case for glassy PS layers atop rubbery PnBMA suggesting some additional factor is affecting the structural relaxation occurring near the glassy-rubbery interface.

  4. Mechanisms of crazing in glassy polymers revealed by molecular dynamics simulations

    NASA Astrophysics Data System (ADS)

    Mahajan, Dhiraj K.; Hartmaier, Alexander

    2012-08-01

    Mechanisms leading to initiation of crazing type failure in a glassy polymer are not clearly understood. This is mainly due to the difficulty in characterizing the stress state and polymer configuration sufficiently locally at the craze initiation site. Using molecular dynamics simulations, we have now been able to access this information and have shown that the local heterogeneous deformation leads to craze initiation in glassy polymers. We found that zones of high plastic activity are constrained by their neighborhood and become unstable, initiating crazing from these sites. Furthermore, based on the constant flow stresses observed in the unstable zones, we conclude that microcavitation is the essential local deformation mode to trigger crazing in glassy polymers. Our results demonstrate the basic difference in the local deformation mode as well as the conditions that lead to either shear-yielding or crazing type failures in glassy polymers. We anticipate our paper to help in devising a new criterion for craze initiation that not only considers the stress state, but also considers local deformation heterogeneities that form the necessary condition for crazing in glassy polymers.

  5. Mechanisms of crazing in glassy polymers revealed by molecular dynamics simulations.

    PubMed

    Mahajan, Dhiraj K; Hartmaier, Alexander

    2012-08-01

    Mechanisms leading to initiation of crazing type failure in a glassy polymer are not clearly understood. This is mainly due to the difficulty in characterizing the stress state and polymer configuration sufficiently locally at the craze initiation site. Using molecular dynamics simulations, we have now been able to access this information and have shown that the local heterogeneous deformation leads to craze initiation in glassy polymers. We found that zones of high plastic activity are constrained by their neighborhood and become unstable, initiating crazing from these sites. Furthermore, based on the constant flow stresses observed in the unstable zones, we conclude that microcavitation is the essential local deformation mode to trigger crazing in glassy polymers. Our results demonstrate the basic difference in the local deformation mode as well as the conditions that lead to either shear-yielding or crazing type failures in glassy polymers. We anticipate our paper to help in devising a new criterion for craze initiation that not only considers the stress state, but also considers local deformation heterogeneities that form the necessary condition for crazing in glassy polymers. PMID:23005778

  6. Temporal disconnectivity of the energy landscape in glassy systems

    NASA Astrophysics Data System (ADS)

    Lempesis, Nikolaos; Boulougouris, Georgios C.; Theodorou, Doros N.

    2013-03-01

    An alternative graphical representation of the potential energy landscape (PEL) has been developed and applied to a binary Lennard-Jones glassy system, providing insight into the unique topology of the system's potential energy hypersurface. With the help of this representation one is able to monitor the different explored basins of the PEL, as well as how - and mainly when - subsets of basins communicate with each other via transitions in such a way that details of the prior temporal history have been erased, i.e., local equilibration between the basins in each subset has been achieved. In this way, apart from detailed information about the structure of the PEL, the system's temporal evolution on the PEL is described. In order to gather all necessary information about the identities of two or more basins that are connected with each other, we consider two different approaches. The first one is based on consideration of the time needed for two basins to mutually equilibrate their populations according to the transition rate between them, in the absence of any effect induced by the rest of the landscape. The second approach is based on an analytical solution of the master equation that explicitly takes into account the entire explored landscape. It is shown that both approaches lead to the same result concerning the topology of the PEL and dynamical evolution on it. Moreover, a "temporal disconnectivity graph" is introduced to represent a lumped system stemming from the initial one. The lumped system is obtained via a specially designed algorithm [N. Lempesis, D. G. Tsalikis, G. C. Boulougouris, and D. N. Theodorou, J. Chem. Phys. 135, 204507 (2011), 10.1063/1.3663207]. The temporal disconnectivity graph provides useful information about both the lumped and the initial systems, including the definition of "metabasins" as collections of basins that communicate with each other via transitions that are fast relative to the observation time. Finally, the two examined

  7. Pattern formation in polymer via electrohydrodynamic instabilities and glassy fracture

    NASA Astrophysics Data System (ADS)

    Pease, Leonard Franklin, III

    Fabrication of micro and nano structures from polymeric materials has attracted significant attention due to their promise of inexpensive, fast throughput and ease of integration into existing fabrication processes. This dissertation describes our contributions to two such processes. In the first process, electrohydrodynamic flow drives a thin polymer film sandwiched between electrodes with an intervening gap into multidomained, hexagonally packed pillars or concentric rings. We model the initial stages of formation by performing a linear stability analysis under the lubrication approximation. We find the presence of free charge at the free interface both decreases the pillar-to-pillars spacing and increases the growth rate. We examined the possible sources of electrostatic field in the absence of an applied voltage to find static charge to be the most likely candidate. In practice, however, the lubrication approximation may not strictly apply in the situations of greatest interest. Accordingly, we contrasted results of the linear stability analysis with and without the lubrication approximation to show that the approximation fails where surface tension is small and electric fields are large, typical of experiments with a polymer/organic liquid instead of air in the gap---precisely the conditions that predict the smallest pillar arrays. Motivated by the discovery of concentric rings, we adapted the form of the perturbation from sinusoids to Bessel functions to predict constant ring-to-ring spacings, constant annular widths and growth rates in agreement with experiment. In the second patterning technique, a thin film sandwiched between two substrates fractures into periodic ridges upon insertion of a razor blade. We investigated the conditions that selected for the presence or absence of the gratings, their fractional coverage, their period, and their alignment. Our key findings indicated that the gratings form from all glassy materials tested with periods of

  8. Direct Imaging of Dynamic Glassy Behavior in a Strained Manganite Film.

    PubMed

    Kundhikanjana, Worasom; Sheng, Zhigao; Yang, Yongliang; Lai, Keji; Ma, Eric Yue; Cui, Yong-Tao; Kelly, Michael A; Nakamura, Masao; Kawasaki, Masashi; Tokura, Yoshinori; Tang, Qiaochu; Zhang, Kun; Li, Xinxin; Shen, Zhi-Xun

    2015-12-31

    Complex many-body interaction in perovskite manganites gives rise to a strong competition between ferromagnetic metallic and charge-ordered phases with nanoscale electronic inhomogeneity and glassy behaviors. Investigating this glassy state requires high-resolution imaging techniques with sufficient sensitivity and stability. Here, we present the results of a near-field microwave microscope imaging on the strain-driven glassy state in a manganite film. The high contrast between the two electrically distinct phases allows direct visualization of the phase separation. The low-temperature microscopic configurations differ upon cooling with different thermal histories. At sufficiently high temperatures, we observe switching between the two phases in either direction. The dynamic switching, however, stops below the glass transition temperature. Compared with the magnetization data, the phase separation was microscopically frozen, while spin relaxation was found in a short period of time. PMID:26765006

  9. Novel ferroelectric liquid crystals consisting glassy liquid crystal as chiral dopants

    NASA Astrophysics Data System (ADS)

    Chen, Huang-Ming Philip; Tsai, Yun-Yen; Lin, Chi-Wen; Shieh, Han-Ping David

    2006-08-01

    A series of ferroelectric liquid crystals consisting new glassy liquid crystals (GLCs) as chiral dopants were prepared and evaluated for their potentials in fast switching ability less than 1 ms. The properties of pure ferroelectric glassy liquid crystals (FGLCs) and mixtures were reported in this paper. In particular, the novel FGLC possessing wide chiral smectic C mesophase over 100 °C is able to suppress smectic A phase of host. The mixture containing 2.0 % GLC-1 performs greater alignment ability and higher contrast ratio than R2301 (Clariant, Japan) in a 2 μm pre-made cell (EHC, Japan). These results indicate that novel FLC mixtures consisting glassy liquid crystals present a promising liquid crystal materials for fast switching field sequential color displays.

  10. Glassiness and exotic entropy scaling induced by quantum fluctuations in a disorder-free frustrated magnet

    PubMed Central

    Klich, I.; Lee, S.-H.; Iida, K.

    2014-01-01

    When spins are arranged in a lattice of triangular motif, the phenomenon of frustration leads to numerous energetically equivalent ground states, and results in exotic states such as spin liquid and spin ice. Here we report an alternative situation: a system, classically a liquid, freezes in the clean limit into a glassy state induced by quantum fluctuations. We call such glassy state a spin jam. The case in point is a frustrated magnet, where spins are arranged in a triangular network of bipyramids. Quantum corrections break the classical degeneracy into a set of aperiodic spin configurations forming local minima in a rugged energy landscape. This is established by mapping the problem into tiling with hexagonal tiles. The number of tessellations scales with the boundary length rather than its volume, showing the absence of local zero-energy modes. Low-temperature thermodynamics is discussed to compare it with other glassy materials. PMID:24686398

  11. Direct Imaging of Dynamic Glassy Behavior in a Strained Manganite Film

    NASA Astrophysics Data System (ADS)

    Kundhikanjana, Worasom; Sheng, Zhigao; Yang, Yongliang; Lai, Keji; Ma, Eric Yue; Cui, Yong-Tao; Kelly, Michael A.; Nakamura, Masao; Kawasaki, Masashi; Tokura, Yoshinori; Tang, Qiaochu; Zhang, Kun; Li, Xinxin; Shen, Zhi-Xun

    2015-12-01

    Complex many-body interaction in perovskite manganites gives rise to a strong competition between ferromagnetic metallic and charge-ordered phases with nanoscale electronic inhomogeneity and glassy behaviors. Investigating this glassy state requires high-resolution imaging techniques with sufficient sensitivity and stability. Here, we present the results of a near-field microwave microscope imaging on the strain-driven glassy state in a manganite film. The high contrast between the two electrically distinct phases allows direct visualization of the phase separation. The low-temperature microscopic configurations differ upon cooling with different thermal histories. At sufficiently high temperatures, we observe switching between the two phases in either direction. The dynamic switching, however, stops below the glass transition temperature. Compared with the magnetization data, the phase separation was microscopically frozen, while spin relaxation was found in a short period of time.

  12. Enhancement of electrogenerated chemiluminescence of luminol by ascorbic acid at gold nanoparticle/graphene modified glassy carbon electrode.

    PubMed

    Dong, Yongping; Gao, Tingting; Zhou, Ying; Chu, Xiangfeng; Wang, Chengming

    2015-01-01

    Gold nanoparticle/graphene (GNP/GR) nanocomposite was one-pot synthesized from water soluble graphene and HAuCl₄ by hydrothermal method and characterized by TEM, Raman spectroscopy, XRD, XPS, UV-vis spectroscopy, and electrochemical impedance spectroscopy (EIS). Electrogenerated chemiluminescence (ECL) of luminol was investigated at the GNP/GR modified glassy carbon electrode (GNP/GR/GCE) and the GNP modified glassy carbon electrode (GNP/GCE) in aqueous solution respectively. The results revealed that one strong anodic ECL peak could be observed at ∼0.8 V at two modified electrodes compared with that at the bare electrode. The intensity of the anodic ECL at the GNP/GR/GCE is weaker than that at the GNP/GCE, which should be due to the synergic effect of the enhancing effect of gold nanoparticles and the inhibiting effect of graphene on anodic luminol ECL. One strong cathodic ECL peak located at ∼-0.8 V could be observed at the GNP/GR/GCE but not at the GNP/GCE, which should be result from the adsorbed oxygen at the graphene film. In the presence of ascorbic acid, the anodic ECL at the GNP/GR/GCE was enhanced more than 8-times, which is more apparent than that at the GNP/GCE. Whereas, the cathodic ECL peak was seriously inhibited at the GNP/GR/GCE. The enhanced ECL intensity at the GNP/GR/GCE varied linearly with the logarithm of ascorbic acid concentration in the range of 1.0 × 10(-8) to 1.0 × 10(-6)mol L(-1) with a detection limit of 1.0 × 10(-9) mol L(-1). The possible ECL mechanism was also discussed. PMID:25022493

  13. Enhancement of electrogenerated chemiluminescence of luminol by ascorbic acid at gold nanoparticle/graphene modified glassy carbon electrode

    NASA Astrophysics Data System (ADS)

    Dong, Yongping; Gao, Tingting; Zhou, Ying; Chu, Xiangfeng; Wang, Chengming

    2015-01-01

    Gold nanoparticle/graphene (GNP/GR) nanocomposite was one-pot synthesized from water soluble graphene and HAuCl4 by hydrothermal method and characterized by TEM, Raman spectroscopy, XRD, XPS, UV-vis spectroscopy, and electrochemical impedance spectroscopy (EIS). Electrogenerated chemiluminescence (ECL) of luminol was investigated at the GNP/GR modified glassy carbon electrode (GNP/GR/GCE) and the GNP modified glassy carbon electrode (GNP/GCE) in aqueous solution respectively. The results revealed that one strong anodic ECL peak could be observed at ∼0.8 V at two modified electrodes compared with that at the bare electrode. The intensity of the anodic ECL at the GNP/GR/GCE is weaker than that at the GNP/GCE, which should be due to the synergic effect of the enhancing effect of gold nanoparticles and the inhibiting effect of graphene on anodic luminol ECL. One strong cathodic ECL peak located at ∼-0.8 V could be observed at the GNP/GR/GCE but not at the GNP/GCE, which should be result from the adsorbed oxygen at the graphene film. In the presence of ascorbic acid, the anodic ECL at the GNP/GR/GCE was enhanced more than 8-times, which is more apparent than that at the GNP/GCE. Whereas, the cathodic ECL peak was seriously inhibited at the GNP/GR/GCE. The enhanced ECL intensity at the GNP/GR/GCE varied linearly with the logarithm of ascorbic acid concentration in the range of 1.0 × 10-8 to 1.0 × 10-6 mol L-1 with a detection limit of 1.0 × 10-9 mol L-1. The possible ECL mechanism was also discussed.

  14. Elastic properties of aspirin in its crystalline and glassy phases studied by micro-Brillouin scattering

    NASA Astrophysics Data System (ADS)

    Ko, Jae-Hyeon; Lee, Kwang-Sei; Ike, Yuji; Kojima, Seiji

    2008-11-01

    The acoustic waves propagating along the direction perpendicular to the (1 0 0) cleavage plane of aspirin crystal were investigated using micro-Brillouin spectroscopy from which C11, C55 and C66 were obtained. The temperature dependence of the longitudinal acoustic waves could be explained by normal anharmonic lattice models, while the transverse acoustic waves showed an abnormal increase in the hypersonic attenuation at low temperatures indicating their coupling to local remnant dynamics. The sound velocity as well as the attenuation of the longitudinal acoustic waves of glassy aspirin showed a substantial change at ˜235 K confirming a transition from glassy to supercooled liquid state in vitreous aspirin.

  15. A Thermodynamic Theory of Solid Viscoelasticity. Part 3: Nonlinear Glassy Viscoelasticity, Stability Constraints, Specifications

    NASA Technical Reports Server (NTRS)

    Freed, Alan; Leonov, Arkady I.

    2002-01-01

    This paper, the last in the series, continues developing the nonlinear constitutive relations for non-isothermal, compressible, solid viscoelasticity. We initially discuss a single integral approach, more suitable for the glassy state of rubber-like materials, with basic functionals involved in the thermodynamic description for this type of viscoelasticity. Then we switch our attention to analyzing stability constraints, imposed on the general formulation of the nonlinear theory of solid viscoelasticity. Finally, we discuss specific (known from the literature or new) expressions for material functions that are involved in the constitutive formulations of both the rubber-like and glassy-like, complementary parts of the theory.

  16. Nature of ThF bonding in crystalline and glassy states using EXAFS and XANES

    NASA Astrophysics Data System (ADS)

    Rao, K. J.; Wong, J.; Shafer, M. W.

    1984-11-01

    A binary glass of thorium and hafnium tetrafluorides (with dopant concentrations of LaF 3) has been investigated using EXAFS and XANES analysis of the L Ill edge spectra of thorium. Results of EXAFS analysis indicate that there is no change in the number of nearest neighbors of thorium ions. However, the intensity of the white line in XANES is significantly higher in the glass. This increase in intensity has been explained semiquantitatively in terms of enhanced covalency of ThF bonding. Since the coordination number of Th 4+ remains constant in both crystalline and glassy states, covalency enhancement seems to be a general characteristic of glassy state of ionic materials.

  17. Characterization of molecular mobility within the glassy matrix of dry seeds using mechanical properties: pea cotyledon as a test study

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Seed glasses form during maturation drying and regulate seed longevity. Seeds continue to age within the glassy state and, even during cryogenic storage, viability eventually declines. Inevitability of aging suggests some level of molecular motion within the glassy matrix and quantifying these “rel...

  18. Soft magnetic properties of bulk FeCoMoPCBSi glassy core prepared by copper mold casting

    NASA Astrophysics Data System (ADS)

    Zhang, Mingxiao; Kong, Fanli; Wang, Anding; Chang, Chuntao; Shen, Baolong

    2012-04-01

    Bulk Fe66Co10Mo3.5P10C4B4Si2.5 glassy core of 10 mm in outer diameter, 6 mm in inner diameter, and 1 mm in thickness was successfully prepared by copper mold casting. The effects of annealing treatments on magnetic properties and microstructure of these cores were investigated. After an optimum annealing treatment, the resulting bulk glassy core exhibits good magnetic properties, i.e., high saturation magnetic flux density of 1.23 T, low coercive force of 1.0 A/m, high maximum permeability of 450 000, respectively. In addition, the glassy core also shows low core loss of 0.4 W/kg at 50 Hz and at maximum magnetic flux density of 1 T. The synthesis of bulk glassy core with excellent magnetic properties is encouraging for enlarging the application field of ferromagnetic bulk glassy alloys.

  19. Fabrication of Glassy and Crystalline Ferroelectric Oxide by Containerless Processing

    NASA Astrophysics Data System (ADS)

    Yoda, Shinichi

    1. Instruction Much effort has been devoted to forming bulk glass from the melt of ferroelectric crystalline materials without adding any network-forming oxides such as SiO2 due to the potential for producing transparent glass ceramics with high dielectric constant and enhanced piezoelectric, pyroelectric and electro-optic effects. However, they require a higher cooling rate than glass formed by conventional techniques. Therefore, only amorphous thin-films have been formed, using rapid quenching with a cooling rate >105 K/s. The containerless processing is an attractive synthesis technique as it can prevent melt contamination, minimize heterogeneous nucleation, and allow melt to achieve deep undercooling for forming metastable phase and glassy material. Recently a new ferroelectric materiel, monoclinic BaTi2 O5 , with Currie temperature as 747 K was reported. In this study, we fabricated a bulk BaTi2 O5 glass from melt using containerless processing to study the phase relations and ferroelectric properties of BaTi2 O5 . To our knowledge, this was the first time that a bulk glass of ferroelectric material was fabricated from melt without adding any network-forming oxide. 2. Experiments BaTi2 O5 sphere glass with 2mm diameter was fabricated using containerless processing in an Aerodynamic Levitation Furnace (ALF). The containerless processing allowed the melt to achieve deep undercooling for glass forming. High purity commercial BaTiO3 and TiO2 powders were mixed with a mole ratio of 1:1 and compressed into rods and then sintered at 1427 K for 10 h. Bulk samples with a mass of about 20 mg were cut from the rod, levitated with the ALF, and then melted by a CO2 laser beam. After quenching with a cooling rate of about 1000 K/s, 2 mm diameter sphere glass could be obtained. To analyze the glass structure, a high-energy x-ray diffraction experiment was performed using an incident photon energy of 113.5 keV at the high-energy x-ray diffraction beamline BL04B2 of SPring-8

  20. Water

    MedlinePlus

    ... www.girlshealth.gov/ Home Nutrition Nutrition basics Water Water Did you know that water makes up more ... to drink more water Other drinks How much water do you need? top Water is very important, ...

  1. Effects of egg load on the oviposition behavior of the glassy-winged sharpshooter

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Egg load (number of mature eggs carried by an adult female) is commonly hypothesized to affect oviposition behavior. The effects of egg load on oviposition behavior of the glassy-winged sharpshooter, Homalodisca vitripennis (Hemiptera: Cicadellidae), were assessed through a series of laboratory bio...

  2. Assessing the post-winter threat of glassy-winged sharpshooter populations

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Glassy-winged sharpshooter (GWSS), Homalodisca vitripennis, appears to be limited to discrete regions within the San Joaquin Valley where winter temperatures are mild and rarely drop below freezing. Prior research indicates that GWSS adults cannot feed when maximum daily temperatures are below 50°F...

  3. Abundance and consumption rate of glassy-winged sharpshooter (Hemiptera: Cicadellidae) on peaches and plums

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Homalodisca vitripennis, also known as the glassy-winged sharpshooter, is a primary vector of phony peach and plum leaf scald diseases caused by Xylella fastidiosa Wells et al. Two of the following scions, (Prunus persica L. Batch cvs. Flordaking and June Gold and Prunus salicina L. cvs. Methley an...

  4. Phylogenetic analysis of heat shock proteins in Glassy-winged sharpshooter

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Four heat shock protein transcripts were produced from the glassy-winged sharpshooter Homalodisca vitripennis (Germar) (Hemiptera: Cicadellidae) which is the major vector of Xylella fastidiosa, the causal agent of Pierce’s disease of grapes. As genomic information has continued to be produced resea...

  5. Assessing the Post-Winter Threat of Glassy-winged Sharpshooter Populations

    Technology Transfer Automated Retrieval System (TEKTRAN)

    After glassy-winged sharpshooter (GWSS), Homalodisca vitripennis, arrived in California, it was believed that the insect would establish throughout much of the northern agricultural production areas. However, GWSS appears to be limited to discrete regions within the San Joaquin Valley where winter ...

  6. Identification of HoCV-1 virus in Texas Glassy-Winged Sharpshooter Populations

    Technology Transfer Automated Retrieval System (TEKTRAN)

    A new strain of leafhopper virus was discovered in leafhoppers which are vectors of Pierce’s disease of grapes. The original leafhopper infecting virus, HoCV-1, was isolated from the glassy-winged sharpshooter, Homalodisca vitripennis, from samples collected in California and Florida. Using the orig...

  7. Substrate-borne vibrational signals in intraspecific communication of glassy-winged sharpshooters (GWSS)

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Exploitation of vibrational signals for suppressing glassy-winged sharpshooter (GWSS) populations could prove to be a useful tool. However, existing knowledge on GWSS vibrational communication is insufficient to implement a management program for this pest in California. Therefore, the objective of ...

  8. Identifying key predators of the glassy-winged sharpshooter in a citrus orchard

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Over 1,500 predators were screened for glassy-winged sharpshooter (GWSS) remains using a GWSS egg-specific monoclonal antibody (MAb) and several GWSS-specific genetic markers. Specimens were collected in 2002 and 2003 from a citrus orchard (Riverside, CA) harboring high densities of GWSS. We found t...

  9. Identifying key predators of the various glassy-winged sharpshooter liestages

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Using glassy-winged sharpshooter (GWSS) egg-specific monoclonal antibody (MAb) and GWSS-specific genetic markers that we previously developed and optimized, the guts of field-collected predators were screened for the presence of GWSS remains. We have examined the guts of over 700 generalist predator...

  10. Glassy-winged sharpshooter oviposition effects on foliar grapevine and red-tipped photinia terpenoid levels

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The glassy-winged sharpshooter (GWSS), Homalodisca vitripennis (Germar) (Hemiptera: Cicadellidae), is an important vector of Xylella fastidiosa, the bacterium that causes Pierce's disease of grapevine and is a threat to grape production throughout the United States. Female GWSS deposit egg masses be...

  11. Glassy-winged sharpshooter oviposition effects on photinia volatile chemistry with implications on egg parasitoid effectiveness

    Technology Transfer Automated Retrieval System (TEKTRAN)

    An effective way to limit incidence of Pierce’s disease of grapevine is to reduce populations of glassy-winged sharpshooter (GWSS), Homalodisca vitripennis (Germar) (Hemiptera: Cicadellidae), which transmit the causal bacterium, Xylella fastidiosa. One strategy is to utilize egg parasitoids such as ...

  12. Effects of feeding on glassy-winged sharpshooter lipid content and egg production

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Glassy-winged sharpshooter females emerge without mature eggs, and females must feed to produce mature eggs. As a result, allocation of incoming resources must be balanced between egg production and maintenance of other critical biological functions. Central to this process is allocation of lipids s...

  13. Molecular evidence for three novel viruses in Glassy-winged Sharpshooters, 'Homalidisca vitripennis' (Hemiptera: Cicadellidae)

    Technology Transfer Automated Retrieval System (TEKTRAN)

    A metagenomic approach was used to identify viral pathogens in the glassy-winged sharpshooter, GWSS, Homalodisca vitripennis (=H. coagulata), is renowned as the principal vector of the plant pathogenic bacterium Xylella fastidiosa which causes a number of economically important diseases including Pi...

  14. Characterization of a new Phytoreovirus species infecting the glassy-winged sharpshooter

    Technology Transfer Automated Retrieval System (TEKTRAN)

    A new virus species of the genus Phytoreovirus was isolated from glassy-winged sharpshooter (GWSS; Homalodisca vitripennis Germar, Hemiptera: Cicadellidae) in California. Double-shelled isometric virus particles (~53 nm) purified from GWSS adults resembled those observed in thin sections of GWSS sa...

  15. Genomic Characterization of a Phytoreovirus species infecting the glassy-winged sharpshooter

    Technology Transfer Automated Retrieval System (TEKTRAN)

    A new Phytoreovirus species was isolated from glassy-winged sharpshooter (GWSS; Homalodisca vitripennis Germar) in California. Double-shelled isometric virus particles purified from adults resembled those observed in thin sections of salivary glands by transmission electron microscopy. Purified vir...

  16. Virus entry and replication in the Glassy-winged sharpshhoter, Homalodisca vitripennis (Hemiptera: Cicadellidae)

    Technology Transfer Automated Retrieval System (TEKTRAN)

    A recently discovered leafhopper viral pathogen was examined to determine the route of virus entry and sites of replication in the glassy-winged sharpshooter, GWSS, (Homalodisca vitripennis, Hemiptera: Cicadellidae). The virus, HoCV-1, has been associated with increased nymphal mortality and is a co...

  17. Optical and mechanical behaviors of glassy silicone networks derived from linear siloxane precursors

    NASA Astrophysics Data System (ADS)

    Jang, Heejun; Seo, Wooram; Kim, Hyungsun; Lee, Yoonjoo; Kim, Younghee

    2016-01-01

    Silicon-based inorganic polymers are promising materials as matrix materials for glass fiber composites because of their good process ability, transparency, and thermal property. In this study, for utilization as a matrix precursor for a glass-fiber-reinforced composite, glassy silicone networks were prepared via hydrosilylation of linear/pendant Si-H polysiloxanes and the C=C bonds of viny-lterminated linear/cyclic polysiloxanes. 13C nuclear magnetic resonance spectroscopy was used to determine the structure of the cross-linked states, and a thermal analysis was performed. To assess the mechanical properties of the glassy silicone networks, we performed nanoindentation and 4-point bending tests. Cross-linked networks derived from siloxane polymers are thermally and optically more stable at high temperatures. Different cross-linking agents led to final networks with different properties due to differences in the molecular weights and structures. After stepped postcuring, the Young's modulus and the hardness of the glassy silicone networks increased; however, the brittleness also increased. The characteristics of the cross-linking agent played an important role in the functional glassy silicone networks.

  18. Exploration for biological control agents in the native range of glassy-winged sharpshooter.

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Surveys in the native range of glassy-winged sharpshooter, Homalodisca vitripennies, are continuting to discover nymphal parasitoids and to determing their ecology and phenology in undisturbed natural areas. Fifteen sites with stands of native Vitis spp. in southeastern Texas have been surveyed mon...

  19. HOST SELECTION AND LOW TEMPERATURE STORAGE OF THE GLASSY-WINGED SHARPSHOOTER, HOMALODISCA COAGULATA

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The egg parasitoid, Gonatocerus ashmedi, is a mymarid wasp that accounts for most of the observed parasitism in California on the glassy-winged sharpshooter (GWSS), Homalodisca coagulata (Say), a vector for Pierce's Disease. In the absence of techniques for propagating the wasp via artificial met...

  20. Entomopathogenic virus entry and replication site in the glassy-winged sharpshooter, Homalodisca vitripennis. (Hemiptera: Cicadellidae)

    Technology Transfer Automated Retrieval System (TEKTRAN)

    We identified the infection pathway of a newly discovered leafhopper virus, HoCV-1, which may be useful as a biological control agent to reduce leafhopper pests. Few biological control agents are currently available for use in the management of leafhoppers. The Glassy-winged sharpshooter, GWSS, Homa...

  1. The Glassy-Winged Sharpshooter Vector of Xylella fastidiosa Harbors a Phytoreovirus

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The glassy-winged sharpshooter (GWSS) vector of Xylella fastidiosa harbors a phytoreovirus species designated as Homalodisca vitripennis reovirus (HoVRV). Double-shelled isometric virus particles purified from GWSS adults resembled those observed in thin sections of GWSS salivary glands by transmis...

  2. THE ROLE OF GLASSY-WINGED SHARPSHOOTER SALIVARY ENZYMES IN INFECTION AND MOVEMENT OF X. FASTIDIOSA

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The purpose of this project is to determine whether a vector’s enzymatic saliva aids the establishment of the few ‘pioneer’ Xylella fastidiosa (Xf) cells that are inoculated into a plant; thus the bacteria would co-localize with the saliva. Previous work showed that watery saliva of glassy-winged ...

  3. Phylogenetic analysis of heat shock proteins in Glassy-winged sharpshooter (Homalodisca vitripennis)

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Heat shock proteins were identified in the glassy-winged sharpshooter, GWSS, Homalodisca vitripennis. The overall importance and function of HSPs lie in their ability to maintain protein integrity and activity during stressful conditions, such as extreme heat, cold, drought, or other stresses. The G...

  4. Rab11 gene identified in glassy-winged sharpshooter (Homalodisca vitripennis)

    Technology Transfer Automated Retrieval System (TEKTRAN)

    This is a first report of a Rab11 protein within leafhoppers. Identification and sequencing of the Rab11 in the glassy-winged sharpshooter, Homalodisca vitripennis (Hemiptera: Cicadellidae) now provides the means to develop gene silencing mechanisms which may be used to suppress leafhopper populatio...

  5. Exploration for biological control agents in the native range of the glassy-winged sharpshooter.

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The glassy-winged sharpshooter (GWSS), Homalodisca vitripennis, is native to Northeastern Mexico and the Southeastern U.S., and the origin of the invasive California populations is reported to be Texas. Most of the entomological and epidemiological information regarding this pest are derived from i...

  6. Grape hosts infested with glassy-winged sharpshooters produce volatile compounds which may attract egg parasitoids

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Glassy-winged sharpshooter (GWSS), Homalodisca vitripennis (Germar), is an important vector of Xylella fastidiosa Wells, which causes Pierce’s disease in grapes. Current management strategies in GWSS infested areas include mass release of the egg parasitoid Gonatocerus ashmeadi Girault and related s...

  7. Microarray analysis of gene expression and diapause in Glassy-winged Sharpshooter (Homalodisca vitripennis: Hemiptera: Cicadellidae)

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The condition of diapause in the glassy-winged sharpshooter, GWSS, Homalodisca vitripennis, is poorly understood. Diapause is better known from other, non hemipteran insects. We used oligonucleotide microarrays to address the specificities of transcriptional responses of adult female GWSS, which wer...

  8. Glassy-winged sharpshooter can use a mechanical mechanism to inoculate Xylella fastidiosa into grapevines

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Xylem-feeding leafhoppers such as the glassy-winged sharpshooter, Homalodisca vitripennis (Cicadellidae: Cicadellinae), are thought to inoculate the bacterium Xylella fastidiosa (Xf) from colonies bound to cuticle of the sharpshooter’s functional foregut (precibarium and cibarium). The mechanism of ...

  9. Sequence polymorphism of a glassy-winged sharpshooter phytoreovirus reveals a bottleneck in the Californian population

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The glassy-winged sharpshooter (GWSS; Homalodisca vitripennis Germar) is an invasive insect introduced to California circa 1989. Native to the southeastern U.S. and northeastern Mexico, GWSS is of economic concern as a vector of the Pierce’s disease bacterium Xylella fastidiosa. Recently, a novel ...

  10. An immunological approach for quantifying predation rates on glassy-winged sharpshooter

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The gut contents of 376 individual predators were assayed for glassy-winged sharpshooter (GWSS) remains using a multitude of ELlSAs designed to detect predation on various GWSS life stages. We found that almost 10% of the predators examined contained GWSS remains in their guts. We recorded 10, 17, a...

  11. A New Phytoreovirus Infecting the Glassy-Winged Sharpshooter (Homalodisca vitripennis)

    Technology Transfer Automated Retrieval System (TEKTRAN)

    A new virus species of the genus Phytoreovirus was isolated from glassy-winged sharpshooter (GWSS), Homalodisca vitripennis Germar (Hemiptera: Cicadellidae), in California and designated here as Homalodisca vitripennis reovirus (HoVRV). Extraction of nucleic acid from GWSS adults collected from thre...

  12. Photoalignment of liquid crystals and development of novel glassy liquid crystals

    NASA Astrophysics Data System (ADS)

    Kim, Chunki

    This thesis consists of two parts: (i) photoalignment of liquid crystals, including a nematic fluid, a glassy-namtic pentafluorene, and a cholesteric glassy liquid crystal; and (ii) development of cholesteric glassy liquid crystals comprising a hybrid chiral-nematic mesogen and of photochromic glassy liquid crystals with dithienylethene cores. Photoalignment behaviors were interpreted in terms of the kinetics of axis-selective photodimerization, the rotational mobility of pendant coumarin monomers, and the coumarin monomer's and dimer's absorption dipoles located by computational chemistry. Coumarin-containing polymethacrylate films were employed to elucidate the roles played by coumarin monomer's and dimer's orientational order, their relative abundance, and the energetics of their interactions with overlying liquid crystals. Under favorable conditions, photoalignment was shown to be comparable to rubbing polymimide film in the ability to orient liquid crystals. A hole-conducting copolymer film comprising triphenylamine and coumarin was used to unravel how the dilution of coumarin monomers, polarization ratio of UV-irradiation to induce dimerization of coumarin, and triplet energy transfer from triphenylamine to coumarin moieties affect the quality of photoalignment and its cross-over behavior. Cholesteric glassy liquid crystals are comprised of a helical stack of quasi-nematic layers frozen in the solid state capable of selective wavelength reflection with simultaneous circular polarization. Potentially applications of this material class include robust non-absorbing circular polarizers, optical notch filters and reflectors, and polarized light-emitters and lasers. To facilitate material synthesis over prior arts, hybrid chiral-nematic mesogens were chemically bonded to benzene via enantiomeric 2-methylpropylene spacers, exhibiting a broad cholesteric fluid temperature range. Phase transition temperatures, glass-forming ability, morphological stability against

  13. Infrared spectra of water-ammonium ices. The elusive 6.8 μm band

    NASA Astrophysics Data System (ADS)

    Galvez, Óscar; Maté, Belén.; Herrero, Victor J.; Fernández-Torre, Delia; Moreno, Miguel A.; Escribano, Rafael

    2010-05-01

    The recent observations made with the Spitzer Space Telescope show that the previously observed 6.8 µm spectral feature is noticeably present in many stellar objects: on young stellar objects, dark cloud star-forming region, etc. (1-2) The most generally accepted carrier for this feature is the NH4+ (nu4 bending mode), although this hypothesis is still under debate. This work presents an investigation on NH4+ in water ices. Frozen solutions of NH4+Cl- and HCOO-NH4+ in water in an astrophysical range of concentrations and temperatures are analysed by infrared spectroscopy. The ices are prepared by hyperquenching of liquid droplets of these solutions on a cold substrate. Our results indicate that, independently of the counter-ion present, when the ammonium ion is surrounded by water molecules the 6.8 µm spectral feature is hardly seen and therefore it cannot suffice to explain the observed spectral feature in the stellar objects (3). References: 1. Boogert, A.C.A. et al. 2008, ApJ, 678, 985. 2. Zasowski, G., Kemper, F., Watson, D.M., Furlan, E., Bohac, C.J., Hull, C., and Green, J.D., 2009, ApJ, 694, 459. 3. B. Maté, O. Gálvez, V. J. Herrero, D. Fernández-Torre, M. A. Moreno, and R. Escribano, 2009, ApJ, 703, L178.

  14. Glassy slags for minimum additive waste stabilization. Interim progress report, May 1993--February 1994

    SciTech Connect

    Feng, X.; Wronkiewicz, D.J.; Bates, J.K.; Brown, N.R.; Buck, E.C.; Dietz, N.L.; Gong, M.; Emery, J.W.

    1994-05-01

    Glassy slag waste forms are being developed to complement glass waste forms in implementing Minimum Additive Waste Stabilization (MAWS) for supporting DOE`s environmental restoration efforts. The glassy slag waste form is composed of various crystalline and metal oxide phases embedded in a silicate glass phase. The MAWS approach was adopted by blending multiple waste streams to achieve up to 100% waste loadings. The crystalline phases, such as spinels, are very durable and contain hazardous and radioactive elements in their lattice structures. These crystalline phases may account for up to 80% of the total volume of slags having over 80% metal loading. The structural bond strength model was used to quantify the correlation between glassy slag composition and chemical durability so that optimized slag compositions were obtained with limited crucible melting and testing. Slag compositions developed through crucible melts were also successfully generated in a pilot-scale Retech plasma centrifugal furnace at Ukiah, California. Utilization of glassy slag waste forms allows the MAWS approach to be applied to a much wider range of waste streams than glass waste forms. The initial work at ANL has indicated that glassy slags are good final waste forms because of (1) their high chemical durability; (2) their ability to incorporate large amounts of metal oxides; (3) their ability to incorporate waste streams having low contents of flux components; (4) their less stringent requirements on processing parameters, compared to glass waste forms; and (5) their low requirements for purchased additives, which means greater waste volume reduction and treatment cost savings.

  15. Quantitative comparison of stylet penetration behaviors of glassy-winged sharpshooter on selected hosts.

    PubMed

    Sandanayaka, W R M; Backus, E A

    2008-08-01

    New Zealand is threatened by invasion of the glassy-winged sharpshooter, Homalodisca vitripennis (Germar) (Hemiptera: Cicadellidae), an important vector of Xylella fastidiosa, a gram-negative bacterium that causes Pierce's disease in grape (Vitis spp.) and scorch diseases in many other horticultural crops. Therefore, an understanding of the host acceptability, feeding behavior, and potential vector efficiency of glassy-winged sharpshooter on New Zealand crops is important. We tested host plant acceptance and feeding behaviors of glassy-winged sharpshooter on three common horticultural crops grown in New Zealand (apple [Malus spp.], grape, and citrus [Citrus spp.]), and a native plant (Metrosideros excelsa [=tomentosa] Richard, pohutukawa), using the electrical penetration graph (EPG) technique. Probing (stylet penetration) behaviors varied among the host plants, primarily due to differences in waveform event durations. Apple and grape were the most accepted host plants, on which glassy-winged sharpshooter spent the majority of its time on the plant probing and readily located and accepted a xylem cell for ingestion. This resulted in long durations of sustained xylem fluid ingestion. In contrast, pohutukawa was the least accepted host. On this plant, glassy-winged sharpshooter spent less time probing and engaged in longer and more frequent testing/searching and xylem-testing activities, rejected xylem cells frequently, and spent less time with stylets resting, before accepting a xylem cell and ultimately performing the same amount of sustained ingestion. Citrus plants contaminated with sublethal insecticide residues were intermediate between these extremes, with some acceptance of xylem, but less ingestion, probably due to presumed partial paralysis of the cibarial muscles. Implications of the results in terms of host plant acceptance and the development of a stylet penetration index are discussed. PMID:18767727

  16. Synthesis of soft/hard magnetic FePt-based glassy alloys with supercooled liquid region

    NASA Astrophysics Data System (ADS)

    Makino, Akihiro; Kazahari, Akihiro; Zhang, Wei; Yubuta, Kunio; Kubota, Takeshi; Inoue, Akihisa

    2008-11-01

    Since the glassy alloys have structural homogeneity on a nanoscopic scale and wide supercooled liquid region, ΔTx (temperature interval between glass transition and crystallization), these materials are recognized as promising micro/nano-materials for nanomachines or micro electro-mechanical systems (MEMS). As one of the micro/nano components, the hard magnetic one is immensely desired. We systematically investigated the effect of metalloids composition in Fe-Pt-metalloids alloys on the glass-forming ability, and developed Fe55Pt25Si16B2P2, Fe55Pt25Si15B3P2 and (Fe0.55Pt0.25Si0.16B0.02P0.02)96Zr4 (at%) glassy alloys with ΔTx of 37 K and 48 K, respectively. With structural change from the glassy phase to a nano-composite structure consisting of L10 FePt phase, the coercivity significantly increases from 15 A/m to 170 kA/m for the former one. There is possibility for making the hard magnetic components by the fabrication in ΔTx followed by annealing for the crystallization of the FePt-based glassy alloys. Considering the high magnetocrystalline anisotropy of the L10 phase, which should lead to room-temperature ferromagnetic stability for component sizes as small as nm-order, these Fe-Pt-based glassy alloys have great potential for fabrication of hard magnetic micro/nano structures.

  17. A novel pattern transfer technique for mounting glassy carbon microelectrodes on polymeric flexible substrates

    NASA Astrophysics Data System (ADS)

    Vomero, Maria; van Niekerk, Pieter; Nguyen, Vivian; Gong, Nick; Hirabayashi, Mieko; Cinopri, Alessio; Logan, Kyle; Moghadasi, Ali; Varma, Priya; Kassegne, Sam

    2016-02-01

    We present a novel technology for transferring glassy carbon microstructures, originally fabricated on a silicon wafer through a high-temperature process, to a polymeric flexible substrate such as polyimide. This new transfer technique addresses a major barrier in Carbon-MEMS technology whose widespread use so has been hampered by the high-temperature pyrolysis process (⩾900 °C), which limits selection of substrates. In the new approach presented, patterning and pyrolysis of polymer precursor on silicon substrate is carried out first, followed by coating with a polymer layer that forms a hydrogen bond with glassy carbon and then releasing the ensuing glassy carbon structure; hence, transferring it to a flexible substrate. This enables the fabrication of a unique set of glassy carbon microstructures critical in applications that demand substrates that conform to the shape of the stimulated/actuated or sensed surface. Our findings based on Fourier transform infared spectroscopy on the complete electrode set demonstrate—for the first time—that carbonyl groups on polyimide substrate form a strong hydrogen bond with hydroxyl groups on glassy carbon resulting in carboxylic acid dimers (peaks at 2660 and 2585 cm-1). This strong bond is further confirmed by a tensile test that demonstrated an almost perfect bond between these materials that behave as an ideal composite material. Further, mechanical characterization shows that ultimate strain for such a structure is as high as 15% with yield stress of ~20 MPa. We propose that this novel technology not only offers a compelling case for the widespread use of carbon-MEMS, but also helps move the field in new and exciting directions.

  18. Square wave voltammetric detection by direct electroreduction of paranitrophenol (PNP) using an organosmectite film-modified glassy carbon electrode.

    PubMed

    Ngassa, Guy B P; Tonlé, Ignas K; Ngameni, Emmanuel

    2016-01-15

    This work describes the development of a low-cost and reliable adsorptive stripping voltammetric method for the detection of PNP in water. Organoclays were prepared by intercalation in various loading amounts of cetyltrimethylammonium ions (CTA(+)) in the interlayer space of a smectite-type clay mineral. Their structural characterization was achieved using several techniques including X-ray diffraction (XRD), N2 adsorption-desorption (BET method) and Fourier Transform Infrared spectroscopy (FTIR) that confirmed the intercalation process and the presence of the surfactant ions within the clay mineral layers. Using [Fe(CN)6](3-) and [Ru(NH3)6](3+) as redox probes, the surface charge and the permeability of the starting clay mineral and its modified counterparts were assessed by multisweep cyclic voltammetry, when these materials were coated on the surface of a glassy carbon electrode (GCE). In comparison with the bare GCE, the organoclay modified electrodes exhibited more sensitive response towards the reduction of paranitrophenol (PNP). Under optimized conditions, a calibration curve was obtained in the concentration range from 0.2 to 5.2µmolL(-1); leading to a detection limit of 3.75×10(-8)molL(-1) (S/N=3). After the study of some interfering species on the electrochemical response of PNP, the developed sensor was successfully applied to the electroanalytical quantification of the same pollutant in spring water. PMID:26592645

  19. Water-Ammonium ICES and the Elusive 6.85 μm Band

    NASA Astrophysics Data System (ADS)

    Maté, B.; Gálvez, O.; Herrero, V. J.; Fernández-Torre, D.; Moreno, M. A.; Escribano, R.

    2009-10-01

    The 6.85 μm band observed in the spectra of young stellar objects has been analyzed recently and the most usually accepted assignment to the ν4 bending mode of NH4 + is still under debate. We present here a laboratory study of frozen solutions of NH4 +Cl- in water in an astrophysical range of concentrations and temperatures. The samples are prepared by hyper-quenching of liquid droplets on a cold substrate. The ν4 band of NH4 +, which is very strong in the pure crystal and in the liquid solution at ambient temperature, becomes almost blurred in IR spectra of the frozen solution. The effect of the chlorine anion is expected to be of little relevance in this study. The experimental results are supported by theoretical calculations, which predict a broad range of weak ν4 features for amorphous samples containing different ammonium environments. The present results indicate that the ammonium ion surrounded by water molecules only cannot suffice to explain this spectral feature. This paper contributes with new evidence to the discussion on the assignment of the 6.85 μm band.

  20. Composition of Crustal Melts at the Source Area: Information from Glassy Melt Inclusions in Anatectic Enclaves

    NASA Astrophysics Data System (ADS)

    Acosta-vigil, A.; Cesare, B.; London, D.; Morgan, G. B., VI; Buick, I.; Hermann, J.; Bartoli, O.; Remusat, L.

    2014-12-01

    Crustal anatexis, together with melt extraction and ascent to upper crustal levels, generate plutons and volcanic edifices of granitoid composition. This process constitutes the main mechanism for the differentiation of the continental crust. A recent breakthrough in the study of crustal anatexis is the discovery of former melt inclusions in peritectic minerals of anatectic rocks. These melt droplets show now as glassy inclusions in rapidly cooled anatectic enclaves within volcanic rocks, or as polycrystalline aggregates (nanogranites) in migmatites. Analysis of glassy inclusions and of rehomogenized nanogranites provide direct information on the composition of crustal melts at the source of crustal magmas, on the extent of equilibration between melt and residue, and on the fluid regime during anatexis. A comprehensive geochemical study (≈350 EMP, 100 LA-ICPMS and 80 nanoSIMS analyses) of matrix glasses and glassy melt inclusions in Pl and Grt of anatectic enclaves within El Hoyazo dacite (Betic Cordillera, S Spain), recording melt compositions during regional anatexis at ≈700-850 °C and 0.5-0.7 GPa, shows that melts are leucogranitic (FeOt+MgO+TiO2=1.0-2.0 wt%), moderately to strongly peraluminous (ASI=1.10-1.25), with H2O concentrations well below saturation (3-5 wt%). They are heterogeneous and spread around the 0.5-0.7 GPa haplogranite H2O-undersaturated eutectics. Glassy inclusions in Pl are more heterogeneous, richer in normative Qtz and H2O, and poorer in FeOt and CaO compared to glassy inclusions in Grt and matrix glass. All glasses have moderate to high concentrations of LILE and low to very low concentrations in FRTE, HFSE and REE. Glass inclusions in Pl and Grt have higher concentrations of LILE, lower concentrations of Y, Zr, REE, and lower values of Th/U compared to matrix glasses. Surprisingly, and in spite of the compositional heterogeneity, glasses are at or close to equilibrium with their residue regarding most of the trace elements, except

  1. Host plant effects on development and reproduction of the glassy-winged sharpshooter, Homalodisca vitripennis (Homoptera: Cicadellidae)

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Development, survivorship, longevity, reproduction and life table parameters of the glassy-winged sharpshooter, Homalodisca vitripennis (Germar), were examined in the laboratory using three host plants, sunflower (Helianthus annuus L.), Chrysanthemum morifolium L. and euonymus (Euonymus japonica Thu...

  2. Direct visualization of photoinduced glassy dynamics on the amorphous silicon carbide surface by STM movies

    NASA Astrophysics Data System (ADS)

    Nguyen, Duc; Nienhaus, Lea; Haasch, Richard T.; Lyding, Joseph; Gruebele, Martin

    2015-03-01

    Glassy dynamics can be controlled by light irradiation. Sub- and above-bandgap irradiation cause numerous phenomena in glasses including photorelaxation, photoexpansion, photodarkening and pohtoinduced fluidity. We used scanning tunneling microscopy to study surface glassy dynamics of amorphous silicon carbide irradiated with above- bandgap 532 nm light. Surface clusters of ~ 4-5 glass forming unit in diameter hop mostly in a two-state fashion, both without and with irradiation. Upon irradiation, the average surface hopping activity increases by a factor of 3. A very long (~1 day) movie of individual clusters with varying laser power density provides direct evidence for photoinduced enhanced hopping on the glass surfaces. We propose two mechanisms: heating and electronic for the photoenhanced surface dynamics.

  3. Connection between NMR and electrical conductivity in glassy chalcogenide fast ionic conductors

    SciTech Connect

    Kim, K.H.

    1995-11-01

    The work documented in this thesis follows the traditional order. In this chapter a general discussion of ionic conduction and of glassy materials are followed by a brief outline of the experimental techniques for the investigation of fast ionic conduction in glassy materials, including NMR and impedance spectroscopy techniques. A summary of the previous and present studies is presented in the last section of this introductory chapter. The details of the background theory and models are found in the Chapter II, followed by the description of the experimental details in Chapter III. Chapter IV of the thesis describes the experimental results and the analysis of the experimental observations followed by the conclusions in chapter V.

  4. Short- and Intermediate-Range Structural Ordering in Glassy Boron Oxide

    NASA Astrophysics Data System (ADS)

    Youngman, R. E.; Haubrich, S. T.; Zwanziger, J. W.; Janicke, M. T.; Chmelka, B. F.

    1995-09-01

    Ordering at short-length scales is a universal feature of the glassy state. Experiments on boron oxide and other materials indicate that ordering on mesoscopic-length scales may also be universal. The high-resolution nuclear magnetic resonance (NMR) measurements of oxygen in boron oxide glass presented here provide evidence for structural units responsible for ordering on short- and intermediate-length scales. At the molecular level, planar BO3/2 units accounted for the local ordering. Oxygen-17 NMR spectra resolved detailed features of the inclusion of these units in boroxol rings, oxygen bridging two rings, and oxygen shared between two nonring BO3/2 units. On the basis of these and corroborative boron-11 NMR and scattering results, boron oxide glass consists of domains that are rich or poor in boroxol rings; these domains are proposed to be the structural basis of intermediate-range order in glassy boron oxide.

  5. Unraveling the Mechanism of Nanoscale Mechanical Reinforcement in Glassy Polymer Nanocomposites.

    PubMed

    Cheng, Shiwang; Bocharova, Vera; Belianinov, Alex; Xiong, Shaomin; Kisliuk, Alexander; Somnath, Suhas; Holt, Adam P; Ovchinnikova, Olga S; Jesse, Stephen; Martin, Halie; Etampawala, Thusitha; Dadmun, Mark; Sokolov, Alexei P

    2016-06-01

    The mechanical reinforcement of polymer nanocomposites (PNCs) above the glass transition temperature, Tg, has been extensively studied. However, not much is known about the origin of this effect below Tg. In this Letter, we unravel the mechanism of PNC reinforcement within the glassy state by directly probing nanoscale mechanical properties with atomic force microscopy and macroscopic properties with Brillouin light scattering. Our results unambiguously show that the "glassy" Young's modulus in the interfacial polymer layer of PNCs is two-times higher than in the bulk polymer, which results in significant reinforcement below Tg. We ascribe this phenomenon to a high stretching of the chains within the interfacial layer. Since the interfacial chain packing is essentially temperature independent, these findings provide a new insight into the mechanical reinforcement of PNCs also above Tg. PMID:27203453

  6. Relaxation Dynamics of Nano Particles Embedded in a Soft Glassy Matrix

    NASA Astrophysics Data System (ADS)

    Basu, Jaydeep; Srivastava, Sunita; Kandar, Ajoy; Mukhopadhyay, Mrinmay; Lurio, Laurence; Sinha, Sunil

    2008-03-01

    Using x-ray photon correlation spectroscopy, we have studied slow, wave vector and temperature dependent microrheology of nano particles embedded in glassy matrix with unique viscoelastic properties. The measurements were done for a polymer matrix (PMMA) using gold nanoparticles as probe. The intensity auto-correlation function exhibits a cross-over from compressed to stretched relaxation behavior on cooling from above the glass transition temperature (Tg) of PMMA. Although stretched exponential relaxation is expected in the glassy state one would expect simple exponential relaxation above the Tg. We also find that the relaxation time (τ), follows τ˜ q-1 dependence indicating super-diffusive motion of nanoparticles. Interestingly, we have also observed subtle effects like length scale dependence of the stretching exponent. This points to the importance of the nanoparticles in modifying the viscoelastic property of the polymer matrix and highlights the strength of this technique in extracting their micro-rheological properties.

  7. Unraveling the Mechanism of Nanoscale Mechanical Reinforcement in Glassy Polymer Nanocomposites

    DOE PAGESBeta

    Cheng, Shiwang; Bocharova, Vera; Belianinov, Alex; Xiong, Shaomin; Kisliuk, Alexander; Somnath, Suhas; Holt, Adam P.; Ovchinnikova, Olga S.; Jesse, Stephen; Martin, Halie J.; et al

    2016-05-20

    The mechanical reinforcement of polymer nanocomposites (PNCs) above the glass transition temperature, Tg, has been extensively researched. However, not much is known about the origin of this effect below Tg. In this paper, we unravel the mechanism of PNC reinforcement within the glassy state by directly probing nanoscale mechanical properties with atomic force microscopy and macroscopic properties with Brillouin light scattering. Our results unambiguously show that the "glassy" Young's modulus in the interfacial polymer layer of PNCs is two-times higher than in the bulk polymer, which results in significant reinforcement below Tg. We ascribe this phenomenon to a high stretchingmore » of the chains within the interfacial layer. Since the interfacial chain packing is essentially temperature independent, these findings provide a new insight into the mechanical reinforcement of PNCs also above Tg.« less

  8. The glassy random laser: replica symmetry breaking in the intensity fluctuations of emission spectra

    PubMed Central

    Antenucci, Fabrizio; Crisanti, Andrea; Leuzzi, Luca

    2015-01-01

    The behavior of a newly introduced overlap parameter, measuring the correlation between intensity fluctuations of waves in random media, is analyzed in different physical regimes, with varying amount of disorder and non-linearity. This order parameter allows to identify the laser transition in random media and describes its possible glassy nature in terms of emission spectra data, the only data so far accessible in random laser measurements. The theoretical analysis is performed in terms of the complex spherical spin-glass model, a statistical mechanical model describing the onset and the behavior of random lasers in open cavities. Replica Symmetry Breaking theory allows to discern different kinds of randomness in the high pumping regime, including the most complex and intriguing glassy randomness. The outcome of the theoretical study is, eventually, compared to recent intensity fluctuation overlap measurements demonstrating the validity of the theory and providing a straightforward interpretation of qualitatively different spectral behaviors in different random lasers. PMID:26616194

  9. In situ PM-IRRAS of a glassy carbon electrode/deep eutectic solvent interface.

    PubMed

    Vieira, Luciana; Schennach, Robert; Gollas, Bernhard

    2015-05-21

    The interface of a 1 : 2 molar choline chloride/ethylene glycol deep eutectic solvent with a glassy carbon electrode has been investigated by polarization modulation reflection-absorption spectroscopy (PM-IRRAS). Temporal spectral changes at open circuit potential show the experiments to be surface sensitive and indicate slow adsorption of electrolyte molecules on the electrode surface. In situ spectroelectrochemical PM-IRRAS measurements reveal characteristic potential-dependent changes of band intensities and wavenumber-shifts in the surface spectra. The potential dependent spectral changes are discussed in terms of adsorption, reduction, desorption and reorientation of choline cations at the interface. Analogies are drawn to the ionic layer structure proposed for the architecture of electrode/ionic liquid interfaces. The results show that in situ PM-IRRAS is generally applicable to glassy carbon electrodes and to electrode interfaces with deep eutectic solvents. PMID:25908481

  10. Unraveling the Mechanism of Nanoscale Mechanical Reinforcement in Glassy Polymer Nanocomposites

    SciTech Connect

    Cheng, Shiwang; Bocharova, Vera; Belianinov, Alex; Xiong, Shaomin; Kisliuk, Alexander; Somnath, Suhas; Holt, Adam P; Ovchinnikova, Olga S; Jesse, Stephen; Martin, Halie J; Etampawala, Thusitha N; Dadmun, Mark D; Sokolov, Alexei P

    2016-01-01

    The mechanical reinforcement of polymer nanocomposites (PNCs) above the glass transition temperature, Tg, has been extensively studied. However, not much is known about the origin of this effect below Tg. In this Letter, we unravel the mechanism of PNC reinforcement within the glassy state by directly probing nanoscale mechanical properties with atomic force microscopy and macroscopic properties with Brillouin light scattering. Our results unambiguously show that the glassy Young s modulus in the interfacial polymer layer of PNCs is two-times higher than in the bulk polymer, which results in significant reinforcement below Tg. We ascribe this phenomenon to a high stretching of the chains within the interfacial layer. Since the interfacial chain packing is essentially temperature independent, these findings provide a new insight into the mechanical reinforcement of PNCs also above Tg.