Freezing of glycerol-water mixtures under pressure

We investigated freezing of pure glycerol as well as glycerol-water (GW) mixtures with 3:1 and 3:2 volume fractions as a function of pressure in the 0-10?GPa range by ruby fluorescence spectroscopy and neutron scattering. We find that the glass transition pressure increases from 5.5?GPa for pure glycerol to 6.5?GPa for the 3:1?GW mixture, with unusually small pressure gradients above. For higher water concentrations close to 3:2, phase separation occurs above 2?GPa where most of the water is expelled in the form of ice VII. The results suggest that glycerol is able to effectively hydrogen bond not more than ≈2.5 H(2)O molecules per glycerol, which seems to support conclusions from molecular dynamics simulations. The data indicate that these fluids could become important as pressure transmitting media for neutron scattering in the 0-7?GPa range, including at low temperatures.     

Localization phenomena in models of ion-conducting glass formers

The mass transport in soft-sphere mixtures of small and big particles as well as in the disordered Lorentz gas (LG) model is studied using molecular dynamics (MD) computer simulations. The soft-sphere mixture shows anomalous small-particle diffusion signifying a localization transition separate from the big-particle glass transition. Switching off small-particle excluded volume constraints slows down the small-particle dynamics, as indicated by incoherent intermediate scattering functions. A comparison of logarithmic time derivatives of the mean-squared displacements reveals qualitative similarities between the localization transition in the soft-sphere mixture and its counterpart in the LG. Nevertheless, qualitative differences emphasize the need for further research elucidating the connection between both models.     

De-mixing dynamics of a binary liquid system in a controlled-pore glass. A neutron spin-echo spectroscopy and small angle neutron scattering study

The temperature-induced microphase separation of the binary liquid system iso-butyric acid+heavy water (iBA + D(2)O) in a mesoporous silica glass (CPG-10-75) of nominal pore width 7.5 nm was investigated by neutron spin-echo spectroscopy (NSE) and neutron small-angle scattering (SANS). Two mixtures of different composition were studied at different scattering angles at temperatures above and below the bulk phase transition temperature. The phase separation in the pore space is found to occur at a lower temperature than the bulk transition and extends over a significant temperature range. The effective diffusion coefficient derived from NSE at low scattering angles is found to decrease by one order of magnitude from 70 degrees C to 20 degrees C. This observation is attributed to the growing size of concentration fluctuations having a cut-off at ca. 8 nm, which corresponds to the mean pore size. The dynamics of the concentration fluctuations appears to be strongly influenced by the confinement in the pores, as it differs strongly from the bulk behaviour. These results are consistent with the preliminary results of the SANS study.     

Dynamics of nanoparticles in a supercooled liquid

The dynamic properties of nanoparticles suspended in a supercooled glass forming liquid are studied by x-ray photon correlation spectroscopy. While at high temperatures the particles undergo Brownian motion the measurements closer to the glass transition indicate hyperdiffusive behavior. In this state the dynamics is independent of the local structural arrangement of nanoparticles, suggesting a cooperative behavior governed by the near-vitreous solvent.     

Experimental evidence for fast heterogeneous collective structural relaxation in a supercooled liquid near the glass transition

We have extended the exploration of microscopic dynamics of supercooled liquids to small wave numbers Q corresponding to the scale of intermediate range order, by developing a new experimental approach for precise data correction for multiple scattering noise in inelastic coherent neutron scattering. Our results in supercooled Ca0.4K0.6(NO3)(1.4) reveal the first direct experimental evidence, after a decade of controversy, that the so-called picosecond process around the glass transition corresponds to a predicted first, faster stage of the structural relaxation. In addition, they show that this process takes the spatial form of fast heterogeneous collective flow of correlated groups of atoms.     

Effect of local molecular ordering on the temperature behavior of the relaxation time of order-parameter fluctuations in the isotropic phase of PAA nematic liquid crystal

The behavior of the relaxation time of order-parameter fluctuations in the isotropic phase of PAA nematic liquid crystal was investigated on the basis of the spectra of depolarized (inelastic) light scattering in a wide temperature range including the immediate vicinity to the temperature of the nematic phase transition. The experimental data were analyzed within the Landau—de Gennes theory. The temperature limits of applicability of the Landau—de Gennes theory to the isotropic-phase dynamic properties are obtained. The minimum correlation length is determined, at which the effect of local ordering on the dynamics of slow orientational motion of isotropic-phase molecules is dominant.     

Characterization of the drastic increase in molecular mobility of a deformed amorphous polymer

Original experiments of dynamic mechanical analysis and small angle x-ray scattering on a deformed amorphous polymer below its glass transition temperature are reported. The mechanical treatment reveals high mobility zones induced by shearing and leads to a drastic increase in the molecular mobility of the system. These domains are evidenced by small angle x-ray scattering measurements, and their geometrical characteristics are independent of the applied deformation. An experimental procedure is proposed to determine an apparent activation energy associated with high mobility domains. The energy values obtained for intermediate modes rise from the beta to the alpha relaxation ones.     

Light-scattering study of a supercooled epoxy resin

The dynamics of the fragile glass-forming liquid diglycidyl ether of bisphenol-A was studied by depolarized Rayleigh-Brillouin light-scattering and photon correlation spectroscopy above the glass transition, in the temperature range from 261 to 473 K and in the frequency range from 1 Hz to 300 GHz. The structural (alpha-) relaxation process was revealed and no signature of the secondary relaxation previously evidenced by dielectric spectroscopy at about 0.1 GHz was observed. The characteristic time of the alpha process differs from that determined by dielectric spectroscopy of an amount, which increases with increasing temperature. The relaxation times were compared with viscosity data to test the predictions of the classic Stokes-Einstein-Debye model. The tau proportional, variant eta behavior was verified for dielectric data, while a fractional power law of viscosity tau proportional, variant eta(0.89) was obtained for light-scattering relaxation times, extending over more than seven decades in viscosity and time. This deviation of light scattering from viscosity data could be interpreted in terms of cooperative motion in the supercooled liquid with a characteristic length xi(a) proportional, variant(T-T0)(-v) where T(0)=229 K is the Vogel temperature and v is close to 2 / 3 which is consistent with the prediction of the fluctuation theory of glass transition.     

Evidence for the weak steric hindrance scenario in the supercooled-state reorientational dynamics

We use molecular-dynamics computer simulations to study the translational and reorientational dynamics of a glass-forming liquid of dumbbells. For sufficiently elongated molecules the standard strong steric hindrance scenario for the rotational dynamics is found. However, for small elongations we find a different scenario--the weak steric hindrance scenario--caused by a new type of glass transition in which the orientational dynamics of the molecule's axis undergoes a dynamical transition with a continuous increase of the nonergodicity parameter. These results are in agreement with the theoretical predictions by the mode-coupling theory for the glass transition.     

Direct observation of the flux-line vortex glass phase in a type II superconductor

The order of the vortex state in La1.9Sr0.1CuO4 is probed using muon-spin rotation and small-angle neutron scattering. A transition from a Bragg glass to a vortex glass is observed, where the latter is composed of disordered vortex lines. In the vicinity of the transition the microscopic behavior reflects a delicate interplay of thermally induced and pinning-induced disorder.     

Aromatic poly(ester carbonate)/poly-(ethylene terephthalate) alloys

When mixtures of poly(ester carbonate) (PEC) and poly(ethylene terephthalate) (PET) containing up to two-thirds of the latter are melt extruded, they produce a single-phase amorphous “alloy.” This alloy is characterized by a sharp, single, composition-dependent glass transition temperature, T_g. When annealed below T_g, the alloy remains unaltered, but when annealed above its T_g, the alloy separates into minute pure-PET crystallites and an amorphous PEC/PET phase. The thermal and dynamic mechanical behavior, crystallization kinetics, and SAXS patterns all strongly suggest the PEC-rich alloys to be solid solutions in which the PET molecules are dispersed individually or in small aggregates containing only a few PET molecules each. Calculations of the interaction parameter and assumed interfacial layer thickness tend to support this suggestion. Use of appropriate solvents allows one to selectively dissolve the PEC and recover from the alloys both PET and PEC in the original purity and molecular weights. Diffusion constants of PET molecules through the amorphous alloys were obtained from studies of PET crystallization above T_g of the alloys. The magnitude of the constants are in the range of expectation. The mechanical properties of the amorphous alloys in the glassy state do not deviate greatly from simple additivity of the respective properties of the parent polymers. However, the melt viscosity of the PEC-rich alloys and their plateau modulus above T show drastic decreases from straight additivity. A qualitative, but not quantitative, explanation of these observations is offered.     

Phase transitions of interfacial water at 165 and 240 K. Connections to bulk water physics and protein dynamics

We are considering water adsorbed as a monolayer on Vycor, a porous silica glass. The interfacial water molecules interact with the substrate through hydrogen bonding with the numerous silanol (Si-OH) groups present all over the surface. This special form of water exhibits peculiar dynamical properties. A combined calorimetric, diffraction, high resolution quasi-elastic and inelastic neutron scattering study shows that interfacial water experiences a glass transition at 165 K and a liquid-liquid transition at 240 K from a low-density to a high density-liquid. We show that this unusual behaviour, compared to the bulk, is due to a strong weakening of the hydrogen-bond strength, possibly due to the reduced number of hydrogen-bonds engaged by water molecules when they are in an interfacial two dimensional situation. The connections of these findings to the physics of bulk water and protein dynamics are discussed.     

Dynamics at the liquid-vapor interface of a supercooled organic glass former

We investigated the dynamics near the liquid-vapor interface of the supercooled model organic glass former dibutyl phthalate by using surface-sensitive x-ray scattering techniques. Our results reveal significant enhancement of the relaxation rate over a wide length-scales range. The analysis of the dispersion relation of long-wavelength surface fluctuations yields a nonzero value of the share modulus near the free surface. At the molecular level, the dynamics in the near surface region (10-15 nm) is inhomogeneous. The mobility is decreasing with increasing distance from the free surface. Below the bulk glass transition, two distinct relaxation times were observed differing by 1 order of magnitude. The observed fast relaxation proves the existence of a high mobility liquidlike surface layer of 10 nm thickness on top of a frozen in bulk system.     

Pressure dependence of fragile-to-strong transition and a possible second critical point in supercooled confined water

By confining water in nanopores of silica glass, we can bypass the crystallization and study the pressure effect on the dynamical behavior in deeply supercooled state using neutron scattering. We observe a clear evidence of a cusplike fragile-to-strong (FS) dynamic transition. Here we show that the transition temperature decreases steadily with an increasing pressure, until it intersects the homogenous nucleation temperature line of bulk water at a pressure of 1600 bar. Above this pressure, it is no longer possible to discern the characteristic feature of the FS transition. Identification of this end point with the possible second critical point is discussed.     

Light scattering from colloids

This paper presents a review of light scattering results on static and dynamic properties of ordered colloidal suspensions of charged polystyrene particles and fractal colloidal aggregates. Our studies on static structure factor,S(Q), of ordered monodisperse colloidal suspensions and binary mixtures of particles with different particle diameters, measured by angle-resolved Rayleigh scattering will be discussed. This will include determination of bulk modulus using gravitational compression and observation of colloidal glass (inferred from splitting of the second peak inS(Q)). Dynamic light scattering, with real time analysis of scattered intensity fluctuations, is used to get information about Brownian dynamics of the particles. Recent advances in the field of light scattering from colloidal aggregates which show fractal geometry will also be discussed.     

Influence of surface interactions on the dynamics of the glass former ortho-terphenyl confined in nanoporous silica

We present results on investigations of the dynamics of the glass forming ortho-terphenyl (oTP) confined in nanoporous silica. Calorimetry experiments showed that the glass transition temperature of the confined liquid, T_gconf, has a non-trivial pore size dependence and is strongly affected by surface interactions. Fluid-wall interactions introduce gradients of structural relaxation times in the pores. The molecules at the surface of the pores are slowed down compared to those at the center of the pores. We focus here on a pore diameter range (7 σ< d < 12 σ, where σ is the molecular diameter), where a large variety of dynamical behavior were observed. Depending on surface properties of the confined media, T _gconf may be smaller or larger than the bulk one. In a quite attractive matrix with a pore size of around 7 nm, the structural relaxation times gradient is important enough to allow the observation of two glass transitions for the same liquid. Effects of fluid wall interactions on the short time dynamics at high temperature were also investigated by quasielastic neutron scattering. The self and collective motions exhibit well above the bulk melting point the same dependence on fluid-wall interactions as at T_g.     

Dynamics of probes in model glassy matrices

The dynamics of diatomic probe molecules in matrices composed of hard spheres are studied using molecular dynamics simulations. The matrix particles are connected to fixed attachment points by strings of length, l, which is varied from l-->infinity (fluid) to 0 ("glass"). The probe diffusion coefficient, D interpolates smoothly between these limits when l is changed. As l is decreased, D displays a transition from a power-law l dependence, which is well fit by the mode-coupling theory expression, to an Arrhenius l dependence. Single particle analysis shows that the hopping motion sets in for l much larger than a critical length, l(c), and Arrhenius behavior occurs when hopping becomes the dominant mode of transport. The system displays dynamic heterogeneity even though there is no growing dynamic correlation length of any kind.     

Anomalous temperature behavior of hypersonic acoustic phonons in a lysozyme crystal

The behavior of acoustic phonons in tetragonal lysozyme crystals is studied using Brillouin scattering over a temperature range from 298 to 330 K. Around 307 K, anomalies in the temperature dependence of the velocity and integral intensity of a quasi-transverse phonon and in the velocity of a quasi-longitudinal phonon are detected. The experimental results are discussed in terms of the current concepts of the dynamics of proteins. The observed anomalies in the behavior of hypersonic acoustic phonons are indicative of a structural phase transition occurring in a lysozyme crystal at 307 K.     

Behavior of the layer compression elastic modulus near,above, and below a smectic C–hexatic I critical point in binary mixtures

We present the first study of the layer compression modulus B carried out near, above and below the Smectic C–Hexatic I critical point in racemic mixtures of methylbutyl phenyl octylbiphenyl-carboxylate (8SI) and the octyloxy biphenyl analog (8OSI), at frequencies ranging from 0.2 Hz to 2 ×103 Hz. The behavior of B as a function of temperature shows a progressive evolution from a first order transition in 8SI to a continuous supercritical behavior in 8OSI. The latter is characterized by an increase in B, which appears above the transition, and which is followed by a leveling off when the temperature is decreased towards the transition. It is proposed that this behavior stems from the relaxation of the hexatic domains which are frozen in the frequency range studied. For the supercritical and near-critical compounds, B exhibits a small dip near the transition temperature, which is visible in the low frequency range only, indicating that the dynamics associated with the critical point is very slow. We also report measurements in the Crystal-J phase of the pure compounds, and show that 8SI behaves mechanically as a hexatic phase and 8OSI as a soft crystal phase.