Stretched exponential relaxation on the hypercube and the glass transition

We study random walks on the dilute hypercube using an exact enumeration Master equation technique, which is much more efficient than Monte Carlo methods for this problem. For each dilution p the form of the relaxation of the memory function q(t) can be accurately parametrized by a stretched exponential over several orders of magnitude in q(t). As the critical dilution for percolation is approached, the time constant tends to diverge and the stretching exponent drops towards 1/3. As the same pattern of relaxation is observed in a wide class of glass formers, the fractal like morphology of the giant cluster in the dilute hypercube appears to be a good representation of the coarse grained phase space in these systems. For these glass formers the glass transition may be pictured as a percolation transition in phase space. Received 16 June 2000 and Received in final form 13 October 2000     

Water and its energy landscape

We present an overview of the recent studies on the properties of the potential energy surface for a simple model of water. We emphasize the relations between PES properties and dynamics in supercooled states for the model and discuss possible future application of the PES studies. Received 13 March 2002     

Dielectric relaxation of poly(ethylenglycol)- b-poly(propylenglycol)-b-poly(ethylenglycol) copolymers above the glass transition temperature

The complex dielectric permittivity has been measured for three poly(ethylenglycol)-b-poly(propylenglycol)-b-poly(ethylenglycol) copolymers with different content of poly(ethylenglycol) (15%, 33% and 80%), and increasing degree of crystallinity (0%, 10% and 20%, respectively). Only the non-crystalline sample shows the normal mode relaxation together with the segmental (α-relaxation) and the Johari-Goldstein (β-relaxation) modes. The crystalline samples show also polarization contributions due to the existence of interfaces between the crystallites and the amorphous phase. The relaxation times of the (α and normal modes can be described by a VFT equation with the same value of T₀. There is a slowing-down of the segmental mode due to the presence of crystallites. The temperature dependence of the α and β relaxations in the copolymers is very similar to that found in pure PPG, while there are significant differences in the case of the normal mode of the non-crystalline sample. The size of the cooperatively rearranging regions CRR, and the width of the glass transition region increase slightly with the degree of crystallinity. The temperature dependence of the size of CRRs is compatible with the prediction of fluctuation theory. No systematic effect of the degree of crystallinity on the β-relaxation has been found. Near T _g the β-relaxation time is close to the primitive time of the coupling model. Received: 31 May 2000     

Pressure amorphization through displacive disorder

After classifying amorphous materials according to their topology, we review a recently proposed theory of pressure amorphization (PA) that arises from some degree of displacive disorder while retaining a crystalline topology. That theory is based on the notion that one or more branches of the phonon spectrum become soft and flat with increasing pressure and is illustrated by a simple model that possesses the range of features displayed by many of the materials which undergo PA with displacive disorder. We report the results of Langevin simulations of the simple model which show how the probability of amorphization increases with the number of unit cells in the system and support our theory. We comment on how to generalize the model for the study of real systems. Received 29 march 2002     

Cooperative motions in a finite size model of liquid silica: an anomalous behavior

Finite size effects on dynamical heterogeneity are studied in liquid silica with Molecular Dynamics simulations using the BKS potential model. When the system size decreases relaxation times are found to increase in accordance with previous results in finite-size simulations and confined liquids. It has been suggested that this increase may be related to a modification of the spatially heterogeneous dynamics in confined liquids. In agreement with this hypothesis we observe a decrease of the spatially heterogeneous dynamics when the size decreases. The spatially heterogeneous dynamics is usually characterized by the dynamical aggregation of the most or the least mobile atoms. However we find that the decrease of the dynamical aggregation associated to the least mobile atoms is much more important than the decrease associated to the most mobile atoms when the size decreases. This result associated with a slowing down of the liquid is surprising as it is expected that the dynamical aggregation of the least mobile atoms should increase the slowing down of the liquid dynamics. The decrease of the heterogeneous behaviour is also in contradiction with the increase of the spatially heterogeneous dynamics observed in liquids confined inside nanopores. However, an increase of the non-Gaussian parameter appears both for the confinement inside nanopores and for the finite size simulations. As the non-Gaussian parameter is usually associated with the heterogeneous dynamics, the increase of the non-Gaussian parameter together with a decrease of the spatially heterogeneous dynamics is also surprising.     

Density-correlator signatures of the vulcanization transition

Certain density correlators, measurable via various experimental techniques, are studied in the context of the vulcanization transition. It is shown that these correlators contain essential information about both the vulcanization transition and the emergent amorphous solid state. Contact is made with various physical ingredients that have featured in experimental studies of amorphous colloidal and gel systems and in theoretical studies of the glassy state. Received 30 September 2000     

Thermal expansion of amorphous Zr Al Cu Ni in the vicinity of the glass transition

The thermal expansion of non-crystalline Zr₆₅Al_7.5Cu_17.5 Ni₁₀ has been studied in the range of the glass transition and in the undercooled liquid using a dilatometric device. The measuring technique used permits reliable experimental results up to 40 K above the glass transition temperature. The linear thermal expansion coefficient obtained is almost constant in the glassy state with a value of . It discontinuously increases at the glass transition temperature yielding a value of in the undercooled liquid. The results are compared with specific heat measurements of the amorphous material in this temperature range and are interpreted in the framework of a cluster model. Received 5 March 1999 and received in final form 11 June 1999     

Apparent correlations between the static length of relaxation and the linear size of dynamic heterogeneity in fragile liquids

The most puzzling aspect of the glass transition observed in laboratory is the decoupling of the dynamics from the structure. As an attempt to reconcile the dynamic and the static lengthscales associated with the glass problem, we discuss the apparent correlations between the static relaxation length, defined as that lengthscale over which the potential energy fluctuation is correlated, with the linear size of the dynamic heterogeneity. The dynamic heterogeneous domains with long life-times, may therefore be linked to the droplets of low potential energy, or the tightly bound regions inside the liquid.     

On the slow dynamics of density fluctuations near the colloidal glass transition

Slow dynamics of density fluctuations near the colloidal glass transition is discussed from a new viewpoint by numerically solving a nonlinear stochastic diffusion equation for the density fluctuations recently proposed by one of the present authors (MT). The effects of spatial heterogeneities on the dynamics of density fluctuations are then investigated in an equilibrium system. The spatial heterogeneities are generated by the nonlinear density fluctuations, while in a nonequilibrium system they are described by a nonlinear deterministic equation for the average number density. The dynamics of equilibrium density fluctuations is thus shown to be quite different from that of nonequilibrium ones, leading to a logarithmic decay followed by less distinct α- and β-relaxation processes. Received 9 March 2002 and Received in final form 19 September 2002     

Heterogeneous dynamics at the glass transition in van der Waals liquids, in the bulk and in thin films

It has been shown over the last few years that the dynamics close to the glass transition is strongly heterogeneous, both by measuring the diffusion coefficient of tagged particles or by NMR studies. Recent experiments have also demonstrated that the glass transition temperature of thin polymer films can be shifted as compared to the same polymer in the bulk. We propose here first a thermodynamical model for van der Waals liquids, which accounts for experimental results regarding the bulk modulus of polymer melts and the evolution of the density with temperature. This model allows us to describe the density fluctuations in such van der Waals liquids. Then, by considering the thermally induced density fluctuations in the bulk, we propose that the 3D glass transition is controlled by the percolation of small domains of slow dynamics, which allows to explain the heterogeneous dynamics close to T _g. We show then that these domains percolate at a lower temperature in the quasi-2D case of thin suspended polymer films and we calculate the corresponding glass transition temperature reduction, in quantitative agreement with experimental results of Jones and co-workers. In the case of strongly adsorbed films, we show that the strong adsorption amounts to enhance the slow domains percolation. This effect leads to 1) a broadening of the glass transition and 2) an increase of T _g in quantitative agreement with experimental results. For both strongly and weakly adsorbed films, the shift in T _g is given by a power law, the exponent being the inverse of that of the correlation length of 3D percolation. Received 21 March 2000 and Received in final form 4 December 2000     

Heterogeneous dynamics at the glass transition in van der Waals liquids: Determination of the characteristic scale

Recent experiments have demonstrated that the dynamics in liquids close to the glass transition temperature is strongly heterogeneous. The characteristic size of these heterogeneities has been measured to be a few nanometers at T _g. We extend here a recent model for describing the heterogeneous nature of the dynamics which allows both to derive this length scale and the right orders of magnitude of the heterogeneities of the dynamics close to the glass transition. Our model allows then to interpret quantitatively small probes diffusion experiments. Received 29 March 2002 and Received in final form 11 November 2002 RID="a" ID="a"e-mail: long@lps.u-psud.fr     

Twist free energy in a spin glass

The field theory of a short range spin glass with Gaussian random interactions, is considered near the upper critical dimension six. In the glassy phase, replica symmetry breaking is accompanied with massless Goldstone modes, generated by the breaking of reparametrization invariance of a Parisi type solution. Twisted boundary conditions are thus imposed at two opposite ends of the system in order to study the size dependence of the twist free energy. A loop-expansion is performed to first order around a twisted background. It is found, as expected but it is non trivial, that the theory does renormalize around such backgrounds, as well as for the bulk. However two main differences appear, in comparison with simple ferromagnetic transitions: (i) the loop expansion yields a (negative) anomaly in the size dependence of the free energy, thereby lifting the lower critical dimension to a value greater than two (ii) the free energy is lowered by twisting the boundary conditions. This situation is common in spin glasses, reflecting the non-positivity of mode multiplicity in replica symmetry breaking, but its physical meaning is still unclear. Received 12 April 2002 / Received in final form 30 July 2002 Published online 19 November 2002     

Enthalpy recovery of a glass-forming liquid constrained in a nanoporous matrix: Negative pressure effects

The T _g of organic liquids confined to nanoporous matrices and that of thin polymer films can decrease dramatically from the bulk value. One possible explanation for this phenomenon is the development of hydrostatic tension during vitrification under confinement that results in a concomitant increase in the free volume. Here we present experimental evidence and modeling results for ortho-terphenyl (o-TP) confined in pores as small as 11.6 nm that indicate that, although there is an important hydrostatic tension in the liquid in the pores, it does not develop until near the reduced T _g of the constrained material --well below the bulk T _g. Enthalpy recovery for the o-TP in the nanopores exhibits accelerated physical aging relative to the bulk, as well as a leveling off of the fictive temperature at equilibrium values greater than the aging temperature. An adaptation of the structural recovery model that incorporates vitrification under isochoric conditions is able to provide a quantitative explanation for the apparently anomalous aging observed in nanopore confined liquids and in thin polymeric films. The results strongly support the existence of an intrinsic size effect as the cause of the reduced T _g. Received 3 September 2001     

Deviations from perfect memory in spin glass temperature cycling experiments

We study the deviations from perfect memory in negative temperature cycle spin glass experiments. It is known that the a.c. susceptibility after the temperature is raised back to its initial value is superimposed to the reference isothermal curve for large enough temperature jumps ΔT (perfect memory). For smaller ΔT, the deviation from this perfect memory has a striking non monotonous behavior: the `memory anomaly' is negative for small ΔT's, becomes positive for intermediate ΔT's, before vanishing for still larger ΔT's. We show that this interesting behavior can be reproduced by simple Random Energy trap models. We discuss an alternative interpretation in terms of droplets and temperature chaos. Received 23 May 2002 Published online 14 October 2002 RID="a" ID="a"e-mail: sasaki@ipno.in2p3.fr     

Euclidean random matrices, the glass transition and the boson peak

In this paper I will describe some results that have been recently obtained in the study of random Euclidean matrices, i.e. matrices that are functions of random points in Euclidean space. In the case of translation invariant matrices one generically finds a phase transition between a phonon phase and a saddle phase. If we apply these considerations to the study of the Hessian of the Hamiltonian of the particles of a fluid, we find that this phonon-saddle transition corresponds to the dynamical phase transition in glasses, that has been studied in the framework of the mode coupling approximation. The boson peak observed in glasses at low temperature is a remanent of this transition. Received 4 May 2002     

Scaling of broadband dielectric data of glass-forming liquids and plastic crystals

The Nagel scaling and the modified scaling procedure proposed recently by Dendzik et al. have been applied to broadband dielectric data on two glass-forming liquids (glycerol and propylene carbonate) and three plastic crystals (ortho-carborane, meta-carborane, and 1-cyano-adamantane). Our data extend the upper limit of the abscissa range to considerably higher values than in previously published analyses. At the highest frequencies investigated, deviations from a single master curve show up which are most pronounced in the Dendzik scaling plot. The loss curves of the plastic crystals do not scale in the Nagel plot, but they fall onto a separate master curve in the Dendzik plot. In addition, we address the question of a possible divergence of the static susceptibility near the Vogel-Fulcher temperature. For this purpose, the low-temperature evolution of the high-frequency wing of the dielectric loss peaks is investigated in detail. No convincing proof for such a divergence can be deduced from the present broadband data. Received 14 June 1999 and Received in final form 4 October 1999     

Advanced memory effects in the aging of a polymer glass

A new kind of memory effect on low frequency dielectric measurements on plexiglass (PMMA) is described. These measurements show that cooling and heating the sample at constant rate give an hysteretic dependence on temperature of the dielectric constant ε. A temporary stop of cooling produces a downward relaxation of ε. Two main features are observed (i) when cooling is resumed ε goes back to the values obtained without the cooling stop (i.e. the low temperature state is independent of the cooling history) (ii) upon reheating ε keeps the memory of all the cooling stops (Advanced memory). The dependence of this effect on frequency and on the cooling rate is analyzed. The memory deletion is studied too. Finally the results are compared with those of similar experiments done in spin glasses and with the famous experiments of Kovacs. Received 24 September 2001 and Received in final form 20 November 2001     

Confinement and processing effects on glass transition temperature and physical aging in ultrathin polymer films: Novel fluorescence measurements

Fluorescence intensity measurements of chromophore-doped or -labeled polymers have been used for the first time to determine the effects of decreasing film thickness on glass transition temperature, T _g, the relative strength of the glass transition, and the relative rate of physical aging below T _g in supported, ultrathin polymer films. The temperature dependence of fluorescence intensity measured in the glassy state of thin and ultrathin films of pyrene-doped polystyrene (PS), poly(isobutyl methacrylate) (PiBMA), and poly(2-vinylpyridine) (P2VP) differs from that in the rubbery state with a transition at T _g. Positive deviations from bulk T _g are observed in ultrathin PiBMA and P2VP films on silica substrates while substantial negative deviations from bulk T _g are observed in ultrathin PS films on silica substrates. The relative difference in the temperature dependences of fluorescence intensity in the rubbery and glassy states is usually reduced with decreasing film thickness, indicating that the strength of the glass transition is reduced in thinner films. The temperature dependence of fluorescence intensity also provides useful information on effects of processing history as well as on the degree of polymer-substrate interaction. In addition, when used as a polymer label, a mobility-sensitive rotor chromophore is demonstrated to be useful in measuring relative rates of physical aging in films as thin as 10 nm. Received 21 August 2001     

Some relevant parameters affecting the glass transition of supported ultra-thin polymer films

We have measured, the thickness dependence of the glass transition temperature T(g)( h), using ellipsometry at variable temperature, for poly(methyl-methacrylate) (PMMA) of various tacticity in confined geometry. We report that several factors significantly affect T(g)( h): i) polymer microstructure (stereoregularity of PMMA) related to local dynamics; ii) interfacial interactions; iii) conformation of the polymer chains. These results raise many fundamental questions on the origin of the thickness-dependent glass transition. Why and how do the interactions with the substrate significantly affect T(g)( h)? Does T(g)( h) depend on the modifications of conformational parameters of the chains (their entropy)? What is the correlation between local dynamics and T(g)( h) in thin films? The aim of this paper is to summarise these open questions, which should stimulate further investigations in the thin polymer film scientific community.