Dynamical heterogeneity and nonlinear susceptibility in supercooled liquids with short-range attraction

Recent work has demonstrated the strong qualitative differences between the dynamics near a glass transition driven by short-ranged repulsion and one governed by short-ranged attraction. Here we study in detail the behavior of nonlinear, higher-order correlation functions that measure the growth of length scales associated with dynamical heterogeneity in both types of systems. We find that this measure is qualitatively different in the repulsive and attractive cases with regards to the wave vector dependence as well as the time dependence of the standard nonlinear four-point dynamical susceptibility. We discuss the implications of these results for the general understanding of dynamical heterogeneity in glass-forming liquids.     

Microstructure and dynamics near an attractive colloidal glass transition

The microstructure and dynamics of a colloidal system interacting via short-ranged interparticle potential is studied by ultra-small-angle x-ray scattering and x-ray photon correlation spectroscopy. A colloidal gas-liquid type transition is induced when the short-ranged attractive interactions attain sufficient magnitude. The development of liquidlike structure is preceded by a systematic transition in the particle dynamics from diffusive to constrained motion and then completely frozen behavior. This demonstrates the existence of a jamming transition induced by strong short-ranged attractive interactions even at low packing fractions.     

Microstructure and rheology near an attractive colloidal glass transition

Microstructure and rheological properties of a thermally reversible short-ranged attractive colloidal system are studied in the vicinity of the attractive glass transition line. At high volume fractions, the static structure factor changes very little but the low frequency shear moduli varies over several orders of magnitude across the transition. From the frequency dependence of shear moduli, fluid-attractive glass and repulsive glass-attractive glass transitions are identified.     

Glass-glass transition and new dynamical singularity points in an analytically solvable p-spin glasslike model

We introduce and analytically study a generalized p-spin glasslike model that captures some of the main features of attractive glasses, recently found by mode coupling investigations, such as a glass-glass transition line and dynamical singularity points characterized by a logarithmic time dependence of the relaxation. The model also displays features not predicted by the mode coupling scenario that could further describe the attractive glasses behavior, such as aging effects with new dynamical singularity points ruled by logarithmic laws or the presence of a glass spinodal line.     

Comparative simulation study of colloidal gels and glasses

Using computer simulations, we identify the mechanisms causing aggregation and structural arrest of colloidal suspensions interacting with a short-ranged attraction at moderate and high densities. Two different nonergodicity transitions are observed. As the density is increased, a glass transition takes place, driven by excluded volume effects. In contrast, at moderate densities, gelation is approached as the strength of the attraction increases. At high density and interaction strength, both transitions merge, and a logarithmic decay in the correlation function is observed. All of these features are correctly predicted by mode coupling theory.     

Equilibrium cluster phases and low-density arrested disordered states: the role of short-range attraction and long-range repulsion

We study a model in which particles interact with short-ranged attractive and long-ranged repulsive interactions, in an attempt to model the equilibrium cluster phase recently discovered in sterically stabilized colloidal systems in the presence of depletion interactions. At low packing fractions, particles form stable equilibrium clusters which act as building blocks of a cluster fluid. We study the possibility that cluster fluids generate a low-density disordered arrested phase, a gel, via a glass transition driven by the repulsive interaction. In this model the gel formation is formally described with the same physics of the glass formation.     

Re-entrant glass transition in a colloid-polymer mixture with depletion attractions

Performing light scattering experiments we show that introducing short-ranged attraction to a colloid suspension of nearly hard spheres by addition of a free polymer produces new glass-transition phenomena. We observe a dramatic acceleration of the density fluctuations amounting to the melting of a colloidal glass. Upon increasing the strength of the attractions the system freezes into another nonergodic state sharing some qualitative features with gel states occurring at lower colloid packing fractions. This re-entrant glass transition is in qualitative agreement with recent theoretical predictions.     

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.     

Self-consistent current relaxation theory for the electron localization problem

The self-consistent current relaxation theory for the Anderson transition is generalized to include quantum interference effects. The influence of long-ranged potential fluctuations as opposed to short-ranged ones is discussed and for dimensionalityd>2 a crossover for the dynamical conductivity from a regime with Wegner scaling to one with the scaling laws for classical percolation is found. Ford=2 an abrupt transition from strong to extremely weak localization is obtained.     

How a liquid becomes a glass both on cooling and on heating

The onset of structural arrest and glass formation in a concentrated suspension of silica nanoparticles in a water-lutidine binary mixture near its consolute point is studied by exploiting the near-critical fluid degrees of freedom to control the strength of an attraction between particles and multispeckle x-ray photon correlation spectroscopy to determine the particles' collective dynamics. This model system undergoes a glass transition both on cooling and on heating, and the intermediate liquid realizes unusual logarithmic relaxations. How vitrification occurs for the two different glass transitions is characterized in detail and comparisons are drawn to recent theoretical predictions for glass formation in systems with attractive interactions.     

Direct imaging of dynamical heterogeneities near the colloid-gel transition

We observe the microscopic dynamics of a suspension of colloids with attractive interaction by confocal fluorescence microscopy to provide a deeper understanding of the relationship between local structure and dynamics near the gel transition. We study the distinct and self-parts of the van Hove density-density correlation function applied to our experimental data. Separable fast and slow populations emerge in the self-part, while the distinct part shows a pronounced signature of dynamic heterogeneities close to the gel transition, dominated by the fast particles. The slow population close to the gel transition shares features with an attraction-driven colloidal glass, including a plateau in the mean squared displacement that provides an estimate for the dynamical localization length.     

Collective dynamics of colloids at fluid interfaces

The evolution of an initially prepared distribution of micron-sized colloidal particles, trapped at a fluid interface and under the action of their mutual capillary attraction, is analyzed by using Brownian dynamics simulations. At a separation λ given by the capillary length of typically 1mm, the distance dependence of this attraction exhibits a crossover from a logarithmic decay, formally analogous to two-dimensional gravity, to an exponential decay. We discuss in detail the adaptation of a particle-mesh algorithm, as used in cosmological simulations to study structure formation due to gravitational collapse, to the present colloidal problem. These simulations confirm the predictions, as far as available, of a mean-field theory developed previously for this problem. The evolution is monitored by quantitative characteristics which are particularly sensitive to the formation of highly inhomogeneous structures. Upon increasing λ the dynamics shows a smooth transition from the spinodal decomposition expected for a simple fluid with short-ranged attraction to the self-gravitational collapse scenario.     

Molecular Dynamics Simulation of Cage Effect in the Glass Transition of Argon

The glass transition process of argon is studied by molecular dynamics simulations with Lennard-Jones potential. The cage effect appears at about 24K. The Lindemann length of argon is found to be 0.55A. Two relaxation processes are clearly observed near the glass transition temperature, which is in agreement with the mode-coupling theory.     

Dynamics of supercooled liquids and understanding the glass transition

The self-consistent mode coupling theory of glass transition is briefly reviewed. The existance of a temperature T_c, higher than the usual calorimetric glass transition temperature, across which the dynamics of the fluid becomes quite different are indicated through different experimental results. Above T_c the viscosity tends to diverge with a power law while for lower temperature this sharp transition is cutoff. Such changes in the transport properties can be understood from the self-consistent mode coupling theory. The relaxation functions predicted by the mode-coupling theory over different time scales are indicated. The models with proper wave-vector dependence are also discussed.     

Transitions in glasses at low temperatures

Length-temperature measurements from ?180°C to the glass transition temperature have been made on a poly(vinyl alkyl ether) series, poly(ethylene terephthalate), and a tetrafluoroethylene-trifluoropropylene copolymer series.

Consistent with low frequency dynamic measurements, the poly(vinyl alkyl ethers) exhibit a glass-glass transition? Tgg [1] between Tg and Tg ?70°C with evidence of another at about ?160 to ?180°C. With increasing side-chain length, the expansion coefficient below Tg- and the magnitude of the g-g transition increase, and the value of the Simha-Boyer free-volume product decreases, suggesting retention of excess free volume by the flexible pendant group. This behavior is analogous to that observed for poly(alkyl methacrylates) except that the latter system exhibited two g-g transitions, the lower of which coincided with Tgg [1] observed here.

Poly(ethylene terephthalate) samples, both amorphous and crystalline, exhibit two T > Tg transitions at about ?85 and ?40°C. Dynamic results resolve only one relaxation in this temperature range.

The glass temperatures of the tetrafluoroethylene-trifluoropropylene copolymer series, as determined by both dilatometry and differential scanning calorimetry, extrapolate to a Tg, for 100% amorphous PTFE of 11-16°C. Two g-g transitions, present in each homo-polymer, persist in the copolymers, indicating that only a small number of molecular units are involved. The magnitude of these relaxations, however, as measured by the change in expansion coefficient, is dependent on copolymer composition.     

Temperature dependence of the slip length in polymer melts at attractive surfaces

Using Couette and Poiseuille flows, we extract the temperature dependence of the slip length, delta, from molecular dynamics simulations of a coarse-grained polymer model in contact with an attractive surface. delta is dictated by the ratio of bulk viscosity and surface mobility. At weakly attractive surfaces, lubrication layers form; delta is large and increases upon cooling. Close to the glass transition temperature Tg, very large slip lengths are observed. At a more attractive surface, a sticky surface layer is built up, giving rise to small slip lengths. Upon cooling, delta decreases at high temperatures, passes through a minimum, and grows for T-->Tg. At strongly attractive surfaces, the Navier-slip condition fails to describe Couette and Poiseuille flows simultaneously. The simulations are corroborated by a schematic, two-layer model suggesting that the observations do not depend on details of the computational model.     

Dielectric relaxations in ultrathin isotactic PMMA films and PS-PMMA-PS trilayer films

The local and cooperative dynamics of supported ultrathin films ( L = 6.4 - 120 nm) of isotactic poly(methyl methacrylate) (i-PMMA, Mn = 118 x 10(3) g/mol) was studied using dielectric relaxation spectroscopy for a wide range of frequencies (0.1 Hz to 10(6) Hz) and temperatures (250 - 423 K). To assess the influence of the PMMA film surfaces on the glass transition dynamics, two different sample geometries were employed: a single layer PMMA film with the film surfaces in direct contact with aluminum films which act as attractive, hard boundaries; and a stacked polystyrene-PMMA-polystyrene trilayer film which contains diffuse PMMA-PS interfaces. For single layer films of i-PMMA, a decrease of the glass transition temperature T(g) by up to 10 K was observed for a film thickness L < 25 nm (comparable to R(EE)), indicated by a decrease of the peak temperature T(alpha) in the loss epsilon(")(T) at low and high frequencies and by a decrease in the temperature corresponding to the maximum in the apparent activation energy E(a)(T) of the alpha-process. In contrast, measurements of i-PMMA sandwiched between PS-layers revealed a slight (up to 5 K) increase in T(g) for PMMA film thickness values less than 30 nm. The slowing down of the glass transition dynamics for the thinnest PMMA films is consistent with an increased contribution from the less mobile PMMA-PS interdiffusion regions.     

Competitive localization of vortex lines and interacting bosons

We present a theory for the localization of three-dimensional vortex lines or two-dimensional bosons with a short-ranged repulsive interaction which are competing for a single columnar defect or potential well. For two vortices we use a necklace model approach to find a new kind of delocalization transition between two different states with a single bound particle. This exchange-delocalization transition is characterized by the onset of vortex exchange on the defect for sufficiently weak vortex-vortex repulsion or sufficiently weak binding energy corresponding to high temperature. We calculate the transition point and order of the exchange-delocalization transition. A generalization of this transition to an arbitrary vortex number is proposed.     

Kinetic Arrest Originating in Competition Between Attractive Interaction and Packing Force

We discuss the situation where attractive and repulsive portions of the interparticle potential both contribute significantly to glass formation. We introduce the square-well potential as prototypical model for this situation, and reject the Baxter model as a useful model for comparison to experiment on glasses, based on our treatment within mode coupling theory. We present explicit results for various well widths, and show that, for narrow wells, there is a useful analytical formula that would be suitable for experimentalists working in the field of colloidal science. We raise the question as to whether, in a more exact treatment, the sticky-sphere limit might have an infinite glass transition temperature or a high but finite one.