Role of Metastable States in Phase Ordering Dynamics

We show that the rate of separation of two phases of different densities (e.g. gas and solid) can be radically altered by the presence of a metastable intermediate phase (e.g. liquid). Within a Cahn-Hilliard theory we study the growth in one dimension of a solid droplet from a supersaturated gas. A moving interface between solid and gas phases (say) can, for sufficient (transient) supersaturation, unbind into two interfaces separated by a slab of metastable liquid phase. We investigate the criteria for unbinding, and show that it may strongly impede the growth of the solid phase.Comment: 4 pages, Latex, Revtex, epsf. Updated two reference

Polydispersity Effects in Colloid-Polymer Mixtures

We study phase separation and transient gelation in a mixture consisting of polydisperse colloids and non-adsorbing polymers, where the ratio of the average size of the polymer to that of the colloid is approximately 0.063. Unlike what has been reported previously for mixtures with somewhat lower colloid polydispersity, the addition of polymers does not expand the fluid-solid coexistence region. Instead, we find a region of fluid-solid coexistence which has an approximately constant width but an unexpected re-entrant shape. We detect the presence of a metastable gas-liquid binodal, which gives rise to two-stepped crystallization kinetics that can be rationalized as the effect of fractionation. Finally, we find that the separation into multiple coexisting solid phases at high colloid volume fractions predicted by equilibrium statistical mechanics is kinetically suppressed before the system reaches dynamical arrest.Comment: 11 pages, 5 figure

Diffusive Evolution of Stable and Metastable Phases II: Theory of Non-Equilibrium Behaviour in Colloid-Polymer Mixtures

By analytically solving some simple models of phase-ordering kinetics, we suggest a mechanism for the onset of non-equilibrium behaviour in colloid-polymer mixtures. These mixtures can function as models of atomic systems; their physics therefore impinges on many areas of thermodynamics and phase-ordering. An exact solution is found for the motion of a single, planar interface separating a growing phase of uniform high density from a supersaturated low density phase, whose diffusive depletion drives the interfacial motion. In addition, an approximate solution is found for the one-dimensional evolution of two interfaces, separated by a slab of a metastable phase at intermediate density. The theory predicts a critical supersaturation of the low-density phase, above which the two interfaces become unbound and the metastable phase grows ad infinitum. The growth of the stable phase is suppressed in this regime.Comment: 27 pages, Latex, eps

Colloidal gelation and non-ergodicity transitions

Within the framework of the mode coupling theory (MCT) of structural relaxation, mechanisms and properties of non-ergodicity transitions in rather dilute suspensions of colloidal particles characterized by strong short-ranged attractions are studied. Results building on the virial expansion for particles with hard cores and interacting via an attractive square well potential are presented, and their relevance to colloidal gelation is discussed.Comment: 10 pages, 4 figures; Talk at the Conference: "Unifying Concepts in Glass Physics" ICTP Trieste, September 1999; to be published in J. Phys.: Condens. Matte

Crystallization of hard-sphere glasses

We study by molecular dynamics the interplay between arrest and crystallization in hard spheres. For state points in the plane of volume fraction ($0.54 \leq phi \leq 0.63$) and polydispersity ($0 \leq s \leq 0.085$), we delineate states that spontaneously crystallize from those that do not. For noncrystallizing (or precrystallization) samples we find isodiffusivity lines consistent with an ideal glass transition at $\phi_g \approx 0.585$, independent of $s$. Despite this, for $s<0.05$, crystallization occurs at $\phi > \phi_g$. This happens on time scales for which the system is aging, and a diffusive regime in the mean square displacement is not reached; by those criteria, the system is a glass. Hence, contrary to a widespread assumption in the colloid literature, the occurrence of spontaneous crystallization within a bulk amorphous state does not prove that this state was an ergodic fluid rather than a glass.Comment: 4 pages, 3 figure

Cellular solid behaviour of liquid crystal colloids. 1. Phase separation and morphology

We study the phase ordering colloids suspended in a thermotropic nematic liquid crystal below the clearing point Tni and the resulting aggregated structure. Small (150nm) PMMA particles are dispersed in a classical liquid crystal matrix, 5CB or MBBA. With the help of confocal microscopy we show that small colloid particles densely aggregate on thin interfaces surrounding large volumes of clean nematic liquid, thus forming an open cellular structure, with the characteristic size of 10-100 micron inversely proportional to the colloid concentration. A simple theoretical model, based on the Landau mean-field treatment, is developed to describe the continuous phase separation and the mechanism of cellular structure formation.Comment: Latex 2e (EPJ style) EPS figures included (poor quality to comply with space limitations

Criticality and phase separation in a two-dimensional binary colloidal fluid induced by the solvent critical behavior

We present an experimental and theoretical study of the phase behavior of a binary mixture of colloids with opposite adsorption preferences in a critical solvent. As a result of the attractive and repulsive critical Casimir forces, the critical fluctuations of the solvent lead to a further critical point in the colloidal system, i.e. to a critical colloidal-liquid--colloidal-liquid demixing phase transition which is controlled by the solvent temperature. Our experimental findings are in good agreement with calculations based on a simple approximation for the free energy of the system.Comment: 5 pages, 5 figures, to be published in Europhysics Letter

Gel transitions in colloidal suspensions

The idealized mode coupling theory (MCT) is applied to colloidal systems interacting via short-range attractive interactions of Yukawa form. At low temperatures MCT predicts a slowing down of the local dynamics and ergodicity breaking transitions. The nonergodicity transitions share many features with the colloidal gel transition, and are proposed to be the source of gelation in colloidal systems. Previous calculations of the phase diagram are complemented with additional data for shorter ranges of the attractive interaction, showing that the path of the nonergodicity transition line is then unimpeded by the gas-liquid critical curve at low temperatures. Particular attention is given to the critical nonergodicity parameters, motivated by recent experimental measurements. An asymptotic model is developed, valid for dilute systems of spheres interacting via strong short-range attractions, and is shown to capture all aspects of the low temperature MCT nonergodicity transitions.Comment: 12 pages, LaTeX, 5 eps figures, uses ioplppt.sty, to appear in J. Phys.: Condens. Matte