Phase behaviour and structure of model colloid-polymer mixtures

Abstract

We study the phase behaviour and structure of model colloid-polymer mixtures. By integrating out the degrees of freedom of the non-adsorbing ideal polymer coils, we derive a formal expression for the effective one-component Hamiltonian of the colloids. Using the two-body (Asakura-Oosawa pair potential) approximation to this effective Hamiltonian in computer simulations, we determine the phase behaviour for size ratios q = p/c = 0.1, 0.4, 0.6, and 0.8, where c and p denote the diameters of the colloids and the polymer coils, respectively. For large q, we find both a fluid-solid and a stable fluid-fluid transition. However, the latter becomes metastable with respect to a broad fluid-solid transition for q0.4. For q = 0.1 there is a metastable isostructural solid-solid transition which is likely to become stable for smaller values of q. We compare the phase diagrams obtained from simulation with those of perturbation theory using the same effective one-component Hamiltonian and with the results of the free-volume approach. Although both theories capture the main features of the topologies of the phase diagrams, neither provides an accurate description of the simulation results. Using simulation and the Percus-Yevick approximation we determine the radial distribution function g(r) and the structure factor S(k) of the effective one-component system along the fluid-solid and fluid-fluid phase boundaries. At state-points on the fluid-solid boundary corresponding to high colloid packing fractions (packing fractions equal to or larger than that at the triple point), the value of S(k) at its first maximum is close to the value 2.85 given by the Hansen-Verlet freezing criterion. However, at lower colloid packing fractions freezing occurs when the maximum value is much lower than 2.85. Close to the critical point of the fluid-fluid transition we find Ornstein-Zernike behaviour and at very dilute colloid concentrations S(k) exhibits pronounced small-angle scattering which reflects the growth of clusters of the colloids. We compare the phase behaviour of this model with that found in studies of additive binary hard-sphere mixtures.