Effects of polymer polydispersity on the phase behaviour of colloid–polymer mixtures

We study the equilibrium behaviour of a mixture of monodisperse hard sphere colloids and polydisperse non-adsorbing polymers at their θ-point, using the Asakura–Oosawa model treated within the free-volume approximation. Our focus is the experimentally relevant scenario where the distribution of polymer chain lengths across the system is fixed. Phase diagrams are calculated using the moment free energy method, and we show that the mean polymer size ξc at which gas–liquid phase separation first occurs decreases with increasing polymer polydispersity δ. Correspondingly, at fixed mean polymer size, polydispersity favours gas–liquid coexistence but delays the onset of fluid–solid separation. On the other hand, we find that systems with different δ values but the same mass-averaged polymer chain length have nearly polydispersity-independent phase diagrams. We conclude with a comparison to previous calculations for a semi-grand-canonical scenario, where the polymer chemical potentials are imposed; there it was found that fluid–solid coexistence was favoured over gas–liquid in some areas of the phase diagram. Our results show that this somewhat counter-intuitive result arose because the actual polymer size distribution in the system is shifted to smaller sizes relative to the polymer reservoir distribution.