Colloid-polymer mixtures may undergo either fluid-fluid phase separation or gelation. This depends on the depth of the quench (polymer concentration) and polymer-colloid size ratio. We present a real-space study of dynamics in phase separating colloid-polymer mixtures with medium-to long-range attractions (polymercolloid size ratio q R = 0.45 − 0.89), with the aim of understanding the mechanism of gelation as the range of the attraction is changed. In contrast to previous studies of short-range attractive systems, where gelation occurs shortly after crossing the equilibrium phase boundary, we find a substantial region of fluid-fluid phase separation. On deeper quenches the system undergoes a continuous crossover to gel formation. We identify two regimes, 'classical' phase separation, where single particle relaxation is faster than the dynamics of phase separation, and 'viscoelastic' phase separation, where demixing is slowed down appreciably due to slow dynamics in the colloid-rich phase. Particles at the surface of the strands of the network exhibit significantly greater mobility than those buried inside the gel strand which presents a method for coarsening. arXiv:1209.3973v1 [cond-mat.soft]

Understanding the phase behaviour of mixtures continues to pose challenges, even for systems that might be considered "simple." Here, we consider a very simple mixture of two colloidal and one non-adsorbing polymer species, which can be simplified even further to a size-asymmetrical binary mixture, in which the effective colloid-colloid interactions depend on the polymer concentration. We show that this basic system exhibits surprisingly rich phase behaviour. In particular, we enquire whether such a system features only a liquid-vapor phase separation (as in one-component colloid-polymer mixtures) or whether, additionally, liquid-liquid demixing of two colloidal phases can occur. Particle-resolved experiments show demixing-like behaviour, but when combined with bespoke Monte Carlo simulations, this proves illusory, and we reveal that only a single liquid-vapor transition occurs. Progressive migration of the small particles to the liquid phase as the polymer concentration increases gives rise to composition inversion-a maximum in the large particle concentration in the liquid phase. Close to criticality, the density fluctuations are found to be dominated by the larger colloids.

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