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We describe three sets of experiments on suspensions of 'hard-sphere' colloids. Suspensions of equal-sized particles exhibit the hard-sphere freezing and glass transitions. Mixtures of spheres of two different sizes can form the ordered binary crystals AB2 and AB13. The addition of non-adsorbing polymer to a one-component suspension leads, through the depletion mechanism, to a range of phase behaviour, which includes colloidal gas, liquid, crystal and gel.

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PACS. 82.70 -Disperse systems. PACS. 64.75 -Solubility, segregation, and mixing.Abstract. -A new treatment of the phase behaviour of a colloid + nonadsorbing polymer mixture is described. The calculated phase diagrams show marked polymer partitioning between coexisting phases, an effect not considered in the usual effective-potential approaches to this problem. We also predict that under certain conditions an area of three-phase coexistence should appear in the phase diagram.Introduction. -Phase separation in colloidal suspensions, induced by the addition of nonadsorbing polymer, is a phenomenon of fundamental interest and considerable technological importance. A theoretical explanation was first advanced by Asakura and Oosawa [1], and also independently by Vrij [2], based on the exclusion of polymer from the region between two colloid particles when their surface-surface separation becomes smaller than the diameter of a free polymer coil. The resulting imbalance in osmotic pressure gives rise to an effective attractive «depletion» force between the colloid particles [3,4]. At high enough concentration of polymer this depletion force causes the suspension to separate into colloid-poor and colloid-rich phases. In the latter the particles can, depending on conditions (see below), be in either liquidlike or crystalline spatial arrangements.To predict the phase diagram of a colloid + polymer mixture, most workers to date have adopted an approach in which the depletion potential (an effective pair potential) is added to the parent interparticle potential; thermodynamic perturbation theory is then used to calculate phase stability boundaries [5,6]. Although experimental studies [6,7] show qualitative agreement with the predictions of these calculations, an important reservation

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