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We review recent work on the phase behaviour of binary charged spheremixtures as a function of particle concentration and composition. Both sizeratios and charge ratios are varied over a wide range. By contrast to hardspheres the long ranged Coulomb interaction stabilizes the crystal phase at lowparticle concentrations and shifts the occurrence of amorphous solids toparticle concentrations considerably larger than the freezing concentration.Depending on size- and charge ratios we observe upper azeotrope, spindle, lowerazeotrope and eutectic types of phase diagrams, all known well from metalsystems. Most solids are of body centred cubic structure. Occasionallystoichiometric compounds are formed at large particle concen-trations. For verylow size ratios entropic effects dominate and induce a fluid-fluid phaseseparation. As for charged spheres also the charge ratio is decisive for thetype of phase behaviour, future experiments with charge variable silica spheresare suggested.

Phase behaviour of deionized binary mixtures of charged colloidal spheres