Colloidal suspensions are widely used to study processes such as melting, freezing and glass transitions. This is because they display the same phase behaviour as atoms or molecules, with the nano- to micrometre size of the colloidal particles making it possible to observe them directly in real space. Another attractive feature is that different types of colloidal interactions, such as long-range repulsive, short-range attractive, hard-sphere-like and dipolar, can be realized and give rise to equilibrium phases. However, spherically symmetric, long-range attractions (that is, ionic interactions) have so far always resulted in irreversible colloidal aggregation. Here we show that the electrostatic interaction between oppositely charged particles can be tuned such that large ionic colloidal crystals form readily, with our theory and simulations confirming the stability of these structures. We find that in contrast to atomic systems, the stoichiometry of our colloidal crystals is not dictated by charge neutrality; this allows us to obtain a remarkable diversity of new binary structures. An external electric field melts the crystals, confirming that the constituent particles are indeed oppositely charged. Colloidal model systems can thus be used to study the phase behaviour of ionic species. We also expect that our approach to controlling opposite-charge interactions will facilitate the production of binary crystals of micrometre-sized particles, which could find use as advanced materials for photonic applications.

We recently reviewed the experimental determination of the volume fraction, f, of hard-sphere colloids, and concluded that the absolute value of f was unlikely to be known to better than AE3-6%. Here, in a second part to that review, we survey effects due to softness in the interparticle potential, which necessitates the use of an effective volume fraction. We review current experimental systems, and conclude that the one that most closely approximates hard spheres remains polymethylmethacrylate spheres sterically stabilised by polyhydroxystearic acid 'hairs'. For these particles their effective hard sphere diameter is around 1-10% larger than the core diameter, depending on the particle size. We argue that for larger colloids suitable for confocal microscopy, the effect of electrostatic charge cannot be neglected, so that mapping to hard spheres must be treated with caution.

We present quantitative three-dimensional real space measurements by confocal microscopy on fluorescently labelled and sterically stabilized dispersions of polymethylmethacrylate spheres dispersed in index and density-matched solvent mixtures with a relative dielectric constant 5 < ε r < 10. In this new model system Debye screening lengths (κ −1) comparable to the particle size (diameter σ) can be realized even for particles with sizes of several micrometres. Moreover, by addition of salt (tetrabutylammonium chloride) κ −1 can be varied and the surface charge of the particles can be set roughly in between the values +100 and −100 mV, as determined by electrophoresis. By a comparison of radial distribution functions and displacements from lattice positions with Monte Carlo computer simulations we found that both the structure in the liquid and the crystallization volume fraction could be described with a Yukawa potential characterized by one set of parameters, a surface potential of 36 mV and κσ = 5, where the particle diameter σ = 2 µm. Anomalous ('phase') behaviour such as extreme long-range repulsions, 'coexistence' of high-density and low-density colloidal crystals and void formation, previously observed for deionized dispersions in water, was observed as well, and can now be studied in a different system without ion exchange resin. These anomalous effects are seen relatively soon after preparing the systems and are absent or short-lived in systems with grounding and at higher salt concentrations.