Colloidal suspensions are widely used to study processes such as melting, freezing1,2,3 and glass transitions4,5. 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 space3,4. Another attractive feature is that different types of colloidal interactions, such as long-range repulsive1,3, short-range attractive5, hard-sphere-like2,3,4 and dipolar3, 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 aggregation6. 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 applications7.

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Ionic colloidal crystals of oppositely charged particles.

Monodisperse colloidal suspensions of micrometre-sized spheres are playing an increasingly important role as model systems to study, in real space, a variety of phenomena in condensed matter physics—such as glass transitions and crystal nucleation1,2,3,4. But to date, no quantitative real-space studies have been performed on crystal melting, or have investigated systems with long-range repulsive potentials. Here we demonstrate a charge- and sterically stabilized colloidal suspension—poly(methyl methacrylate) spheres in a mixture of cycloheptyl (or cyclohexyl) bromide and decalin—where both the repulsive range and the anisotropy of the interparticle interaction potential can be controlled. This combination of two independent tuning parameters gives rise to a rich phase behaviour, with several unusual colloidal (liquid) crystalline phases, which we explore in real space by confocal microscopy. The softness of the interaction is tuned in this colloidal suspension by varying the solvent salt concentration; the anisotropic (dipolar) contribution to the interaction potential can be independently controlled with an external electric field ranging from a small perturbation to the point where it completely determines the phase behaviour. We also demonstrate that the electric field can be used as a pseudo-thermodynamic temperature switch to enable real-space studies of melting transitions. We expect studies of this colloidal model system to contribute to our understanding of, for example, electro- and magneto-rheological fluids.

A colloidal model system with an interaction tunable from hard sphere to soft and dipolar

As one increases the concentration of a colloidal suspension, the system exhibits a dramatic increase in viscosity. Beyond a certain concentration, the system is said to be a colloidal glass; structurally, the system resembles a liquid, yet motions within the suspension are slow enough that it can be considered essentially frozen. For several decades, colloids have served as a valuable model system for understanding the glass transition in molecular systems. The spatial and temporal scales involved allow these systems to be studied by a wide variety of experimental techniques. The focus of this review is the current state of understanding of the colloidal glass transition, with an emphasis on experimental observations. A brief introduction is given to important experimental techniques used to study the glass transition in colloids. We describe features of colloidal systems near and in glassy states, including increases in viscosity and relaxation times, dynamical heterogeneity and ageing, among others. We also compare and contrast the glass transition in colloids to that in molecular liquids. Other glassy systems are briefly discussed, as well as recently developed synthesis techniques that will keep these systems rich with interesting physics for years to come.

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The Physics of the Colloidal Glass Transition

We studied the free fluid-fluid interface in a phase-separated colloid-polymer dispersion with laser scanning confocal microscopy and directly observed thermally induced capillary waves at the interface in real space. Experimental results for static and dynamic correlation functions validate the capillary wave model down to almost the particle level. The ultralow interfacial tension, the capillary length, and the capillary time are found to be in agreement with independent measurements. Furthermore, we show that capillary waves induce the spontaneous breakup of thin liquid films and thus are of key importance in the process of droplet coalescence.

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Direct visual observation of thermal capillary waves.

The creation of a new material often starts from the design of its constituent building blocks at a smaller scale. From macromolecules to colloidal architectures, to granular systems, the interactions between basic units of matter can dictate the macroscopic behaviour of the resulting engineered material and even regulate its genesis. Information can be imparted to the building units by altering their physical and chemical properties. In particular, the shape of building blocks has a fundamental role at the colloidal scale, as it can govern the self-organization of particles into hierarchical structures and ultimately into the desired material. Herein we report a simple and general approach to generate an entire zoo of new anisotropic colloids. Our method is based on a controlled deformation of multiphase colloidal particles that can be selectively liquified, polymerized, dissolved and functionalized in bulk. We further demonstrate control over the particle functionalization and coating by realizing patchy and Janus colloids.

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Shaping colloids for self-assembly

We report a single step procedure to prepare monodisperse colloidal poly(methyl)methacrylate (PMMA) particles where fluorescent dyes are incorporated into the polymer network. The particles are sterically stabilized against flocculation by poly(12-hydroxystearic acid). The fluorescent dyes are RITC (rhodamine isothiocyanate)-aminostyrene (RAS) and 4-methylaminoethylmethacrylate-7-nitrobenzo-2-oxa-1,3-diazol (NBD-MAEM), which are prepared from (commercially available) RITC and 4-chloro-7-nitrobenzo-2-oxa-1,3-diazol (NBD-Cl), respectively, as starting materials. The particles can be grown larger with nonfluorescent PMMA. Examples of the usefulness of these model particles in colloid science are given.

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Gilles Bosma

Papers

Preparation of monodisperse, fluorescent PMMA-latex colloids by dispersion polymerization.