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 nucleation. 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.

The effect of salt on the dynamics of water molecules follows the Hofmeister series. For some "structure-making" salts, the self-diffusion coefficient of the water molecules, D, decreases with increasing salt concentration. For other "structure-breaking" salts, D increases with increasing salt concentration. In this work, the concentration and temperature dependence of the self-diffusion of water in electrolyte solutions is studied using molecular dynamics simulations and pulsed-field-gradient NMR experiments; temperature-dependent viscosities are also independently measured. Simulations of rigid, nonpolarizable models at room temperature show that none of the many models tested can reproduce the experimentally observed trend for the concentration dependence of D; that is, the models predict that D decreases with increasing salt concentration for both structure-breaking and structure-making salts. Predictions of polarizable models are not in agreement with experiment either. These results suggest that many popular water models do not accurately describe the dynamic nature of the hydrogen bond network of water at room temperature. The simulations are in qualitative agreement, however, with experimental results for the temperature dependence of water dynamics; simulations and experiment show an Arrhenius dependence of D with temperature, T, with added salt, that is, ln D ∼ 1/T, over a range of temperatures above the freezing point of water.

Systems of spherical colloidal particles mimic the thermodynamics of atomic crystals. Control of interparticle interactions in colloids, which has recently begun to be extensively exploited, gives rise to rich phase behaviours as well as crystal structures with nanoscale and micron-scale lattice spacings. This provides model systems in which to study fundamental problems in condensed matter physics, such as the dynamics of crystal nucleation and melting, and the nature of the glass transition, at experimentally accessible lengthscales and timescales. Tunable control of these interactions provides reversible control. This will enable quantitative studies of phase transition kinetics as well as the creation of advanced materials with switchability of function and properties.

The nature of solid-solid phase transformations has been a long-standing question spanning the fields of metallurgy and condensed-matter physics, with applications from metallic alloys and ceramics to modern shape-memory materials. In spite of the importance of solid-to-solid transformations in many areas of materials science and condensed-matter physics and the numerous experimental and theoretical studies, a deep understanding of the microstructural changes and the underlying kinetic mechanisms is still missing. In this work, we establish a versatile model system composed of micron-scale ionic microgel colloids, where we not only probe the single-particle kinetics in real space and real time but also tune the phase transition in a multiple-parameter space. In the presence of an imposed electric field, a face-centered cubic (FCC) crystal transforms diffusively into a body-centered tetragonal (BCT) crystal via nucleation and growth. In the reverse direction, however, the BCT phase transforms cooperatively into a long-lived metastable body-centered orthorhombic phase, which only relaxes back to the equilibrium FCC when annealed at higher temperatures. The kinetics is thus either diffusive or martensitic depending on the path, and we believe that these two path-dependent transitions provide the first real-space, particle-level insights of diffusive and martensitic transformations, respectively, in a single system.