C. Patrick Royall

Ionic colloidal crystals of oppositely charged particles.

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.

Complex Plasmas and Colloidal Dispersions: Particle-resolved Studies of Classical Liquids and Solids

Interdisciplinary Research: Scientific Background Basic Properties of Complex Plasmas and Colloidal Dispersions: Charging, Interactions, Major Forces Examples of Particle-Resolved Studies: Static Liquid Structure Liquid-Solid Phase Transitions Kinetics of Liquids Hydrodynamics and Rheology at the Discreteness Limit Nonequilibrium Phase Transitions Binary Mixtures Tunable Interactions Anisotropic Particles.

The role of local structure in dynamical arrest

CPR would like to acknowledge the Royal Society for financial support and European Research Council (ERC Consolidator Grant NANOPRS, project number 617266).

Nonequilibrium sedimentation of colloids on the particle scale

We investigate sedimentation of model hard-sphere-like colloidal dispersions confined in horizontal capillaries using laser scanning confocal microscopy, dynamical density functional theory, and Brownian dynamics computer simulations. For homogenized initial states we obtain quantitative agreement of the results from the respective approaches for the time evolution of the one-body density distribution and the osmotic pressure on the walls. We demonstrate that single-particle information can be obtained experimentally in systems that were initialized further out of equilibrium such that complex lateral patterns form.

Applications of environmental scanning electron microscopy to colloidal aggregation and film formation

Abstract Environmental scanning electron microscopy (ESEM) is a rather new form of electron microscopy, which permits the observation of hydrated samples in their native state, and also does not require that insulators are coated with a conducting layer. These two factors make it ideal for studying colloidal dispersions as they aggregate and/or film form. This paper describes the application of ESEM to three situations involving aggregating latices. Firstly the nature of fractal structures grown from aggregating acrylic latices is discussed, with a comparison given of the behaviour with and without added salt as the screening between particles is altered. Secondly the behaviour of vinyl latices is considered. The impact of the addition of starch, both modified and unmodified, upon the particle size distribution and ability to film form is examined. Finally, the structures which form when the hard inorganic component silica is added to acrylic latices are explored. Together these three examples illustrate some of the many strengths of the ESEM in the field of colloidal dispersions and aggregates.

Re-entrant melting and freezing in a model-system of charged colloids

We studied the phase behavior of charged and sterically stabilized colloids using confocal microscopy in a low polarity solvent (dielectric constant 5.4). Upon increasing the colloid volume fraction we found a transition from a fluid to a body centered cubic crystal at 0.0415+/-0.0005, followed by reentrant melting at 0.1165+/-0.0015. A second crystal of different symmetry, random hexagonal close packed, was formed at a volume fraction around 0.5, similar to that of hard spheres. We attribute the intriguing phase behavior to the particle interactions that depend strongly on volume fraction, mainly due to the changes in the colloid charge. In this low polarity system the colloids acquire charge through ion adsorption. The low ionic strength leads to fewer ions per colloid at elevated volume fractions and consequently a density-dependent colloid charge.

Measuring colloidal interactions with confocal microscopy

We use confocal laser scanning microscopy to measure interactions in colloidal suspensions. By inverting the radial distribution function, determined by tracking the particle coordinates, we obtain the effective interaction between the colloidal particles. Although this method can be applied to arbitrary colloidal interactions, here we demonstrate its efficacy with two well-known systems for which accurate theories are available: a colloid-polymer mixture and binary hard spheres. The high sensitivity of this method allows for the precise determination of complex interactions, as exemplified, for example, by the accurate resolution of the oscillatory effective potential of the binary hard sphere system. We argue that the method is particularly well suited for the determination of attractive forces.

Identification of long-lived clusters and their link to slow dynamics in a model glass former

We study the relationship between local structural ordering and dynamical heterogeneities in a model glass-forming liquid, the Wahnström mixture. A novel cluster-based approach is used to detect local energy minimum polyhedral clusters and local crystalline environments. A structure-specific time correlation function is then devised to determine their temporal stability. For our system, the lifetime correlation function for icosahedral clusters decays far slower than for those of similarly sized but topologically distinct clusters. Upon cooling, the icosahedra form domains of increasing size and their lifetime increases with the size of the domains. Furthermore, these long-lived domains lower the mobility of neighboring particles. These structured domains show correlations with the slow regions of the dynamical heterogeneities that form on cooling towards the glass transition. Although icosahedral clusters with a particular composition and arrangement of large and small particles are structural elements of the crystal, we find that most icosahedral clusters lack such order in composition and arrangement and thus local crystalline ordering makes only a limited contribution to this process. Finally, we characterize the spatial correlation of the domains of icosahedra by two structural correlation lengths and compare them with the four-point dynamic correlation length. All the length scales increase upon cooling, but in different ways.

Identification of structure in condensed matter with the topological cluster classification

We describe the topological cluster classification (TCC) algorithm. The TCC detects local structures with bond topologies similar to isolated clusters which minimise the potential energy for a number of monatomic and binary simple liquids with m ≤ 13 particles. We detail a modified Voronoi bond detection method that optimizes the cluster detection. The method to identify each cluster is outlined, and a test example of Lennard-Jones liquid and crystal phases is considered and critically examined.

Lane formation in driven mixtures of oppositely charged colloids

We present quantitative experimental data on colloidal laning at the single-particle level. Our results demonstrate a continuous increase in the fraction of particles in a lane for the case where oppositely charged particles are driven by an electric field. This behavior is accurately captured by Brownian dynamics simulations. By studying the fluctuations parallel and perpendicular to the field we identify the mechanism that underlies the formation of lanes.