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 study gelation in suspensions of model colloidal particles with short-ranged attractive and long-ranged repulsive interactions by means of three-dimensional fluorescence confocal microscopy. At low packing fractions, particles form stable equilibrium clusters. Upon increasing the packing fraction the clusters grow in size and become increasingly anisotropic until finally associating into a fully connected network at gelation. We find a surprising order in the gel structure. Analysis of spatial and orientational correlations reveals that the gel is composed of dense chains of particles constructed from face-sharing tetrahedral clusters. Our findings imply that dynamical arrest occurs via cluster growth and association.

The advent of autonomous self-propulsion has instigated research towards making colloidal machines that can deliver mechanical work in the form of transport, and other functions such as sensing and cleaning. While much progress has been made in the last 10 years on various mechanisms to generate self-propulsion, the ability to steer self-propelled colloidal devices has so far been much more limited. A critical barrier in increasing the impact of such motors is in directing their motion against the Brownian rotation, which randomizes particle orientations. In this context, here we report directed motion of a specific class of catalytic motors when moving in close proximity to solid surfaces. This is achieved through active quenching of their Brownian rotation by constraining it in a rotational well, caused not by equilibrium, but by hydrodynamic effects. We demonstrate how combining these geometric constraints can be utilized to steer these active colloids along arbitrary trajectories.

We report the equilibrium self-assembly of binary crystals of oppositely charged colloidal microspheres at high density. By varying the magnitude of the charge on near equal-sized spheres we show that the structure of the binary crystal may be switched between face-centered cubic, cesium chloride, and sodium chloride. We interpret these transformations in terms of a competition between entropic and Coulombic forces.

In this work, we show that the asymmetrical distribution of mass at the surface of catalytic Janus swimmers results in the devices preferentially propelling themselves upward in a gravitational field. We demonstrate the existence of this gravitaxis phenomenon by observing the trajectories of fueled Janus swimmers, which generate thrust along a vector pointing away from their metallically coated half. We report that as the size of the spherical swimmer increases, the propulsive trajectories are no longer isotropic with respect to gravity, and they start to show a pronounced tendency to move in an upward direction. We suggest that this effect is due to the platinum caps asymmetric mass exerting an increasing influence on the azimuthal angle of the Janus sphere with size, biasing its orientation toward a configuration where the heavier propulsion generating surface faces down. This argument is supported by the good agreement we find between the experimentally observed azimuthal angle distribution for the Janus swimmers and predictions made by simple Boltzmann statistics. This gravitaxis phenomenon provides a mechanism to autonomously control and direct the motion of catalytic swimming devices and so enable a route to make autonomous transport devices and develop new separation, sensing, and controlled release applications.

The phoretic mechanisms at stake in the propulsion of asymmetric colloids have been the subject of debates during the past years. In particular, the importance of electrokinetic effects on the motility of Pt-PS Janus sphere was recently discussed. Here, we probe the hydrodynamic flow field around a catalytically active colloid using particle tracking velocimetry both in the freely swimming state and when kept stationary with an external force. Our measurements provide information about the fluid velocity in the vicinity of the surface of the colloid, and confirm a mechanism for propulsion that was proposed recently. In addition to offering a unified understanding of the nonequilibrium interfacial transport processes at stake, our results open the way to a thorough description of the hydrodynamic interactions between such active particles and understanding their collective dynamics.

The ability to control the degree of spin, or rotational velocity, for catalytic swimming devices opens up the potential to access well defined spiralling trajectories, enhance cargo binding rate, and realise theoretically proposed behaviour such as chiral diffusion. Here we assess the potential to impart a well-defined spin to individual catalytic Janus swimmers by using glancing angle metal evaporation onto a colloidal crystal to break the symmetry of the catalytic patch due to shadowing by neighbouring colloids. Using this approach we demonstrate a well-defined relationship between the glancing angle and the ratio of rotational to translational velocity. This allows batches of colloids with well-defined spin rates in the range 0.25 to 2.5 Hz to be produced. With reference to the shape and thickness variations across the catalytically active shapes, and their propulsion mechanism we discuss the factors that can lead to the observed variations in rotational propulsion.

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