Microelectrophoresis of Silica Rods Using Confocal Microscopy.

The electrophoretic mobility and the zeta potential (ζ) of fluorescently labeled colloidal silica rods, with an aspect ratio of 3.8 and 6.1, were determined with microelectrophoresis measurements using confocal microscopy. In the case where the colloidal particles all move at the same speed parallel to the direction of the electric field, we record a xyz-stack over the whole depth of the capillary. This method is faster and more robust compared to taking xyt-series at different depths inside the capillary to obtain the parabolic flow profile, as was done in previous work from our group. In some cases, rodlike particles do not move all at the same speed in the electric field, but exhibit a velocity that depends on the angle between the long axis of the rod and the electric field. We measured the orientation-dependent velocity of individual silica rods during electrophoresis as a function of κa, where κ-1 is the double layer thickness and a is the radius of the rod associated with the diameter. Thus, we determined the anisotropic electrophoretic mobility of the silica rods with different sized double layers. The size of the double layer was tuned by suspending silica rods in different solvents at different electrolyte concentrations. We compared these results with theoretical predictions. We show that even at already relatively high κa when the Smoluchowski limiting law is assumed to be valid (κa > 10), an orientation dependent velocity was measured. Furthermore, we observed that at decreasing values of κa the anisotropy in the electrophoretic mobility of the rods increases. However, in low polar solvents with κa < 1, this trend was reversed: the anisotropy in the electrophoretic mobility of the rods decreased. We argue that this decrease is due to end effects, which was already predicted theoretically. When end effects are not taken into account, this will lead to strong underestimation of the experimentally determined zeta potential.

Dynamic self-organization of side-propelling colloidal rods: experiments and simulations.

In recent years, there is a growing interest in designing artificial analogues of living systems, fueled not only by potential applications as 'smart micro-machines', but also by the demand for simple models that can be used to study the behavior of their more complex natural counterparts. Here, we present a facile, internally driven, experimental system comprised of fluorescently labeled colloidal silica rods of which the self-propulsion is powered by the decomposition of H2O2 catalyzed by a length-wise half Pt coating of the particles in order to study how shape anisotropy and swimming direction affect the collective behavior. We investigated the emerging structures and their time evolution for various particle concentrations in (quasi-)two dimensional systems for three aspect ratios of the rods on a single particle level using a combination of experiments and simulations. We found that the dynamic self-organization relied on a competition between self-propulsion and phoretic attractions induced by phoresis of the rods. We observed that the particle clustering behavior depends on the concentration as well as the aspect ratio of the rods. Our findings provide a more detailed understanding of dynamic self-organization of anisotropic particles and the role the propulsion direction plays in internally driven systems.

Phase diagram of binary colloidal rod-sphere mixtures from a 3D real-space analysis of sedimentation-diffusion equilibria.

Self-assembly of binary particle systems offers many new opportunities for materials science. Here, we studied sedimentation equilibria of silica rods and spheres, using quantitative 3D confocal microscopy. We determined not only pressure, density and order parameter profiles, but also the experimental phase diagram exhibiting a stable binary smectic liquid-crystalline phase (Sm2). Using computer simulations we confirmed that the Sm2-phase can be stabilized by entropy alone, which opens up the possibility of combining new materials properties at a wide array of length scales.

Confinement Induced Plastic Crystal-to-Crystal Transitions in Rodlike Particles with Long-Ranged Repulsion.

Colloidal particles in geometrical confinement display a complex variety of packing structures different from their three-dimensional (3D) bulk counterpart. Here, we confined charged rodlike colloids with long-ranged repulsions to a thin wedge-shaped cell and show, by quantitative 3D confocal microscopy, that not only their positional but also their orientational order depends sensitively upon the slit width. Synchronized with transitions in lattice symmetry and number of layers confinement induces plastic crystal-to-crystal transitions. A model analysis suggests that this complex sequence of more or less rotationally ordered states originates from the subtle competition between the electrostatic repulsion of a rod with the wall and with its neighbors.

Orientation of a dielectric rod near a planar electrode.

We present experimental and theoretical results on suspensions of silica rods in DMSO-water, subjected to an applied electric field. The experimental results indicate that, if the electrode used for generating the electric field is in direct contact with the suspension, a fraction of the rods close to the electrode surface does not stand parallel to the field but instead lies flat on the electrode when the field is switched on. To explain these results theoretically, we modify the coupled dipole method to include "image dipoles", and find that a rod close to the electrode experiences not only the expected global potential energy minimum at an orientation parallel to the electric field, but also a local minimum several times the thermal energy in depth for orientations parallel to the electrode surface. Additionally, we indicate how the magnitude of the potential energy depends on the electric field strength and include results not only for negatively polarizable (which correspond to the aforementioned experimental system), but also for positively polarizable rods.

Switching plastic crystals of colloidal rods with electric fields.

When a crystal melts into a liquid both long-ranged positional and orientational order are lost, and long-time translational and rotational self-diffusion appear. Sometimes, these properties do not change at once, but in stages, allowing states of matter such as liquid crystals or plastic crystals with unique combinations of properties. Plastic crystals/glasses are characterized by long-ranged positional order/frozen-in-disorder but short-ranged orientational order, which is dynamic. Here we show by quantitative three-dimensional studies that charged rod-like colloidal particles form three-dimensional plastic crystals and glasses if their repulsions extend significantly beyond their length. These plastic phases can be reversibly switched to full crystals by an electric field. These new phases provide insight into the role of rotations in phase behaviour and could be useful for photonic applications.