Matthew T. Sullivan

Electrostatics at the oil–water interface, stability, and order in emulsions and colloids

Oil–water mixtures are ubiquitous in nature and are particularly important in biology and industry. Usually additives are used to prevent the liquid droplets from coalescing. Here, we show that stabilization can also be obtained from electrostatics, because of the well known remarkable properties of water. Preferential ion uptake leads to a tunable droplet charge and surprisingly stable, additive-free, water-in-oil emulsions that can crystallize. For particle-stabilized (“Pickering”) emulsions we find that even extremely hydrophobic, nonwetting particles can be strongly bound to (like-charged) oil–water interfaces because of image charge effects. These basic insights are important for emulsion production, encapsulation, and (self-)assembly, as we demonstrate by fabricating a diversity of structures in bulk, on surfaces, and in confined geometries.

The role of feedback in microfluidic flow-focusing devices

A model was developed for the analysis of steady and unsteady bubble generation frequencies in a microfluidic flow-focusing device. In both cases, the generation frequency depends on the downstream influence of bubbles created by the flow-focusing device, which provides a source of feedback. For steady-state generation of bubbles, this feedback explains the relationships among frequency, gas pressure and liquid flow rate in our experiments as well as gives a physical explanation for previously observed frequency relations. The role of feedback is also exploited to explain unsteady behaviour; we develop a numerical model and analytical expressions that agree with experimental measurements.

Concentrating colloids with electric field gradients. I. Particle transport and growth mechanism of hard-sphere-like crystals in an electric bottle

This work concerns the use of electric field gradients to manipulate the local particle concentration in a hard-sphere-like suspension. Inside a specially designed electric bottle, we observed our colloids to collect in the regions of lowest field strength (negative dielectrophoresis). This allows for the use of larger field gradients and stronger dielectrophoretic forces than in the original electric bottle design, which was based on positive dielectrophoresis [M. T. Sullivan et al., Phys. Rev. Lett. 96, 015703 (2006)]. We used confocal scanning laser microscopy to quantitatively follow the time-dependent change in the particle density and the suspension structure. Within a few days, the dielectrophoretic compression was seen to initiate a heterogeneouslike growth of large single crystals, which took place far out-of-equilibrium. The crystals had a random hexagonal close-packed structure and displayed an intriguing growth mechanism, during which the entire crystal was continuously transported, while growing both on the high-field and the low-field sides, although at different rates. After switching off the electric field, the compressed crystals were found to relax to a lower packing fraction and melt, at a much slower rate than the crystal growth. Besides revealing the particular (far out-of-equilibrium) crystal growth mechanism in these electric bottles, our observations also shed light on the role of the different particle transport processes in the cell and some of the relevant tuning parameters. This is useful for different types of experiments, for instance, focusing more on melting, homogeneous crystallization, or the glass transition.