Patterns in Drying Drops Dictated by Curvature-Driven Particle Transport.

Patterns generated by controlled evaporation of droplets containing colloids are dictated by internally generated flows. This advective particle transport is crucial to the efficacy of printing and coating processes and is also an elegant route to the self-assembly of particles. We propose a novel particle transport route, which involves adsorption of particles to the interface and subsequent curvature-driven migration of the particles along the interface. This interface-mediated transport can be exploited to control the distribution of particles in the dried patterns, which we experimentally elucidate by achieving gravity-induced drop shape changes. Our experiments demonstrate that the interplay between the bulk and the interfacial transport leads to strikingly different patterns: while dried aqueous sessile drops of colloidal dispersions produce well known "coffee-rings", dried pendant drops lead to "coffee-eyes". We support our experimental findings using scaling arguments. In previous studies, the effect of gravity-induced change in drop shape on the patterns formed in drying drops has been neglected. However, we show that the structure of the patterns formed by the colloidal particles after solvent evaporation is markedly different when the drops are deformed by gravity.

Frequency-Dependent Microelectrophoresis Study of Colloids with Tunable Surface Charge.

Nonaqueous poly(methyl methacrylate) (PMMA) colloidal suspensions in a solvent that is simultaneously matched in both density and refractive index have been important for real-space studies of colloidal self-assembly, but their complex electrostatic character remains largely unexplored. Electrophoresis is a powerful tool for determining the surface potential and charge of the colloidal suspension; however, because of refractive index matching, standard electrophoresis measurements are not feasible. We carry out microscope-based microelectrophoresis measurements on PMMA colloids in cyclohexyl bromide and cis-trans decalin to measure particle charge as a function of salt concentration in both DC and frequency-variable AC fields. The colloid charge depends on salt concentration and reverses sign near 0.35 µM, providing evidence that solution ions are actively modifying the colloid surface. The frequency dependence of the electrophoretic mobility yields the characteristic time scale for electric double-layer polarization and provides intriguing evidence for Manning condensation and polyion formation.