Electrophoresis of a weakly charged dielectric fluid droplet in a cylindrical pore.

Electrophoresis of a weakly charged dielectric droplet with constant surface charge density in a chargeless cylindrical pore is investigated theoretically in this study, focusing on the boundary confinement effect of the double layer, which in turn determines the ultimate motion of the droplet. A patched pseudo-spectral method based on the Chebyshev polynomial is adopted to solve the resulting governing fundamental electrokinetic equations. Mobility reversal, among other interesting phenomena, is observed when the droplet is in a narrow cylindrical pore. No such observation was made in the corresponding motion of a rigid particle. The droplet with a thick double layer may even move against the prediction based on the Coulomb electrostatic law, for instance, a positively charged droplet may move against the electric field. The significant enhancement of the motion-deterring double layer polarization due to the severe steric boundary confinement within a narrow cylindrical pore is found to be responsible for this seemingly peculiar phenomenon. Moreover, smaller droplets may move in the opposite direction of the larger ones. The results are useful in capillary electrophoresis involving droplets in particular and migration of droplets through narrow channels in general.

Electrophoresis of a dielectric droplet with constant surface charge density.

Electrophoresis of a dielectric fluid droplet with constant surface charge density is investigated theoretically in this study. A pseudo-spectral method based on Chebyshev polynomials is adopted to solve the governing electrokinetic equations. It is found, among other things, that the larger the electrolyte strength in the ambient solution is, the slower the droplet moves in general. This is due to the strong screening effect of the large amount of indifferent counterions in the neighborhood of the droplet, with no reinforcement of potential-determining ions adsorbing to the droplet surface. The droplet comes to a complete halt eventually. Critical points are discovered for highly charged droplets, at which the droplet surface becomes immobile and the interior fluid stops recirculating. The droplet moves like a rigid particle with constant mobility regardless of its viscosity, a situation referred to as the "solidification phenomenon." The deadlock between the spinning motions on the charged droplet surface induced by the electric driving force and the hydrodynamic driving force respectively is responsible for this peculiar phenomenon. This is also observed for a dielectric droplet with constant surface electric potential. We demonstrate here that it occurs in the constant surface charge density situation as well.