Bistable colloidal orientation in polar liquid near a charged wall

Abstract

We examine the translation and rotation of an uncharged spheroidal colloid in polar solvents (water) near a charged flat surface. We solve the nonlinear Poisson-Boltzmann equation outside of the colloid in two dimensions for all tilt angles $\theta$ with respect to the surface normal. The colloid's size is assumed to be comparable to the Debye's length and hence field gradients are essential. The Maxwell stress tensor, including the ideal gas pressure of ions, is integrated over the colloid's surface to give the total force and torque on the colloid. From the torque we calculate the effective angular potential $U_{\rm eff}(\theta)$. The classical behavior where the colloid tends to align in the direction perpendicular to the surface (parallel to the field, $\theta=0$) is retrieved at large colloid-surface distances or small surface potentials. We find a surprising transition whereby at small separations or large potentials the colloid aligns parallel to the surface ($\theta=90^\circ$). Moreover, this colloid orientation is amplified at a finite value of the aspect ratio. This transition may have important consequences to flow of colloidal suspensions or as a tool to switch layering of such suspensions near a surface.