The effect of electrode kinetics on electrophoretic forces

[Display omitted] ► Particle–wall interactions during electrophoretic deposition are explored. ► The relationship between electrokinetics and electrode kinetics is presented. ► Forces arise from electroosmosis both on electrode surfaces and proximal particles. ► Finite element analysis allows specification of arbitrary electrode reactivity. ► Electrokinetic flows and forces were computed and are systematically described. Electric fields are commonly used to deposit colloidal particles on electrode surfaces and can even be used in directed assembly. The electric field beneath each particle changes as the particle approaches the wall; the proximity of the wall breaks the fore/aft symmetry and drives complicated flows that exert forces on the particle. While two limiting cases have been partially analyzed, constant electrode potential and uniform current density, the full problem has not been explored. Here, the electroosmotic flows in the region between the particle and the electrode are analyzed and the forces are computed for arbitrary electrode kinetic boundary conditions. Finite element analysis is employed to explore the effect of the current distribution beneath a particle on the net force acting on it. Previously established dimensionless kinetic parameters are used to scale between the two limiting cases. The forces on particles are an order of magnitude larger than the bulk electrophoretic force and are profoundly sensitive to the current distribution beneath the particle as it approaches the electrode.