Dielectric-solid polarization at strong fields: Breakdown of Smoluchowski's electrophoresis formula

We investigate the thin-double-layer electrophoretic drift of a uniformly charged dielectric particle, driven by an intense electric field comparable to the transverse Debye-layer field. Under these circumstances, solid polarization affects the leading-order electrokinetic transport in the fluid by inducing a nonuniform zeta-potential distribution. The resulting expression for the particle velocity is accordingly nonlinear in the applied field. The electrophoretic "mobility"-the ratio of this velocity and the applied field-depends upon two parameters, the first quantifying the surface-charge densitythe second constituting the product of the solid-to-liquid permittivity ratio and the scaled applied-field magnitude. At weak values of this product, solid polarization results in field-cubed deviations from Smoluchowski's velocity; at large values of it, the particle velocity is a slowly increasing function of the applied field, essentially varying with its logarithm. The transition between these two limits features a shift from zeta-potential proportionality to a charge-density proportionality. For all values of the two governing parameters solid polarization acts so as to reduce the electrophoretic velocity relative to the Smoluchowski limit.