At large zeta potentials, surface conduction becomes appreciable in thin-double-layer electrokinetic transport. In the linear weak-field regime, where this effect is quantified by the Dukhin number, it is manifested in non-Smoluchowski electrophoretic mobilities. In this paper we go beyond linear response, employing the recently derived macroscale model of Schnitzer and Yariv [“Macroscale description of electrokinetic flows at large zeta potentials: Nonlinear surface conduction,” Phys. Rev. E 86, 021503 (2012)] as the infrastructure for a weakly nonlinear analysis of spherical-particle electrophoresis. A straightforward perturbation in the field strength is frustrated by the failure to satisfy the far-field conditions, representing a non-uniformity of the weak-field approximation at large distances away from the particle, where salt advection becomes comparable to diffusion. This is remedied using inner-outer asymptotic expansions in the spirit of Acrivos and Taylor [“Heat and mass transfer from single spheres in Stokes flow,” Phys. Fluids 5, 387 (1962)], with the inner region representing the particle neighborhood and the outer region corresponding to distances scaling inversely with the field magnitude. This singular scheme furnishes an asymptotic correction to the electrophoretic velocity, proportional to the applied field cubed, which embodies a host of nonlinear mechanisms unfamiliar from linear electrokinetic theories. These include the effect of induced zeta-potential inhomogeneity, animated by concentration polarization, on electro-osmosis and diffuso-osmosis; bulk advection of salt; nonuniform bulk conductivity; Coulomb body forces acting on bulk volumetric charge; and the nonzero electrostatic force exerted upon the otherwise screened particle-layer system. A numerical solution of the macroscale model validates our weakly nonlinear analysis.
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