A charged colloidal particle suspended in an electrolyte experiences electroviscous stresses arising from motion-driven electrohydrodynamic phenomena. Under certain conditions, the additional contribution from electroviscous drag forces to the total drag experienced by the moving particle can lead to measurable deviations of particle diffusion coefficients from values predicted by the well known Stokes-Einstein relation that describes diffusive behavior of small particles in an unbounded charge-free fluid. In this study, we investigate the role of electroviscous stresses on nanoparticle diffusion in confined geometries using both simulations and experiment. We compare our experimental measurements with the results of a numerically solved continuum model based on the Poisson-Nernst-Planck-Stokes system of equations and find good agreement between experiment and theory. Depending on the radius of the counterion species in solution and the degree of confinement, we find that the viscous drag on polystyrene nanoparticles can be augmented by approximately 10–$25\%$ compared to the values predicted by pure hydrodynamic models in the absence of free charge in the fluid. This enhancement corresponds approximately to a 5–$10\%$ increase compared to the electroviscous contribution for a charged particle in an unbounded fluid. Contrary to recent reports in the experimental literature, we find neither experimental nor theoretical evidence of an anomalously large enhancement of electroviscous forces on a confined charged nanoparticle in solution.

• Received 19 May 2020
• Revised 29 July 2020
• Accepted 20 September 2020

DOI:https://doi.org/10.1103/PhysRevE.102.042607