Dielectric dispersion of colloidal suspensions in the presence of stern layer conductance: particle size effects

In this work, we discuss the role that particle size plays in the manifestations of surface conduction on the dielectric response of colloidal dispersions. To that aim, experimental data on the dielectric constant of polystyrene suspensions of two different particle diameters (23 and 530 nm) are first compared to the predictions of a classical or standard model (E. H. B. DeLacey and L. R. White, J. Chem. Soc. Faraday Trans. 2 77, 2007 (1983)), and it is found that, while the latter explains reasonably the dielectric behavior of the smallest particles, it considerably underestimates the phenomenon in the case of large particles. To explain these results in terms of contributions of ion motions in the inner region of the double layer of the particles, the approach followed by C. S. Mangelsdorf and L. R. White (J. Chem. Soc. Faraday Trans. 86, 2859 (1990)) is used to incorporate surface conductance in the theory of dielectric response of suspensions. In ac fields it is found that the model considerably improves the comparison between theory and experiment, whereas its use seems unnecessary for the smallest particles, where, whatever the combination used for the parameters of the theory, its predictions do not differ from the standard theory. Only in the case of the larger particles studied does the introduction of surface conductance play any role. A comparison between both types of theoretical results in a wide range of particle sizes demonstrates that Stern layer conductance always increases the magnitude of the low-frequency dielectric constant of suspensions, but its effect is less important the smaller the particle size and the larger the zeta potential for fixed ionic conditions in the dispersion medium