Electrokinetics of heterogeneous interfaces.

The influence of surface heterogeneity of various types on electrokinetic parameters is reviewed. The scope of the paper covers classical electrokinetic phenomena characterized by linear dependence of electrokinetic parameters vs. related driving forces. Neither non-linear effects nor the effects of non-equilibrium electric double layer are considered. A historical description of hydrodynamic aspect of electrokinetic phenomena exploiting the slip plane idea is briefly outlined. Attempts to estimate the slip plane location by comparing the diffuse layer and zeta potential values for some model systems are presented. The surface heterogeneity was divided into three categories. Heterogeneity of the first type was related to geometrical morphology of an interfacial region characterized by a considerable surface development producing a three-dimensional interfacial region. The effects of solid roughness, hairy surface, dense polymer layers and gel-like layers are discussed here. The very high surface conductivity detected for such interfaces seems to be a good indicator of the presence of structured layers of this type. Heterogeneous interfaces of the second class cover systems exhibiting non-uniform distribution of surface charge. The non-uniform surface charge distribution can be either of a molecular (discrete charges) or of a microscale (two-dimensional micropatches or three-dimensional structures formed by polyelectrolyte multilayers). The last class of systems examined includes interfaces composed of charged substrate covered by charged bulky objects (particles). In comparison to the homogeneous surfaces, adsorbed charged particles modify both hydrodynamic flow and the electrostatic field significantly altering the electrokinetic parameters. The new description of electrokinetics of composed interfaces presented here takes into account both hydrodynamic and electric field modification and is free of the previously assumed slip plane shift caused by adsorbed objects. This theoretical approach verified by experiments performed on well defined model systems can be successfully applied to the interpretation of experimental data obtained for surfaces covered by objects difficult to detect.