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We present a method to determine the local surface charge of solid-liquid interfaces from Atomic Force Microscopy (AFM) measurements that takes into account shifts of the adsorption/desorption equilibria of protons and ions as the cantilever tip approaches the sample. We recorded AFM force distance curves in dynamic mode with sharp tips on heterogeneous silica surfaces partially covered by gibbsite nano-particles immersed in an aqueous electrolyte with variable concentrations of dissolved NaCl and KCl at pH 5.8. Forces are analyzed in the framework of Derjaguin-Landau-Verwey-Overbeek (DLVO) theory in combination with a charge regulation boundary that describes adsorption and desorption reactions of protons and ions. A systematic method to extract the equilibrium constants of these reactions by simultaneous least-squared fitting to experimental data for various salt concentrations is developed and is shown to yield highly consistent results for silica-electrolyte interfaces. For gibbsite-electrolyte interfaces, the surface charge can be determined, yet, an unambiguous identification of the relevant surface speciation reactions is not possible, presumably due to a combination of intrinsic chemical complexity and heterogeneity of the nano-particle surfaces.

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Collective effects on thermophoresis of aqueous particle suspensions are studied experimentally and theoretically. A microfluidic device is used to characterize thermophoretic transport of 100 nm, 500 nm and 1 mm particles of various concentrations in deionized (DI) water. Our experimental findings show two interesting collective effects on the Soret coefficient of colloids: (i) for smaller particles (e.g., 100 nm and 500 nm), a sign change of the Soret coefficient is observed when increasing the particle concentration; (ii) for larger particles (e.g., 1 mm), a negative Soret coefficient is always seen. A model is derived to account for the collective effect on the thermophoresis of colloids using the well-known Derjaguin-Landau-Verwey-Overbeek (DLVO) theory that combines the van der Waals (VDW) attraction and the electric double layer (EDL) repulsion. Such DLVO interactions in an inhomogeneous particle suspension can exert an additional force on particles and thus modify the mass transport of particles under both temperature and concentration gradients and also alter the corresponding Soret coefficient.It is found that the proposed theoretical model can favorably explain our experimental observations.

Electroosmotic flow of Power-law fluids over a surface with arbitrary zeta potentials is analyzed. The governing equations including the nonlinear Poisson-Boltzmann equation, the Cauchy momentum equation and the continuity equation are solved to seek exact solutions for the electroosmotic velocity, shear stress, and dynamic viscosity distributions inside the electric double layer. Specifically, an expression for the general Smoluchowski velocity is obtained for electroosmosis of Power-law fluids in a fashion similar to the classic Smoluchowski velocity for Newtonian fluids. The existing Smoluchowski slip velocities under two special cases, (i) for Newtonian fluids with arbitrary zeta potentials and (ii) for Power-law fluids with small zeta potentials, can be recovered from our derived formula. It is interesting to note that the general Smoluchowski velocity for non-Newtonian Power-law fluids is a nonlinear function of the electric field strength and surface zeta potentials; this is due to the coupling electrostatics and non-Newtonian fluid behavior, which is different from its counterpart for Newtonian fluids. This general Smoluchowski velocity is of practical significance in determining the flow rates in microfluidic devices involving non-Newtonian Power-law fluids.

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