We report a experimental study of the motion of 1μm single particles interacting with functionalized walls at low and moderate ionic strengths conditions. The 3D particle's trajectories were obtained by analyzing the diffracted particle images (point spread function). The studied particle/wall systems include negatively charged particles interacting with bare glass, glass covered with polyelectrolytes and glass covered with a lipid monolayer. In the low salt regime (pure water) we observed a retardation effect of the short-time diffusion coefficients when the particle interacts with a negatively charged wall; this effect is more severe in the perpendicular than in the lateral component. The decrease of the diffusion as a function of the particle-wall distance h was similar regardless the origin of the negative charge at the wall. When surface charge was screened or salt was added to the medium (10mM), the diffusivity curves recover the classical hydrodynamic behavior. Electroviscous theory based on the thin electrical double layer (EDL) approximation reproduces the experimental data except for small h. On the other hand, 2D numerical solutions of the electrokinetic equations showed good qualitative agreement with experiments. The numerical model also showed that the hydrodynamic and Maxwellian part of the electroviscous total drag tend to zero as h → 0 and how this is linked with the merging of both EDL's at close proximity.
Keywords: Brownian motion; colloids; electroviscous effects; low Reynolds number flows; microfluidics; particle diffusion; statistical physics.
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