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The accurate measurement of wall zeta potentials and solute–surface interaction length scales for electrolyte and non-electrolyte solutes, respectively, is critical to the design of many biomedical and microfluidic applications. We present a novel microfluidic approach using diffusioosmosis for measuring either the zeta potentials or the characteristic interaction length scales for surfaces exposed to, respectively, electrolyte or non-electrolyte solutes. When flows containing different solute concentrations merge in a junction, local solute concentration gradients can drive diffusioosmotic flow due to electrokinetic, steric, and other interactions between the solute molecules and solid surfaces. We demonstrate a microfluidic system consisting of a long, narrow pore connecting two large side channels in which solute concentration gradients drive diffusioosmosis within the pore, resulting in predictable fluid velocity/pressure and solute profiles. Furthermore, we present analytical results and a methodology to determine the zeta potential or interaction length scale for the pore surfaces based on the solute concentrations in the main side channels, the flow rate in the pore, and the pressure drop across the pore. We apply this method to the experimental data of Lee et al. to predict the zeta potentials of their system, and we use 3D numerical simulations to validate the theory and show that end effects caused by the junctions are negligible for a wide range of parameters. Because the dynamics in the proposed system are driven by diffusioosmosis, this technique does not suffer from certain disadvantages associated with the use of sensitive electronics in traditional zeta potential measurement approaches such as streaming potential, streaming current, or electroosmosis. To the best of our knowledge this is the first flow-based approach to characterize surface/solute interactions with non-electrolyte solutes. 

The diffusiophoretic motion of suspended colloidal particles under one-dimensional solute gradients is solved using numerical and analytical techniques. Similarity solutions are developed for the injection and withdrawal dynamics of particles into semi-infinite pores. Furthermore, a method of characteristics formulation of the diffusion-free particle transport model is presented and integrated to realize particle trajectories. Analytical solutions are presented for the limit of small particle diffusiophoretic mobility Γ p relative to the solute diffusivity D s for particle motions in both semi-infinite and finite domains. Results confirm the build up of local maxima and minima in the propagating particle front dynamics. The method of characteristics is shown to successfully predict particle motions and the position of the particle front, although it fails to accurately predict suspended particle concentrations in the vicinity of sharp gradients, such as at the particle front peak seen in some injection cases, where particle diffusion inevitably plays an important role. Results inform the design of applications in which the use of applied solute gradients can greatly enhance particle injection into and withdrawal from pores.