Collective diffusion coefficient of a charged colloidal dispersion: interferometric measurements in a drying drop

In the present work, we use Mach–Zehnder interferometry to thoroughly investigate the drying dynamics of a 2D confined drop of a charged colloidal dispersion. This technique makes it possible to measure the colloid concentration field during the drying of the drop at a high accuracy (about 0.5%) and with a high temporal and spatial resolution (about 1 frame per s and 5 μm per pixel). These features allow us to probe mass transport of the charged dispersion in this out-of-equilibrium situation. In particular, our experiments provide the evidence that mass transport within the drop can be described by a purely diffusive process for some range of parameters for which the buoyancy-driven convection is negligible. We are then able to extract from these experiments the collective diffusion coefficient of the dispersion D(φ) over a wide concentration range φ = 0.24–0.5, i.e. from the liquid dispersed state to the solid glass regime, with a high accuracy. The measured values of D(φ) ≃ 5–12D₀ are significantly larger than the simple estimate D₀ given by the Stokes–Einstein relation, thus highlighting the important role played by the colloidal interactions in such dispersions.