Evaporation Dynamics of Surfactant-Laden Droplets on a Superhydrophobic Surface: Influence of Surfactant Concentration

Surfactant-laden sessile droplet evaporation plays a crucial role in a variety of omnipresent natural and technological applications, such as drying, coating, spray, and inkjet printing. Surfactant molecules can adsorb easily on interfaces and, hence, destructively ruin the useful gas-trapping wetting state (i.e., Cassie-Baxter, CB) of a drop on superhydrophobic (SH) surfaces. However, the influence of surfactant adsorption or concentration on evaporation modes has been rarely investigated so far. Here, we investigate the evaporation dynamics of aqueous didodecyldimethylammonium bromide (DDAB) sessile droplet on SH surfaces made of regular hydrophobic micropillars, with various dimensionless surfactant concentrations (C_S), primarily using experiments. We find that all drops initially form a CB state with a pinned base radius and evaporate in a mode of constant contact radius (CCR). Water and low-C_S (=0.02) drop subsequently evaporate with a constant contact angle (CCA) mode, followed by a CCR mode and, eventually, a mixed-mode. By contrast, high-C_S (of 0.25-1) droplets undergo a complex mixed mode, with rapidly increasing base radius, and finally a mixed mode, with slowly decreasing base radius and contact angle. The experimental data reveal that contact-angle-dependent evaporative mass flux, ṁ, collapses onto a nearly universal curve depending on C_S. For the low-C_S (of 0-0.25) drops, ṁ is lower and consistent with an evaporative cooling model, whereas high-C_S (of 0.5-1) droplets are consistent with a pure vapor-diffusive model. We further show that the critical C_S delineating these two evaporative models correlates with saturated surfactant adsorption on both liquid-solid and liquid-vapor interfaces.