Size-Dependent Dried Colloidal Deposit and Particle Sorting via Saturated Alcohol Vapor-Mediated Sessile Droplet Spreading.

We experimentally and theoretically investigate a distinct problem of spreading, evaporation, and the associated dried deposits of a colloidal particle-laden aqueous sessile droplet on a surface in a saturated alcohol vapor environment. In particular, the effect of particle size on monodispersed suspensions and efficient self-sorting of bidispersed particles have been investigated. The alcohol vapor diffuses toward the droplet's curved liquid-vapor interface from the far field. The incoming vapor mass flux profile assumes a nonuniform pattern across the interface. The alcohol vapor molecules are adsorbed at the liquid-vapor interface, which eventually leads to absorption into the droplet's liquid phase due to the miscibility. This phenomenon triggers a liquid-vapor interfacial tension gradient and causes a reduction in the global surface tension of the droplet. This results in a solutal Marangoni flow recirculation and spontaneous droplet spreading. The interplay between these phenomena gives rise to a complex internal fluid flow within the droplet, resulting in a significantly modified and strongly particle-size-dependent dried colloidal deposit. While the smaller particles form a multiple ring pattern, larger particles form a single ring, and additional "patchwise" deposits emerge. High-speed visualization of the internal liquid-flow revealed that initially, a ring forms at the first location of the contact line. Concurrently, the Marangoni flow recirculation drives a collection of particles at the liquid-vapor interface to form clusters. Thereafter, as the droplet spreads, the smaller particles in the cluster exhibit a "jetlike" outward flow, forming multiple ring patterns. In contrast, the larger particles tend to coalesce together in the cluster, forming the "patchwise" deposits. The widely different response of the different-sized particles to the internal fluid flow enables an efficient sorting of the smaller particles at the contact line from bidispersed suspensions. We corroborate the measurements with theoretical and numerical models wherever possible.