Buoyancy-induced on-the-spot mixing in droplets evaporating on nonwetting surfaces.

We investigate hitherto-unexplored flow characteristics inside a sessile droplet evaporating on heated hydrophobic and superhydrophobic surfaces and propose the use of evaporation-induced flow as a means to promote efficient "on-the-spot" mixing in microliter-sized droplets. Evaporative cooling at the droplet interface establishes a temperature gradient that induces buoyancy-driven convection inside the droplet. An asymmetric single-roll flow pattern is observed on the superhydrophobic substrate, in stark contrast with the axisymmetric toroidal flow pattern that develops on the hydrophobic substrate. The difference in flow patterns is attributed to the larger height-to-diameter aspect ratio of the droplet (of the same volume) on the superhydrophobic substrate, which dictates a single asymmetric vortex as the stable buoyancy-induced convection mode. A scaling analysis relates the observed velocities inside the droplet to the Rayleigh number. On account of the difference in flow patterns, Rayleigh numbers, and the reduced solid-liquid contact area, the flow velocity is an order of magnitude higher in droplets evaporating on a superhydrophobic substrate as compared to hydrophobic substrates. Flow velocities in all cases are shown to increase with substrate temperature and droplet size: The characteristic time required for mixing of a dye in an evaporating sessile droplet is reduced by ∼8 times on a superhydrophobic surface when the substrate temperature is increased from 40 to 60 °C. The mixing rate is ∼15 times faster on the superhydrophobic substrate compared to the hydrophobic surface maintained at the same temperature of 60 °C.