The evaporation of colloidal drop on a substrate with a pinned contact line usually results in a ring stain (the so-called coffee-ring effect). In this paper, we present an investigation of the evaporation of sessile picoliter droplets of binary solvent mixtures containing fumed silica nanoparticles (NPs). The internal flows in ethanol/water droplets are suppressed, and a uniform deposit morphology is achieved with a low loading (0.2-0.5 vol %) of hydrophobic fumed silica NPs. The effective control of the particle deposit morphology is based on a rapid sol-gel transition assisted by preferential evaporation of ethanol. For droplets of dilute suspensions, the fumed silica NPs tend to agglomerate and form an elastic network quickly, starting from the region close to the three-phase contact line and below the gas-liquid interface and growing toward the interior of the droplet as the solvents evaporate and the surface descends. Higher silica particle concentrations, lower ethanol concentrations, and weaker Marangoni flows all contribute to the sol-gel transition and hence to the suppression of the coffee-ring effect.
Keywords: Marangoni flow; binary droplet; deposit morphology; hydrophobic nanoparticles; inkjet printing; sol−gel transition.