Deposits from evaporating emulsion drops

The processes in which droplets evaporate from solid surfaces, leaving behind distinct deposition patterns, have been studied extensively for variety of solutions. In this work, by combining different microscopy techniques (confocal fluorescence, video and Raman) we investigate pattern formation and evaporation-induced phase change in drying oil-in-water emulsion drops. This combination of techniques allows us to perform drop shape analysis while visualizing the internal emulsion structure simultaneously. We observe that drying of the continuous water phase of emulsion drops on hydrophilic surfaces favors the formation of ring-like zones depleted of oil droplets at the contact line, which originate from geometrical confinement of oil droplets by the meniscus. From such a depletion zone, a "coffee ring" composed of surfactant molecules forms as the water evaporates. On all surfaces drying induces emulsion destabilization by coalescence of oil droplets, commencing at the drop periphery. For hydrophobic surfaces, the coalescence of the oil droplets leads to a uniform oil film spreading out from the initial contact line. The evaporation dynamics of these composite drops indicate that the water in the continuous phase of the emulsion drops evaporates predominantly by diffusion through the vapor, showing no large differences to the evaporation of simple water drops.