A coarse-grained lattice gas model is developed to study pattern forming processes in drying drops containing surfactant. By performing Monte Carlo simulations of the model, the coupled dynamics of surfactant and liquid evaporation and the resulting oscillatory dynamics at the contact line are elucidated. We show that the coupled drop dynamics and the resulting final deposition patterns can be altered by adsorption kinetics. For slow adsorption rates, surfactant molecules recirculate along with colloidal particles and the area covered by the surfactant on the surface grows from the contact line as the initial concentration of the surfactant increases. This leads to coffee-ring patterns with wide rim areas upon drying or to multi-ring patterns depending on the surfactant concentration. For fast adsorption rates, a surfactant skin covers the entire surface area during the early phase of evaporation. This suppresses the coffee ring effect, and uniform patterns are obtained independent of surfactant concentration. The results suggest that the distribution of surfactant on the surface is critical in determining final deposition patterns and that understanding of the skin-forming process of the surfactant on the surface can help in manipulating the delicate pattern forming process of particles in evaporating drops.

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http://dx.doi.org/10.1039/c7sm01224aDOI Listing

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