Evaporation of Sessile Drops Containing Colloidal Rods: Coffee-Ring and Order–Disorder Transition

Liquid drops containing insoluble solutes when dried on solid substrates leave distinct ring-like deposits at the periphery or along the three-phase contact line–a phenomena popularly known as the coffee-ring or the coffee stain effect. The formation of such rings as well as their suppression is shown to have applications in particle separation and disease diagnostics. We present an experimental study of the evaporation of sessile drops containing silica rods to elucidate the structural arrangement of particles in the ring, an effect of the addition of surfactant and salt. To this end, the evaporation of aqueous sessile drops containing model rod-like silica particles of aspect ratio ranging from ∼4 to 15 on a glass slide is studied. We first show that when the conditions such as (1) solvent evaporation, (2) nonzero contact angle, (3) contact line pinning, (4) no surface tension gradient driven flow, and (5) repulsive particle–particle/particle–substrate interactions, that are necessary for the formation of the coffee-ring are met, the suspension drops containing silica rods upon evaporation leave a ring-like deposit. A closer examination of the ring deposits reveals that several layers of silica rods close to the edge of the drop are ordered such that the major axis of the rods are oriented parallel to the contact line. After the first few layers of ordered arrangement of particles, a random arrangement of particles in the drop interior is observed indicating an order–disorder transition in the ring. We monitor the evolution of the ring width and particle velocity during evaporation to elucidate the mechanism of the order–disorder transition. Moreover, when the evaporation rate is lowered, the ordering of silica rods is observed to extend over large areas. We demonstrate that the nature of the deposit can be tuned by the addition of a small quantity of surfactant or salt