Segregation in Drying Binary Colloidal Droplets

When a colloidal suspension droplet evaporates from a solid surface, it leaves a characteristic deposit in the contact region. These deposits are common and important for many applications in printing, coating, or washing. By the use of superamphiphobic surfaces as a substrate, the contact area can be reduced so that evaporation is almost radially symmetric. While drying, the droplets maintain a nearly perfect spherical shape. Here, we exploit this phenomenon to fabricate supraparticles from bidisperse colloidal aqueous suspensions. The supraparticles have a core-shell morphology. The outer region is predominantly occupied by small colloids, forming a close-packed crystalline structure. Toward the center, the number of large colloids increases and they are packed amorphously. The extent of this stratification decreases with decreasing the evaporation rate. Complementary simulations indicate that evaporation leads to a local increase in density, which, in turn, exerts stronger inward forces on the larger colloids. A comparison between experiments and simulations suggest that hydrodynamic interactions between the suspended colloids reduce the extent of stratification. Our findings are relevant for the fabrication of supraparticles for applications in the fields of chromatography, catalysis, drug delivery, photonics, and a better understanding of spray-drying.