Nonadditive Interactions Unlock Small-Particle Mobility in Binary Colloidal Monolayers

We examine the organization and dynamics of binary colloidal monolayers composed of micron-scale silica particles interspersed with smallerdiameter silica particles that serve as minority component impurities. These binary monolayers are prepared at the surface of ionic liquid droplets over a range of size ratios (sigma = 0.16-0.66) and are studied with low-dose minimally perturbative scanning electron microscopy (SEM). The high resolution of SEM imaging provides direct tracking of all particle coordinates over time, enabling a complete description of the microscopic state. In these bidisperse size mixtures, particle interactions are nonadditive because interfacial pinning to the droplet surface causes the equators of differently sized particles to lie in separate planes. By varying the size ratio, we control the extent of nonadditivity in order to achieve phase behavior inaccessible to additive 2D systems. Across the range of size ratios, we tune the system from a mobile small-particle phase (sigma < 0.24) to an interstitial solid (0.24 < sigma < 0.33) and furthermore to a disordered glass (sigma > 0.33). These distinct phase regimes are classified through measurements of hexagonal ordering of the large-particle host lattice and the lattice's capacity for smallparticle transport. Altogether, we explain these structural and dynamic trends by considering the combined influence of interparticle interactions and the colloidal packing geometry. Our measurements are reproduced in molecular dynamics simulations of 2D nonadditive disks, suggesting an efficient method for describing confined systems with reduced dimensionality representations.

Automated summary

We investigated the organization and dynamics of binary colloidal monolayers composed of micron-scale silica particles interspersed with smaller diameter silica particles. By varying the size ratio, we controlled the degree of nonadditivity to achieve phase behavior inaccessible to additive 2D systems. The distinct phase regimes were classified based on measurements of hexagonal ordering and small particle transport capacity.