Two-step migration of particles in evaporating bimodal suspension films at high Peclet numbers

During the drying of bimodal colloidal suspensions containing particles of various sizes, smaller particles preferentially migrate to the top surface under particular drying conditions, leading to undesirable drying defects in batteries and in other coating applications. Despite extensive previous studies, the migration mechanism is far from being understood because few in situ observations are available to support the hypotheses. To remedy this, we use real-time photoluminescence (PL) microscopy to investigate the migration of small fluorescent latex particles co-dispersing with large nonemissive latex particles. Comparing the measured PL intensity with that predicted by a model allows us to determine the quantity of small particles near the evaporating surface. The results reveal that the fluorescent particles segregate in two steps: The primary segregation occurs early in the evaporation stage, whereas the secondary stepwise migration occurs when the air–liquid interface invades the particle consolidation layer. The latter migration is attributed to the flow-induced motion of small particles that move through interstitial spaces between large particles.