Stratification Mechanism in the Bidisperse Colloidal Film Drying Process: Evolution and Decomposition of Normal Stress Correlated with Microstructure.

The evolution of the normal stress and microstructure in the drying process of bidisperse colloidal films is studied using the Brownian dynamics simulation. Here, we show that the formation process of small-on-top stratification can be explained by normal stress development. At high 's, a stratified layer with small particles is formed near the interface. The accumulated particles near the interface induce the localization of normal stress so that the normal stress at the interface increases from the beginning of drying. We analyze this stress development from two points of view, on the global length scale and particle length scale. On the global length scale, the localization of normal stress is quantified by the scaled normal stress difference between the interface and substrate. For all 's tested in this study, the scaled normal stress difference increases until the accumulation region reaches the substrate. After the maximum, the stress difference remains at the maximum at lower 's, while it decreases at higher 's. The microstructural analysis shows that this stress development is explained through the evolution of the particle contact number distribution at the interface and substrate. On the particle length scale, we derive the scaled local force applied to each type of particle by decomposing the local normal stress. At high 's, the scaled local force for the large particle is large compared to that for the small particle near the interface, indicating that the large particles are strongly pushed away from the interface. Associating the volume fraction profile with the local force field, we suggest that the strong scaled force for the large particle is attributed to the significant increase in the average number of small particles in contact with large ones. This study has significance in probing the drying mechanism of bidisperse colloidal films and the stratification mechanism.