Rotation and Retention Dynamics of Rod-Shaped Colloids with Surface Charge Heterogeneity in Sphere-in-Cell Porous Media Model.

Colloid surface charge heterogeneity was incorporated into a three-dimensional trajectory model, which simulated particle translation and rotation via a force/torque analysis, to study the transport and retention dynamics of rod-shaped colloids over a wide size range in porous media under unfavorable conditions (energy barriers to deposition exist). Our previous study Li , K. ; Ma , H. Deposition Dynamics of Rod-Shaped Colloids during Transport in Porous Media under Favorable Conditions , Langmuir , 2018 , 34 , 9 , 2967 - 2980 , 10.1021/acs.langmuir.7b03983 for rod transport under favorable conditions (lacking energy barriers) demonstrated that particle rotation due to the coupled effect of flow hydrodynamics and Brownian rotation governed rod transport and retention. In this work, we showed that the shape of a colloid affected both transport process and colloid-collector interactions, but shape alone could not make rods to overcome energy barriers of over tens of kT for attachment under unfavorable conditions. The location of colloid surface heterogeneity did not affect transport but predominantly affected colloid-surface interactions by influencing the likelihood of heterogeneity patches facing the collector due to particle rotation. For surface heterogeneity located on the end(s) of a colloid, rods displayed enhanced retention compared with spheres; for surface heterogeneity located on the middle band, rods showed less retention compared with spheres. It was more effective to arrest a traveling rod when surface heterogeneity was located on the end relative to the side, because the tumbling motion greatly increased the likelihood of the end to intercept collector surfaces, and also because a rod would experience less repulsion with an end-on orientation relative to the collector surface compared to a side-on orientation due to the curvature effect. The influences of the particle aspect ratio on retention strongly depended upon the location of colloid surface heterogeneity. Our findings demonstrated that rods had distinct rotation and retention behaviors from spheres under conditions typically encountered in the environment; thus, particle rotation should be considered when studying the transport process of nonspherical colloids or spherical particles with inhomogeneous surface properties.