Theoretical analysis of the local orientation effect and the lift-hyperlayer mode of rodlike particles in field-flow fractionation.

We investigated theoretically the effects of the cross-stream migration and the local average orientation of rodlike particles on the shape-based separation using field-flow fractionation. The separation behavior was analyzed by comparing the retention ratios of spheres and rods. The retention ratio of a rod was evaluated through the derivation of its cross-sectional concentration profile by considering the rod migration and the local average orientation. Our study in various flow conditions showed that the rod migration, caused by the hydrodynamic interaction with a wall, can affect the separation behavior as a lift-hyperlayer mode. We also demonstrated that the local average orientation, which is a function of a local shear rate and a rotational diffusivity, results in the transverse diffusivity that is different from its perpendicular diffusivity. These results suggest that the experimental separation behaviors of rods in field-flow fractionation may not be fully explained by the current theory based on the normal mode and the steric mode. We also characterized each condition where one of the normal mode, the steric mode of spheres, and the lift-hyperlayer mode of rods is dominant.