Investigation of Polymer Chain Diffusion Behavior in Thin Slits Formed by Patch-Patterned Surfaces: Influence of Patch Properties

Langmuir. 2024 Dec 31;40(52):27659-27666. doi: 10.1021/acs.langmuir.4c04264. Epub 2024 Dec 18.

Abstract

The diffusion dynamics of polymer chains within a narrow slit formed by two patch-patterned surfaces is investigated utilizing Langevin dynamics simulations. These surfaces feature periodically arranged attractive patches of size L and period d, with a staggered configuration of (0.5d, 0.5d) offsets along the x and y axes. When d is fixed, the polymer chain exhibits normal diffusion over long time scales, with the translational diffusion coefficient Dxy gradually decreasing to zero as L increases. Notably, our findings reveal four distinct diffusion modes: free-diffusion mode for LL1, where the polymer chain is mainly in a desorption state; adsorption-desorption mode for L1 < LL2, involving transitions from a single-patch adsorption state to a desorption state; exchange-patch mode for L2 < LL3, where the polymer chain switches between a single-patch adsorption state and an upper-lower double-patch adsorption state by exchanging patches; and nondiffusion mode for L > L3, where the polymer chain is primarily in a pinned state. Furthermore, as the patch attraction strength εps increases, Dxy decreases due to an increase in the adsorption time of the polymer chain. Simultaneously, critical patch size thresholds L1, L2, and L3, exhibit a decreasing trend. These observations highlight the significant influence of the confining slit and patch properties on the diffusion behavior of polymer chains.