Molecular rheology of unentangled polymer melts in nanochannels

Abstract

We investigate the rheological properties of non-Newtonian melts of short polymer chains at the molecular level, with a focus on nanoscale confinement. Using a combination of all-atom molecular dynamics (MD) and coarse-grained simulations, we examine the behavior of oligomer melts with various topologies under non-equilibrium conditions. Our findings reveal significant deviations in the microscopic stress tensor under steady-state shear compared to predictions from continuum models, highlighting the limitations of the Oldroyd-B and generalized Phan-Thien–Tanner (gPTT) models in capturing nanoscale phenomena. We demonstrate that these deviations result in excess viscoelastic stress, which diminishes with decreasing confinement and vanishes in bulk systems. This excess stress is linked to the spatial orientation of carbon-carbon bonds near surfaces, where adsorbed chains form effective polymer brush-like layers. Additionally, we explore the effects of chain rigidity, surface-oligomer attraction, and molecular variables on rheological responses, providing a comprehensive understanding of the interplay between molecular-scale phenomena and macroscopic behavior in confined polymeric systems.