Intrinsic chain stiffness in flexible linear polymers under extreme confinement

Abstract

Polymer behaviors at interfaces or in narrowly confined systems have important implications in a variety of practical applications, including polymer processing, polymer films, adhesion, polymer nanocomposites, lubricants, and biological membranes. However, the physics behind the distinctive structural and dynamic features created by confinement remain elusive. Experimental, theoretical, and computational studies on the basic structures of dense linear polymers at solid surfaces or in nanoconfined systems have produced contradictory results. In this study, we resolve this controversial issue by elucidating the underlying fundamental characteristics of two-dimensional monolayer melt systems composed of flexible linear chains using both atomistic and coarse-grained molecular dynamics simulations. The present findings provide basic guidelines for future theoretical and experimental analyses of two-dimensional or narrowly confined polymeric systems.