Coupled Effects of Substrate Adhesion and Intermolecular Forces on Polymer Thin Film Glass-Transition Behavior

Intermolecular noncovalent forces between polymer chains influence the mobility and glass-transition temperature (Tg), where weaker interchain interactions, all else being the same, typically results in lower bulk polymer Tg. Using molecular dynamics simulations, here we show that this relation can become invalid for supported ultrathin films when the substrate–polymer interaction is extremely strong and the polymer–polymer interactions are much...