Is the Molecular Weight Dependence of the Glass Transition Temperature Caused by a Chain End Effect? (2303.15399v4)

Abstract: The immense dependence of the glass transition temperature $T_g$ on molecular weight $M$ is one of the most fundamentally and practically important features of polymer glass formation. Here, we report on molecular dynamics simulation of three model linear polymers of substantially different complexity demonstrating that the 70-year-old canonical explanation of this dependence (a simple chain end dilution effect) is likely incorrect at leading order. Our data shows that end effects are present only in relatively stiff polymers and, furthermore, that the magnitude of this end effect diminishes on cooling. Instead, we find that $T_g(M)$ trends are instead dominated by shifts in $T_g$ throughout the entire polymer chain rather than through a chain end effect. We show that these data are consistent with a generic two-barrier model of $T_g$ and its $M$-dependence, motivated by the Elastically Collective Nonlinear Langevin Equation (ECNLE) theory. More broadly, this work indicates both a need to reassess the canonical understanding of $T_g(M)$ in linear polymers (and macromolecules at large) and an opportunity to reveal new glass formation physics with renewed study of $M$ effects on $T_g$.