Sub-Rouse modes in polymer thin films: Coupling to density and responding to physical aging

The presence of sub-Rouse modes in bulk polymers with length scale and relaxation times in between the segmental α-relaxation and the Rouse modes had long been justified by theoretical consideration, and found in many experimental studies. The sub-Rouse modes had been seen directly in creep compliance measurements of polymer thin films by McKenna and co-workers. On decreasing film thickness, the sub-Rouse modes shift to shorter times like the segmental α-relaxation, but the shift of the former is less than the latter. We had used the sub-Rouse modes and the segmental mode to explain the two transitions found by ellipsometry in freestanding high molecular weight PS films by Pye and Roth (PR). The upper transition at a higher temperature originates from the sub-Rouse modes, and the lower transition comes from the segmental α-relaxation. On the other hand, PR suggested that the upper and the lower transitions both came from the segmental α-relaxation, and the upper transition occurs in ∼90% of the material. In this paper we use dielectric relaxation data of freestanding films to rule out their suggestion. Furthermore, we demonstrate by experimental evidences that the sub-Rouse modes are coupled to density, and respond to physical aging to validate our interpretation.