Thermal Properties and Segmental Dynamics of Polymer Melt Chains Adsorbed on Solid Surfaces

The glass transition of supported polystyrene (PS) and poly(2-vinylpyridine) (P2VP) thin films in the vicinity of the substrate interface was studied by using a nanoplasmonic sensing (NPS) method. This "nanocalorimetric" approach utilizes localized surface plasmon resonance from two-dimensional arrangements of sensor nanoparticles deposited on SiO2-coated glass substrates. The NPS results demonstrated the existence of a high glass transition temperature (Tg,high) along with the bulk glass transition temperature (Tg,bulk ≈ 100 °C for PS and P2VP) within the thin films: Tg,high ≈ 160 °C for PS and Tg,high ≈ 200 °C for P2VP. To understand the origin of the Tg,high, we also studied the thermal transitions of lone polymer chains strongly adsorbed onto the substrate surface using solvent rinsing. Interestingly, the NPS data indicated that the Tg,high is attributed to the adsorbed polymer chains. To provide a better understanding of the mechanism of the Tg,high, molecular dynamics simulations were performed on a PS film adsorbed on hydrophobic and hydrophilic substrates. The simulation results illuminated the presence of a higher density region closest to the substrate surface regardless of the magnitude of the polymer–solid interactions. We postulate that the highly packed chain conformation reduces the free volume at the substrate interface, resulting in the Tg,high. Moreover, the simulation results revealed that the deviation of the Tg,high from the bulk Tg,bulk becomes larger as the polymer–substrate interaction increases, which is in line with the experimental findings.