Molecular motions of different scales at thin polystyrene film surface by lateral force microscopy

Lateral force microscopy (LFM) was used to probe the molecular motions at thin polystyrene film surface. The effect of the applied load on the LFM measurements was investigated by presenting both the LFM results and the surface morphology after several scans over the same area. Depending on the loads, the scanning can be nonperturbative (without alternating the surface morphology) or perturbative (patterning the surface). Temperature-dependent LFM measurements were conducted in order to determine the apparent transitions at the surface. Perturbative scans under high loads (e.g., 150 nN) witnessed that the apparent transitions shifted to low temperatures with an increasing scan rate, while the transitions behaved oppositely under lower loads (1, 10, and 20 nN). The heating effect is suggested to account for the behavior under high loads. According to our results from nonperturbative LFM, the apparent glass transition temperature (T(g)s) is more than 10 K lower than the bulk value. Moreover, rate-dependent LFM measurements were performed under 1 nN in order to detect the surface molecular motions. Time-temperature superposition yields a master curve exhibiting three apparent relaxation peaks. The molecular motions at the surface are discussed on the context of the coupling model.