We performed neutron reflectivity measurements on multilayered polymer thin films consisting of alternatively stacked deuterated polystyrene (d-PS) and hydrogenated polystyrene (h-PS) layers ∼200 Å thick as a function of temperature covering the glass-transition temperature T(g), and we found a wide distribution of T(g) as well as a distribution of the thermal expansivity α within the thin films, implying the dynamic heterogeneity of the thin films along the depth direction. The reported anomalous film thickness dependences of T(g) and α were reasonably understood in terms of the distributions, showing that the surface mobile layer and the bottom hard interfacial layer are, respectively, responsible for the depressions of T(g) and α with decreasing film thickness. The molecular mobility in each layer is also discussed in relation to the distribution of T(g), based on the results on mutual diffusion at the layer interface.

Depending on the degree of short chain branch (SCB) incorporation, the crystallization behavior and resultant crystalline structure drastically change in polyethylene with precisely spaced branches. In polyethylene with hexyl branches precisely spaced on every 21st carbon (HB21), only crystallization mediated by a transient hexagonal phase without incorporation of the SCB was observed. On the other hand, in polyethylene with ethyl branches precisely spaced on every 21st carbon (EB21), crystallization behavior was strongly dependent on the crystallization temperature. A thin lamella was formed through crystallization mediated by a hexagonal phase and no thickening occurred at 5–8 °C, while thickening of the transient hexagonal lamellae occurred at 10–15 °C, and one SCB seemed to be incorporated into a crystal stem. At 17 °C, no thickening of the hexagonal phase occurred and a hexagonal phase with sufficient lamella thickness was directly formed from the melt. At 21–28 °C, crystallization mediated by hexago..

We have studied the glass transition temperature (T(g)) and molecular mobility of polystyrene (PS) thin films near the interface between the polymer thin film and substrate with bilayer thin films consisting of surface hydrogenated PS (h-PS) and bottom deuterated PS (d-PS) using neutron reflectivity. With decreasing the thickness of the bottom d-PS layer, T(g) near the interface between the polymer thin film and substrate increased compared to bulk T(g) and a drastic increase of T(g) was observed for the bottom d-PS layer <155 Å thick. The orientation of polymer chains at the interface is supposed to be related to the increase of T(g) near the interface between the polymer and substrate. The polymer chain mobility decreased with thickness even for the bottom d-PS layer with no discernible change of T(g). It is considered that the numerous contacts between polymer chains and substrate are related to the decrease of mobility near the interface between the polymer thin film and substrate.

We studied the distribution of glass transition temperature (Tg) through neutron reflectivity in a poly(methyl methacrylate) (PMMA) thin film supported on a silicon substrate with a five-layered PMMA thin film consisting of deuterated-PMMA and hydrogenated-PMMA. The depth distribution of Tg was successfully observed in the PMMA thin film. Compared to the previously reported distribution of Tg in a polystyrene thin film, the presence of a long-range interfacial effect, supposedly caused by an interaction between PMMA and the substrate, is considered to be responsible for the differences in both the distribution of Tg and the thickness dependence of Tg in both polymers. Therefore, it is expected that the thickness dependence of Tg reported for single-layered polymer thin films can, in principle, be understood from the viewpoint of the difference in the depth distribution of Tg.

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