The dielectric

The question of whether the glass transition temperature in thin polymer films depends on the film thickness or not has given rise to heated debate for almost two decades now. One of the most puzzling findings is the seemingly universal thickness independence of the dielectric α-relaxation observed for supported films. It is puzzling not only in view of the fact that other techniques or other geometries sometimes showed a significant shift of $T_{\text{g}}$ as a function of film thickness, but more so, because computer simulations for all types of polymer film models revealed changes in the structure and dynamics close to a hard surface or a free surface. Our results suggest to explain this apparent contradiction by the fact that only within 1–2 nm from the wall the density changes are sufficiently large to alter the dynamics. Additionally, the wall desorption kinetics, which introduces a new energy scale (at least for simple van der Waals attraction), is enslaved to the α-relaxation at low temperatures

Legislative Documents

Also, variously referred to as: House bills; House documents; House legislative documents; legislative documents; General Court documents

Structure and Dynamics of Asymmetric Poly(styrene‑<i>b</i>‑1,4-isoprene) Diblock Copolymer under 1D and 2D Nanoconfinement

The impact of 1- and 2-dimensional (2D) confinement on the structure and dynamics of poly­(styrene-<i>b</i>-1,4-isoprene) P­(S-<i>b</i>-I) diblock copolymer is investigated by a combination of Scanning Electron Microscopy (SEM), Atomic Force Microscopy (AFM), Grazing-Incidence Small-Angle X-ray Scattering (GISAXS), and Broadband Dielectric Spectroscopy (BDS). 1D confinement is achieved by spin coating the P­(S-<i>b</i>-I) to form nanometric thin films on silicon substrates, while in the 2D confinement, the copolymer is infiltrated into cylindrical anodized aluminum oxide (AAO) nanopores. After dissolving the AAO matrix having mean pore diameter of 150 nm, the SEM images of the exposed P­(S-<i>b</i>-I) show straight nanorods. For the thin films, GISAXS and AFM reveal hexagonally packed cylinders of PS in a PI matrix. Three dielectrically active relaxation modes assigned to the two segmental modes of the styrene and isoprene blocks and the normal mode of the latter are studied selectively by BDS. The dynamic glass transition, related to the segmental modes of the styrene and isoprene blocks, is independent of the dimensionality and the finite sizes (down to 18 nm) of confinement, but the normal mode is influenced by both factors with 2D geometrical constraints exerting greater impact. This reflects the considerable difference in the length scales on which the two kinds of fluctuations take place