Polymers of Intrinsic Microporosity (PIMs) of high performance have developed as materials with a wide application range in gas separation and other energy-related fields. Further optimization and long-term behavior of devices with PIMs require an understanding of the structure-property relationships including physical aging. In this context the glass transition plays a central role, but with conventional thermal analysis a glass transition is usually not detectable for PIMs before their thermal decomposition. Fast scanning calorimetry provides evidence of the glass transition for a series of PIMs, as the time scales responsible for thermal degradation and for the glass transition are decoupled by employing ultrafast heating rates of tens of thousands K s-1. The investigated PIMs were chosen considering the chain rigidity. The estimated glass transition temperatures follow the order of the rigidity of the backbone of the PIMs.

A combination of nanosized dielectric relaxation (BDS) and thermal spectroscopy (SHS) was utilized to characterize the dynamics of thin films of poly(vinyl methyl ether) (PVME) (thicknesses: 7-160 nm). For the BDS measurements, a recently designed nanostructured electrode system is employed. A thin film is spin-coated on an ultraflat highly conductive silicon wafer serving as the bottom electrode. As top electrode, a highly conductive wafer with nonconducting nanostructured SiO nanospacers with heights of 35 or 70 nm is assembled on the bottom electrode. This procedure results in thin supported films with a free polymer/air interface. The BDS measurements show two relaxation processes, which are analyzed unambiguously for thicknesses smaller than 50 nm. The relaxation rates of both processes have different temperature dependencies. One process coincides in its position and temperature dependence with the glassy dynamics of bulk PVME and is ascribed to the dynamic glass transition of a bulk-like layer in the middle of the film. The relaxation rates were found to be thickness independent as confirmed by SHS. Unexpectedly, the relaxation rates of the second process obey an Arrhenius-like temperature dependence. This process was not observed by SHS and was related to the constrained fluctuations in a layer, which is irreversibly adsorbed at the substrate with a heterogeneous structure. Its molecular fluctuations undergo a confinement effect resulting in the localization of the segmental dynamics. To our knowledge, this is the first report on the molecular dynamics of an adsorbed layer in thin films.

The complex effects of nanoparticles on a thermosetting material based on an anhydride-cured DGEBA/boehmite nanocomposite with different particle concentrations are considered.

For the first time, the molecular mobility of two linear-shaped tetramethylated guanidinium triflate ionic liquid crystals (ILCs) having different lengths of alkyl chains was investigated using a combination of broadband dielectric spectroscopy (BDS) and specific heat spectroscopy (SHS). By self-assembly, these ILCs can form a hexagonal ordered mesophase besides plastic crystalline phases and the isotropic state. Three dielectric active processes were found using BDS for both samples. At low temperatures, a γ-process in the plastic crystalline state is observed which is assigned to localized fluctuations of methyl groups including nitrogen atoms in the guanidinium head. At higher temperatures but still in the plastic crystalline state, an α-process takes place. An α-process was detected using SHS but with a completely different temperature dependence of the relaxation times than that of the α-relaxation. This result is discussed in detail, and different molecular assignments of the processes are suggested. At even higher temperatures, electrical conductivity is detected and an increase in the DC conductivity by four orders of magnitude at the phase transition from the plastic crystalline to the hexagonal columnar mesophase is found. This result is traced to a change in the charge transport mechanism from a delocalized electron hopping in the stacked aromatic systems (in the plastic phase) to one dominated by an ionic conduction in the quasi-1D ion channels formed along the supermolecular columns in the ILC hexagonal mesophases.

For the first time, dielectric and calorimetric investigations of a homologous series of Janus polynorbornenes with rigid main backbones and flexible −Si(OR) 3 side groups of differing length alkyl chains (R = propyl, butyl, hexyl, octyl, and decyl) is reported. Generally, this class of polymers has some potential for applications in the field of gas separation membranes. Two dielectrically active processes are observed at low temperatures, denoted as βand α-relaxation. The former can be assigned to localized fluctuations, while the latter is related to the glassy dynamics of the flexible −Si(OR) 3 side groups, creating a nanophase separation in both the alkyl chain-rich and backbone-rich domains. This is confirmed through temperature-modulated differential scanning calorimetry (TMDSC) measurements and X-ray scattering experiments. The glass transition temperatures of the backbone rich domains, which are beyond or near to their degradation temperatures in terms of conventional DSC, are determined for the first time using fast scanning calorimetry employing both fast heating and cooling rates. This is complemented with scattering experiments that show how the size of the alkyl chain-rich domains increases with the side chain length. Alongside these results, a significant conductivity contribution was observed for all poly(tricyclononenes) with −Si(OR) 3 side groups, which is interpreted in terms of a percolation model.