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The increasing demand for energy efficient separation processes fosters the development of new high performance polymers as selective separation layers for membranes. PIM-1 is the archetypal representative of the class of polymers of intrinsic microporosity (PIM) which are considered most promising in this sector, especially for gas separations. Since their introduction, PIMs stimulated a vast amount of research in this field and meanwhile evolved to the state of the art in membrane technology for gas separation. The major obstacle for extending the practical membrane application is their strong tendency to physical aging. For the first time, investigations by broadband dielectric spectroscopy (BDS) addressing molecular dynamics and conductivity in PIM 1 are presented. As chain packing during film formation from the casting solution and physical aging are key factors determining the separation performance of PIMs as membrane materials, characterization of the molecular mobility in such materials as revealed by BDS will provide valuable information for further development and optimization.
According to basic phenomenological models describing the solution-diffusion based mechanism of penetrant diffusion in dense polymers, a connection between the diffusive transport of gas molecules in a polymeric matrix and the molecular mobility of that matrix on a certain length scale is, in principle, established for a long time. However, experimental data directly showing this correlation are rare. The investigation of a series of nanocomposites based on a polyhedral oligomeric silsesquioxane (POSS) and a polycarbonate matrix allows a systematic change of the molecular mobility on a local length scale (β-relaxation) and of the corresponding activation energy EA, both determined by broadband dielectric spectroscopy. Independently, activation energies of penetrant diffusion (ED) of these nanocomposites were determined for N2, O2, CO2, and CH4 and a clear linear correlation between the two activation energies was established for the first time.
The molecular mobility of four liquid crystalline epoxy compounds was studied by dielectric spectroscopy in a wide range of frequency (10-1109 Hz). All the investigated materials form a nematic liquid crystalline phase at temperatures above 60 °C, one of them additionally exhibits a smectic A phase. Two of the compounds have molecules composed of a mesogen and two symmetric tails with eight alkyl groups each. Their properties were compared with the homologous pair having two alkyl groups in each tail. The length of the carbon chain influences the temperature range of the mesophase, which was also observed in this study. Characteristic relaxation processes were observed in the different mesophases. These processes were quantitatively analyzed and the estimated parameters were discussed in detail in dependence of the structure of the materials.
Dielectric spectroscopy (10-2 Hz to 106 Hz) was employed to investigate the molecular dynamics of hyperbranched polyesters where the number of the generation is systematically varied from 2 to 5. As a first result, the dielectric properties depends strongly on the generation of the hyperbranched polymers. For higher generations (3 to 5) at temperatures below Tg two relaxation processes are observed, a γ-process at lower temperatures and a β-process at higher ones. The apparent activation energies are around 100 kJ/mol which seems to be too high for truly localized processes. For the Generation 2, only the γ-process is observed. For all investigated polymers the dielectric α-relaxation could not be observed because of strong conductivity effects. Therefore, the conductivity is systematically analyzed which obeys the peculiarities found to be characteristic for semiconducting disordered materials. Especially, the Barton/Nakajima/Namikawa relationship is found to be valid.