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The molecular dynamics of addition-type poly(tricyclononenes) with Si-substituted bulky side groups has been investigated by a combination of neutron time-of-flight and neutron backscattering spectroscopy methods on a time scale from 0.1 ps to ca. 3 ns. The investigated poly(tricyclononenes) PTCNSi1 and PTCNSi2g both bear a high microporosity which makes them promising candidates for active separation layers for gas separation membranes. At least for larger gas molecules it is assumed that the pathways for diffusion require an enlargement of pre-existing micropores in terms of an activated zone. A low temperature relaxation process was found for both polymers by the performed neutron scattering experiments. This process was assigned to the methyl group rotation. It was analysed in terms of a jump diffusion in a three-fold potential. The analysis of the dependence of the elastic incoherent structure factor on the scattering vector yields the number of methyl groups which might be immobilized. For PTCNSi1 (3 methyl groups in the monomeric unit) it was found that all methyl groups take part in the methyl group rotation whereas for PTCNSi2g (6 methyl groups in monomeric unit) a considerable number of methyl groups are blocked in their rotation. This immobilization of methyl groups is due to the sterically demanding arrangement of the methyl groups in PTCNSi2g. This conclusion is further supported by the result that the activation energy for the methyl group rotation is three times higher for PTCNSi2g than that of PTCNSi1.
We introduce azobenzene-functionalized polyelectrolyte multilayers as efficient, inexpensive optoacoustic transducers for hyper-sound strain waves in the GHz range. By picosecond transient reflectivity measurements we study the creation of nanoscale strain waves, their reflection from interfaces, damping by scattering from nanoparticles and propagation in soft and hard adjacent materials like polymer layers, quartz and mica. The amplitude of the generated strain ε∼5×10−4 is calibrated by ultrafast X-ray diffraction.
The molecular dynamics of two addition type polynorbornenes, exo-PNBSiand PTCNSi1, bearing microporosity has been investigated by broadbanddielectric spectroscopy, fast scanning calorimetry, and neutron scattering. Bothpolymers have the same side groups but different backbones. Due to theirfavorable transport properties, these polymers have potential applications inseparation membranes for gases. It is established in literature that molecularfluctuations are important for the diffusion of small molecules through poly-mers. For exo-PNBSi, two dielectric processes are observed, which are assignedto Maxwell/Wagner/Sillars (MWS) process due to blocking of charge carriersat internal voids or pore walls. For PTCNSi1, one MWS-polarization process isfound. This points to a bimodal pore-size distribution for exo-PNBSi. A glasstransition for exo-PNBSi and for PTCNSi1 could be evidenced for the first timeusing fast scanning calorimetry. For Tgand the corresponding apparent activa-tion energy, higher values were found for PTCNSi1 compared to exo-PNBSi.For both polymers, the neutron scattering data reveal one relaxation process.This process is mainly assigned to methyl group rotation probably overlayedby carbon–carbon torsional fluctuations.
Quasielastic neutron scattering by employing a combination of time-of-flight and backscattering techniques is carried out to explore the molecular mobility of a polymer of intrinsic microporosity (PIM-1) at microscopic time scales in comparison with a high-performance polyimide. Molecular fluctuations can change the structure of the temporary network of micropores and open or close pathways for gas molecules. Therefore, the investigation might help to understand the selectivity of PIMs in gas separation processes. The performed neutron scattering experiments provide evidence for a low-temperature relaxation process, which was assigned to methyl group rotation. This methyl group rotation was analyzed in terms of jump diffusion in a three-fold potential. The analysis results in a fraction of methyl groups which are immobilized. For PIM-1 it was found that the fraction of immobilized methyl groups decreases with increasing temperature up to 350 K. At higher temperatures the number of immobilized methyl group increases gain due to an underlying relaxation process. This motional process on a somewhat larger length scale might lead to a reversible structural rearrangement which partially hinders the strongly localized methyl group rotation. In addition, it was found that the activation energy for the methyl group rotation for PIM-1 and the polyimide is significantly higher than for conventional polymers.
The molecular dynamics of the triphenylene-based discotic liquid crystal HAT6 is investigated by broadband dielectric spectroscopy, advanced dynamical calorimetry and neutron scattering. Differential scanning calorimetry in combination with X-ray scattering reveals that HAT6 has a plastic crystalline phase at low temperatures, a hexagonally ordered liquid crystalline phase at higher temperatures and undergoes a clearing transition at even higher temperatures. The dielectric spectra show several relaxation processes: a localized gamma-relaxation a lower temperature and a so called alpha-2-relaxation at higher temperatures. The relaxation rates of the alpha-2-relaxation have a complex temperature dependence and bear similarities to a dynamic glass transition. The relaxation rates estimated by hyper DSC, Fast Scanning calorimetry and AC Chip calorimetry have a different temperature dependence than the dielectric alpha-2-relaxation and follows the VFT-behavior characteristic for glassy dynamics. Therefore, this process is called alpha-1-relaxation. Its relaxation rates show a similarity with that of polyethylene. For this reason, the alpha-1-relaxation is assigned to the dynamic glass transition of the alkyl chains in the intercolumnar space. Moreover, this process is not observed by dielectric spectroscopy which supports its assignment. The alpha-2-relaxation was assigned to small scale translatorial and/or small angle fluctuations of the cores.
The neutron scattering data reveal two relaxation processes. The process observed at shorter relaxation times is assigned to the methyl group rotation. The second relaxation process at longer time scales agree in the temperature dependence of its relaxation rates with that of the dielectric gamma-relaxation.