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High performance polymers of intrinsic microporosity (PIMs) have emerged as novel materials with broad applications from gas separation to electronic devices. Sufficiently rigid, even contorted polymer chains show only limited molecular mobility, therefore undergo inefficient packing and give rise to intrinsic microporosity with pore size generally smaller than 1 nm and BET surface areas larger than 700 m2/g. Further performance optimization and long-term stability of devices incorporating PIMs rely on our understanding of structure-processing-property relationships and physical aging, in which glass transition plays a key role. Up to now no glass transition temperature (Tg) of PIMs could be detected with conventional thermal analysis techniques before degradation. Decoupling the time scales responsible for the glass transition and the thermal decomposition is a reliable strategy to overcome this. This was achieved by employing fast scanning calorimetry (FSC) based on a chip sensor, which is capable to heat and cool a small sample (ng-range) with ultrafast rates of several ten thousand K/s. FSC provides definitive evidence of glass transition of a series of PIMs with a special consideration on the chain rigidity. The determined glass transition temperature of these PIMs follows the order of the rigidity of their backbone structures. FSC provides the first clear-cut experimental evidence of the glass transition of PIM-EA-TB with a Tg of 663 K, PIM-1 of 644 K and PIM-DMDPH-TB of 630 K at a heating rate of 1Χ104 K/s. Local fluctuations are featured in glass transition of highly rigid PIMs. As conformational changes are prevented by the backbone rigidity, the glass transition must rather be assigned to local small scale fluctuations.
Polymeric membranes represent a cost- and energy efficient solution for gas separation. Recently superglassy polymers with high free volume outperform many conventional dense polymers in terms of gas permeability and selectivity. However, such materials with a high fractional free volume (FFV) are prone to pronounced physical aging. The initial microporous structures approach a denser state via local chain rearrangements which results in a dramatic reduction in the gas permeability. For the first time, dielectric spectroscopy with state-of-the-art high-resolution analyzers was employed to investigate the molecular mobility and physical aging of two representative groups of superglassy polymers: PIMs (PIM-1 & PIM-EA-TB) and Si-containing polynobornenes (PTCNSi1 & PTCNSi2). The dielectric behavior of the solution-cast polymeric films was measured by isothermal frequency scans during the different heating cycles in a broad temperature range. Structural relaxation of the films was observed during the measurements. Multiple dielectric processes following Arrhenius behavior were observed for all the investigated polymers. Moreover, they all showed conductivity in the glassy state. The significant increase in the conductivity with increasing temperature especially for PIMs is explained in terms of the formation of local intermolecular agglomerated structures due to interaction of π-electrons in aromatic moieties of the polymer backbone.
Thermal and dynamic glass transition of ultrathin films of homopolymers and a miscible polymer blend
(2017)
Despite the decade long controversial discussion on the effect of nanometer confinement on the glass transition temperature (Tg) of ultrathin polymer films, there is still no consistent picture. Here, the dynamic calorimetric glass transition of ultrathin films of a blend, which is miscible in the bulk, is directly investigated by specific heat spectroscopy. By a self-assembling process, a nanometer thick surface layer with a higher molecular mobility is formed at the polymer/air interface. By measuring the dynamic calorimetric Tg in dependence on the film thickness, it was shown that the Tg of the whole film was strongly influenced by that nanometer thick surface layer, with a lower Tg. Since the observed thickness dependence of the dynamic Tg is similar to the thickness dependence of the Tg for thin films of homopolymers, it is concluded that also for homopolymer a highly mobile surface layer is relevant for the widely observed Tg depression.
Super glassy polymers such as poly(trimethylsilylpropyne) (PTMSP) or polymers with intrinsic microporosity (PIMs) play an important role in the current development of membrane materials for gas separation because of their high permeability and selectivity. Unfortunately, such materials which have a high fractional free volume (FFV) are prone to pronounced physical aging. The initial microporous structures approach a more dense state via local chain rearrangements which results in a dramatic reduction in the gas permeability. For the first time, broadband dielectric spectroscopy was employed to investigate the molecular dynamics of two representative groups of super glassy polymers: PIMs (PIM-1 & PIM-EA-TB) and Si-containing polynobornenes (PTCNSi1 & PTCNSi2). The dielectric behavior of the solution-cast polymeric films was measured by isothermal frequency scans during the different heating cycles in a broad temperature range. Structural relaxation of the films was observed during the measurements. Molecular relaxation processes following Arrhenius behavior with unusually high activation energies were observed for all the investigated polymers. The PIMs showed furthermore a significant conductivity in the glassy state which is explained with the formation of local intermolecular agglomerated structures due to interaction of π-electrons in aromatic moieties of the polymer backbone.