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Polymeric membranes represent a low-cost, energy efficient solution for gas separation. Recently polymers of intrinsic microporosity (PIMs) have emerged as prestigious membrane materials featuring a large concentration of pores smaller than 1 nm, a BET surface area larger than 700 m2/g and high gas permeability and selectivity. Unusual chain structure combining rigid segments with sites of contortion gives rise to the intrinsic microporosity. However, this novel class of glassy polymers are prone to pronounced physical aging. The initial microporous structures approach a denser state via local small scale fluctuataions, leading to a dramatic reduction in the gas permeabilities. For the first time, dielectric relaxation spectroscopy with state-of-the-art high-resolution analyzers was employed to investigate three representative PIMs with a systematic change in chain rigidity: PIM-EA-TB 〉 PIM-1 〉 PIM-MDPH-TB. The molecular mobility, the charge transport and their response upon heating (aging) in the polymers were measured in a broad temperature range through isothermal frequency scans during different heating / cooling cycles. Multiple dielectric processes following Arrhenius behavior were observed for the investigated polymers. Local fluctuations, Maxwell-Wagner-Sillars (MWS) polarization and structural relaxation phenomena were discussed and attempted to be correlated with the structural features of PIMs. Moreover, all PIMs showed conductivity in the glassy state. The significant increase in the conductivity with increasing temperature far below the glass transition temperature of PIMs is explained in terms of the loosely packed microporous structure and the formation of local intermolecular agglomerates due to interaction of π-electrons in aromatic moieties of the polymer backbone.
Over the past decades research on the molecular dynamics of miscible polymer blends is of topical interest in the literature, to understand the segmental mobility of individual components, as it is affected by blending. In general, miscible polymer blends exhibit a complex dynamic behavior. For an A/B blend the relaxation times of component A and component B are affected by the spatial local compositional heterogeneity, present in binary systems on a microscopic level, regardless of the macroscopic homogeneity. Here, a combination of broadband dielectric and specific heat spectroscopy was employed to study the dynamically asymmetric PVME/PS blend with seven different compositions, focusing on samples with high PS contents. Considering that PS is dielectrically invisible, BDS is a powerful technique to study the response of PVME, as it is affected by PS segments. Here, three separate relaxation processes were found by dielectric investigations, related to confined or constrained PVME segments due to the spatial local compositional heterogeneities, which is in contrary to the previous literature findings [1]. Moreover, the dielectric data was compared with results obtained by specific heat spectroscopy, where a fourth relaxation process was found, due to the cooperative fluctuations of PVME and PS.
[1] Colmenero, J., Arbe, A. Soft Matter, 2007, 3, 1474.
Over the past decades research on the molecular dynamics of miscible polymer blends are of topical interest in the literature, in an attempt to understand the segmental mobilty of individual components, as it is affected by blending. In general, miscible polymer blends exhibit a complex behavior of the molecular mobility. For an A/B blend the relaxation times of component A and component B are affected by the spatial local compositional heterogeneity, present in binary systems on a microscopic level, regardless of the macroscopic homogeneity. Here, a combination of broadband dielectric and specific heat spectroscopy was employed to study the dynamically asymmetric PVME/PS blend with seven different compositions, focusing on samples with high PS contents. Considering that PS is dielectrically invisible, BDS is a powerful technique to study the response of PVME, as it is affected by PS segments. In this work the well-known binary relaxation times distribution of PVME in a blend, originating from the spatial local heterogeneity, was studied over ten decades in frequency, for the first time in literature. Secondly, one of the detected processes, α’-relaxation, shows a crossover from high-temperature behavior (system in equilibrium) towards a low temperature regime, where PS undergoes the thermal glass transition, resulting in confined segmental dynamics of PVME within a frozen network of PS. Here, we introduce a precise mathematical tool to distinguish between the temperature dependency regimes of the process, and examine the composition dependence of the crossover temperature, detected by dielectric spectroscopy. Moreover, the dielectric data was compared in detail with results obtained by specific heat spectroscopy. This comparison provides new insights in the dynamics and dynamic heterogeneity of the PVME/PS blend system.
Dynamics of nanoscopically confined PVME in thin films of an asymmetric miscible PVME/PS blend
(2018)
In recent years, substantial efforts have been devoted to investigating nanoscopic confinement of polymers, and its effect on glassy dynamics. Broadband Dielectric Spectroscopy (BDS) was used to study the dynamics of ultra-thin films of PVME/PS 50/50 wt% blend, employing a novel nano-structured capacitor sample arrangement. The investigated system shows a complex dynamic behavior. First, an α-relaxation, related to a bulk-like layer was found. Second, an α’-relaxation was observed, characteristic for dynamically asymmetric blends, where the out of equilibrium dynamics is attributed to weakly-cooperative PVME segments relaxing within a frozen environment of PS segments. Third, for thinnest films, an Arrhenius-like process was dominant in the dielectric spectra, indicating localized fluctuations of the segments. Relaxation rates of this process resembled that of the degenerated α-relaxation of the adsorbed layer, found for pure PVME [1], thus it was assigned accordingly. For thinnest films, this process undergoes a further confinement, due to the topological constraints, introduced by PS. Such multiple confinement effect has not been reported for ultra-thin films of polymer blends, before this study [2].
[1] Madkour, S. et al. ACS Appl. Mater. Interfaces 2017, 9, 7535.
[2] Madkour, S. et al. ACS Appl. Mater. Interfaces 2017, 9, 37289.
In well-annealed thin polymer films, with non-repulsive polymer/substrate interactions, an irreversibly adsorbed layer is expected to form. These adsorbed layers have shown great potential for technological applications. However, their growth kinetics and molecular dynamics are still not fully understood. This is partially due to the hard accessibility of these layers in thin films. Here, the irreversibly adsorbed layers of homopolymer thin films are revealed by solvent-leaching experiments. First, the growth kinetics of these layers is investigated as a function of annealing times and original film thickness. The thickness, topography and quality of the adsorbed layer is controlled with Atomic Force Microscopy (AFM). Secondly, the molecular mobility of the adsorbed layer is investigated with Broadband Dielectric Spectroscopy (BDS). A recently developed nanostructured capacitor is employed to measure the adsorbed layers with a free surface layer. The results are quantitatively compared and discussed with respect to recently published work.