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Polymeric membranes represent a cost- and energy-efficient solution for gas separation. Recently Polymers of Intrinsic Microporosity (PIMs) have been in a great interest because of their outstanding BET surface area larger than 700m2/g and pore size smaller than 1 nm. PIMs are a promising candidate in gas separation with high permeability and appealing selectivity due to their inefficient packing derived from a combination of ladder-like rigid segments with sites of contortion. However, it is recognized this class of polymers suffer from decrease in performance with time due to physical aging. The initial microporous structures approach a denser state via local chain rearrangements, leading to a dramatic reduction in permeability. As chain packing during film casting and physical aging are the key factors determine the performance in separation applications, characterization of the molecular mobility in these materials has been proved to provide valuable information. In recent research on PIM-1 the archetypal PIM, a molecular relaxation process with high activation energy together with a significant conductivity in the glassy state has been found and explained with the formation of local intermolecular agglomerates due to interaction of π-electrons in aromatic moieties of the polymer backbone. In this work, the dielectric behavior of the polymeric films and their response upon heating (aging) were measured by isothermal frequency scans during different heating/cooling cycles in a broad temperature range down to 133K for the first time. Multiple dielectric processes following Arrhenius behavior were observed. Local fluctuations, Maxwell-Wagner-Sillars (MWS) polarization and structural relaxations were discussed correlating to structural-properties of PIM-1. Up to now, no other work has studied the role of porosity and thermal history of PIM-1 film in dielectric processes. The goal is by eliminating thermal history and considering storing conditions provide better understanding on aging and plasticizing in high free volume glassy polymer PIM-1.
Predicting nonlinear physical aging of glasses from equilibrium relaxation via the material time
(2022)
The noncrystalline glassy state of matter plays a role in virtually all fields of materials science and offers complementary properties to those of the crystalline counterpart. The caveat of the glassy state is that it is out of equilibrium and therefore exhibits physical aging, i.e., material properties change over time. For half a century, the physical aging of glasses has been known to be described well by the material-time concept, although the existence of a material time has never been directly validated. We do this here by successfully predicting the aging of the molecular glass 4-vinyl-1,3-dioxolan-2-one from its linear relaxation behavior. This establishes the defining property of the material time. Via the fluctuation-dissipation theorem, our results imply that physical aging can be predicted from thermal-equilibrium fluctuation data, which is confirmed by computer simulations of a binary liquid mixture.
Polymers with intrinsic microporosity are promising candidates for the active separation layer in gas separation membranes. Here, the vibrational density of states (VDOS) for PIM-1, the prototypical polymer with intrinsic microporosity, is investigated by means of inelastic neutron scattering. The results are compared to data measured for a more conventional high-performance polyimide used in gas separation membranes (Matrimid). The measured data show the characteristic low frequency excess contribution to VDOS above the Debye sound wave level, generally known as the Boson peak in glass-forming materials. In comparison to the Boson peak of Matrimid, that of PIM-1 is shifted to lower frequencies. This shift is discussed considering the microporous, sponge-like structure of PIM-1 as providing a higher compressibility at the molecular scale than for conventional polymers. For an annealed PIM-1 sample, the Boson peak shifts to higher frequencies in comparison to the un-annealed sample. These changes in the VDOS of the annealed PIM-1 sample are related to changes in the microporous structure as confirmed by X-ray scattering.
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.
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.