Polymers of intrinsic microporosity (PIMs) are receiving increasing attention from the membrane community because of their high gas and vapor permeability. Recently a novel ethanoanthracene-based PIM synthesized by Troger's base formation (PIM-EA-TB) was reported to have exceptional transport properties, behaving as a polymer molecular sieve membrane. In the present work, an extensive investigation of the structural, mechanical, and transport properties of this polymer, both by experimental analysis and by molecular simulation, offers deep insight into the behavior of this polymer and gives an explanation for its remarkable performance as a membrane material. Transport properties were determined by the barometric time-lag method, by the volumetric method with gas chromatographic or mass spectrometric gas analysis, and by gravimetric sorption measurements, yielding all basic transport parameters, permeability (P), diffusivity (D), and solubility (S). Upon alcohol treatment, PIM-EA-TB exhibited a much stronger permeability increase than archetypal "benchmark" polymer PIM-1, with performance above the Robeson upper bound for several gas pairs. This is in part due to an extremely high gas solubility in PIM-EA-TB, higher than in PIM-1. The experimental data were supported by extensive modeling studies of the polymer structure and the spatial arrangement of its free volume. Modeling confirms that the high gas permeability must be attributed to the large fractional free volume of the polymer. The simulated free volume size distribution in PIM-EA-TB is in agreement with the average experimental free volume elements size determined by PALS and 129 Xe NMR analysis. The modeled spatial arrangement of the free volume revealed a slightly lower interconnectivity of the FV elements in PIM-EA-TB compared to PIM-1. Along with its higher chain rigidity, determined by analysis of the torsion angles in the polymer model, this was identified as the main reason for its stronger size sieving behavior and relatively high permselectivity. A number of peculiarities in the behavior of PIMs will also be discussed here, explaining discrepancies between results published in the literature by different laboratories, the effect of their thermomechanical history, aging, or conditioning, and the influence of the measurement technique and of the experimental conditions on the results. This makes this study of inestimable value for unifying the results of different experimental techniques and fully understanding the transport properties.

The d.c. electrical conductivity of polyacrylate sodium salt and poly(acrylic acid) aqueous solutions of different molecular weights from 2 to 200 kD has been investigated in a wide range of polymer concentration, covering both the semidilute (unentangled and entangled) and concentrated regimes. The data have been analyzed on the basis of a modified version of the Manning theory of counterion condensation, to cover the semidilute regime, taking into account scaling arguments recently proposed by Dobrynin et al. (Macromolecules 1995, 28, 1859). This analysis, on the basis of the conductivity model we have adopted, provides evidence for a fraction of free counterions that increases with the polymer concentration until the semidilute-concentrated crossover concentration is reached, suggesting that, in the concentration range investigated, the effective charge on the polyion is dependent on the polymer concentration. Moreover, at the higher concentrations investigated, our data suggest that a regime is attained where electrostatic blobs overlap, strongly affecting the electrical transport properties of the solution and causing a progressive reduction of the free counterion concentration.

A comparative study of five different experimental and computational methods is presented for the characterization of the overall free volume (FV) and the free volume element (FVE) size and shape distribution in amorphous glassy perfluoropolymers (PFPs). Experimental results from the photochromic probe (PCP) method, positron annihilation lifetime spectroscopy (PALS), and inverse gas chromatography (IGC) were confronted with literature data from 129 Xe NMR spectroscopy, and the experimental data were further compared with molecular dynamics (MD) simulations and a combination of MD studies and the wellknown Bondi method as well as a modified Bondi method. An evaluation of the advantages and the limits of each method is presented. This is the first reported study on a so vast number of complementary techniques applied on a single glassy polymer, in this case Hyflon AD perfluoropolymer, and is also the first successful application of the photochromic probe technique in such materials. In two different grades of Hyflon AD, the polymer with the highest content of the stiff cyclic comonomer was found to have a slightly larger average FVE size but a lower void concentration, explaining the nearly identical density and fractional free volume (FFV) of the two samples. PALS furthermore demonstrated a similar trend for solution-cast samples in comparison with melt-pressed samples, the latter having FVEs with a smaller size but a higher concentration. The data from IGC seem to correspond most closely to those of the PCP method. Differences between the results from the individual techniques derive mainly from the fundamentally diverse nature of the various probing methods but also from the different capacity to take into account the FVE shape. Only MD simulation studies, using detailed atomistic packing models, can give such deep insight into the spatial arrangement of the FVEs directly. Besides giving the highest level of detail, MD simulations can thus help to understand the possible limits of the experimental methods. Knowledge of their free volume distribution is of fundamental importance to gain more insight into the mass transport phenomena in these materials, relevant for their successful application in the emerging field of synthetic membranes for gas and vapor separations.

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