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Three polystyrene (PS)/clay hybrid systems have been prepared via in situ polymerization of styrene in the presence of unmodified sodium montmorillonite (Na‐MMT) clay, MMT modified with zwitterionic cationic surfactant octadecyldimethyl betaine (C18DMB) and MMT modified with polymerizable cationic surfactant vinylbenzyldimethyldodecylammonium chloride (VDAC). X‐ray diffraction and TEM were used to probe mineral layer organization and to expose the morphology of these systems. The PS/Na‐MMT composite was found to exhibit a conventional composite structure consisting of unintercalated micro and nanoclay particles homogeneously dispersed in the PS matrix. The PS/C18DMB‐MMT system exhibited an intercalated layered silicate nanocomposite structure consisting of intercalated tactoids dispersed in the PS matrix. Finally, the PS/VDAC‐MMT system exhibited features of both intercalated and exfoliated nanocomposites. Systematic statistical analysis of aggregate orientation, characteristic width, length, aspect ratio, and number of layers using multiple TEM micrographs enabled the development of representative morphological models for each of the nanocomposite structures. Oxygen barrier properties of all three PS/clay hybrid systems were measured as a function of mineral composition and analyzed in terms of traditional Nielsen and Cussler approaches. A modification of the Nielsen model has been proposed, which considers the effect of layer aggregation (layer stacking) on gas barrier. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 1733–1753, 2007

Systematic divergences in the orthopositronium (o-Ps) annihilation lifetimes, τ3, and intensities, I 3, are observed, when comparing melt-crystallized and cold-crystallized poly(ethylene terephthalate) (PET) as a function of crystallinity. Following a previous analysis of corresponding deviations in oxygen permeability, the divergences in I 3 and τ3 are traced to distinct characteristic values for the probability of o-Ps formation and o-Ps lifetime in the rigid amorphous phase (RAF) associated with the crystalline lamellae and the mobile amorphous regions (MAF) which are unperturbed by the presence of the crystal phase. Utilizing independent information on the volume fractions of RAF and MAF, a quantitative analysis of the o-Ps annihilation parameters is possible.

A coincidence between the temperature‐dependent hole (free volume) fraction h above the glass transition temperature, derived from lattice‐hole theory, and the corresponding function hPs obtained from positronium lifetime spectroscopy has been previously observed for four polystyrene fractions ranging from 4000 to 400,000 in molar mass. This result was based on the assumed proportionality of hPs and the product of the orthopositronium intensity I3 and the mean cavity volume, the proportionality constant C being molar mass dependent. However, a recent analysis of the data based on volume arguments by Olson and Jamieson revealed systematic departures between the two sets of free volume functions. We reexamine the situation by departing from the customary assumption of spherical cavities, and allowing for nonspherical geometries represented by prismatic or cylindrical disks. Agreement between spectroscopic and thermodynamic functions ensues with fixed, temperature‐independent asymmetry factors decreasing with increasing molar mass. These tentative findings suggest that systematic studies of melts with varying chain flexibility and molar mass should be attempted. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 2225–2229, 2005

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