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This research effort investigated the influence of confinement on the physical aging behavior of thin and ultrathin glassy polymer membranes. Membrane permeability changes with time due to physical aging, and for reasons not completely understood, the rate of permeability change can become orders of magnitude faster in films thinner than one micron. Special experimental techniques were developed to enable the study of free standing, ultrathin glassy polymer films using gas permeability measurements. The gas transport properties and physical aging behavior of free-standing glassy polysulfone (PSF) and Matrimid® films from 18-550 nm thick are presented. Physical aging persists in glassy films approaching the length scale of individual polymer coils. The membranes exhibited significant reductions in gas permeability and increases in selectivity with aging time. Additionally, the influence of physical aging on the free volume profile in thin PSF films was investigated using variable energy positron annihilation lifetimespectroscopy (PALS). The films exhibited decreasing o-Ps lifetime during physical aging, while o-Ps intensity remained constant. The o-Ps lifetime was reduced at lower implantation energies, indicating smaller free volume elements near the film surface. Thin films aged dramatically faster than bulk PSF and the PALS results agree favorably to behavior tracked by gas permeability measurements. The physical aging behavior of ultrathin films with different previous histories was also studied. The state of these materials was modulated by various conditioning treatments. Regardless of the previous history, the nature of the aging response was consistent with the aging behavior of an untreated film that was freshly quenched from above Tg, i.e., permeability decreased and pure gas selectivity increased with aging time. However, the extent of aging-induced changes in transport properties of these materials depended strongly on previous history. The properties of these ultrathin films deviate dramatically from bulk behavior, and the nature of these deviations is consistent with enhanced mobility and reduced Tg in ultrathin films, which allows them to reach a lower free volume state more quickly than bulk material. The Struik physical aging model was extended to account for the influence of film thickness on aging, and was shown to accurately describe the experimental data. / text

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published_or_final_version / abstract / toc / Physics / Master / Master of Philosophy

published_or_final_version / Physics / Master / Master of Philosophy

No description available.

This thesis investigates the application of low energy electron irradiation to 1,3,5-trimethylbenzene films to test whether site-selective C–H bond cleavage can be achieved in a molecule presenting both aliphatic and aromatic target sites. IRRAS was used to characterize the orientation of vapour-deposited 1,3,5-trimethylbenzene on Au(111) and alkanethiolated gold under UHV and cryogenic conditions. On both substrates, the disordered as-deposited films were transformed by thermal treatment, producing two film structures – within the first 4-monolayers, aromatic rings lie nearly parallel to the metal surface, while molecules in additional layers are more upright. Low energy electron irradiation (0-10 eV) produced no dissociations in 1,3,5-trimethylbenzene; however, low energy electron transmission spectra indicate charge accumulates at interstitial sites in the mesitylene film, decelerating subsequent incident electrons. These decelerated electrons traverse the charged film and are reaccelerated, inducing dissociations in the underlying SAM. Contrary to literature claims, 1,3,5-trimethylbezene is a poor molecule for adsorption studies such as BET as the initial adsorption is disordered and thermodynamically unstable.

No description available.

No description available.