How Do Organic Vapors Swell Ultra-Thin PIM-1 Films?

Dynamic sorption of ethanol and toluene vapor into ultra-thin supported PIM-1 films down to 6 nm are studied with a combination of in-situ spectroscopic ellipsometry and in-situ X-ray reflectivity. Both ethanol and toluene significantly swell the PIM-1 matrix and, at the same time, induce persistent structural relaxations of the frozen-in glassy PIM-1 morphology. For ethanol below 20 nm three effects were identified. First, the swelling magnitude at high vapor pressures is reduced by about 30% as compared to thicker films. Second, at low penetrant activities (below 0.3 p/p0) films below 20 nm are able to absorb slightly more penetrant as compared with thicker films despite similar swelling magnitude. Third, for the ultra-thin films the onset of the dynamic penetrant-induced glass transition Pg has been found to shift to higher values indicating higher resistance to plasticization. All of these effects are consistent with a view where immobilization of the super-glassy PIM-1 at the substrate surface leads to an arrested, even more rigid and plasticization-resistant, yet still very open, microporous structure. PIM-1 in contact with the larger and more condensable toluene shows very complex, heterogeneous swelling dynamics and two distinct penetrant-induced relaxation phenomena, probably associated with the film outer surface and the bulk, are detected. Following the direction of the penetrant's diffusion the surface seems to plasticize earlier than the bulk and the two relaxations remain well separated down to 6 nm film thickness, where they remarkably merge to form just a single relaxation.