No abstract

Ellipsometry and X-ray reflectivity were used to characterize the mass density and the glass transition temperature of supported polystyrene (PS) thin films as a function of their thickness. By measuring the critical wave vector (qc) on the plateau of total external reflection, we evidence that PS films get denser in a confined state when the film thickness is below 50 nm. Refractive indices (n) and electron density profiles measurements confirm this statement. The density of a 6 nm (0.4 gyration radius, Rg) thick film is 30% greater than that of a 150 nm (10Rg) film. A depression of 25 °C in glass transition temperature (Tg) was revealed as the film thickness is reduced. In the context of the free volume theory, this result seems to be in apparent contradiction with the fact that thinner films are denser. However, as the thermal expansion of thinner films is found to be greater than the one of thicker films, the increase in free volume is larger for thin films when temperature is raised. Therefore, the free volume reaches a critical value at a lower Tg for thinner films. This critical value corresponds to the onset of large cooperative movements of polymer chains. The link between the densification of ultrathin films and the drop in their Tg is thus reconciled. We finally show that at their respective Tg(h) all films exhibit a critical mass density of about 1.05 g/cm(3) whatever their thickness. The thickness dependent thermal expansion related to the free volume is consequently a key factor to understand the drop in the Tg of ultrathin films.

Mechanical properties of lipidic membranes such as their bending rigidity are governing liposome morphology and play an important role in processes like membrane fusion and adhesion. Force versus deformation measurements are the most direct means to determine this, but so far experimental data is scarce and mainly stems from techniques that are limited to giant vesicles. We present atomic force microscope force spectroscopy as a method allowing force-deformation measurements of submicron vesicles. Bending rigidities of small unilamellar dipalmitoylphosphatidylcholine (DPPC) liposomes (R<200 nm) can be derived from the force-deformation data using analytical models based on shell theory and are in good agreement with independent measurements.