The glass transition behavior of ultra-thin supported polymer films is discussed controversially in the literature for around 20 years. Substantial efforts have been archived to understand it. In this contribution, a combination of methods sensitive to bulk properties of a system, like dielectric or specific heat spectroscopy with surface analytics, for instance, atomic force microscopy (AFM), contact angle measurements, and X-ray photoelectron spectroscopy (XPS) were employed to study the glass transition of ultra-thin supported films. All investigations were carried out on identically prepared and treated samples. Different systems with different complexities going from more or less flexible homopolymers over rigid main chain macromolecules to polymer blends have been studied. For the investigated flexible macromolecules, the dynamic glass transition temperature estimated within the frame of the linear response approach is independent of the film thickness down to several nanometers and identical to the bulk value. For polystyrene it was found the thermal glass transition temperatures can depend on the film thickness. This different behavior is not well understood till now and needs further experimental clarification. For the investigated main chain polymers polycarbonate and polysulfone. Dynamic and thermal glass transition temperature estimated from the dielectric measurements increases with decreasing film thickness. This is discussed in the frame of a strong interaction of the polymer segments with the surface of the substrate. In general for homopolymers, the interaction energy of the polymer segments with the substrate surface cannot be considered as the only parameter, which is responsible for the change in the thermal glass transition with the film thickness. For the investigated miscible blend system of polystyrene/poly(vinyl methyl ether) at a composition of 50/50 wt-% a decrease of the dynamic glass transition temperature with decreasing film thickness is found. This is explained by the formation of a poly(vinyl methyl ether)-rich surface layer with a higher molecular mobility.
Detailed atomistic simulations were carried out for swelling polymer/gas systems related to experimental sorption and dilation data for CO2 and CH4 in three glassy polymers (polysulfone PSU, the polyimide 6FDA-TrMPD, and a polymer of intrinsic microporosity PIM-1) at 308 K (35 °C) and pressures up to 50 bar. Corresponding experiments were performed with a gravimetric sorption balance and a dilatometer based on a capacitance distance sensor. For each polymer/gas system molecular packing models were prepared and equilibrated for two reference states: the pure polymer is taken as reference for the respective 'unswollen' state and similarly the state of the highest penetrant pressure reached in the corresponding experiment is taken to represent the 'swollen' state. Models for the latter were constructed in agreement with experimental data (pressure, temperature, gas concentration and volume dilation). Concentration–pressure isotherms of each polymer/gas system were obtained using Grand Canonical Monte Carlo (GCMC) simulations for both reference states (depleted of gas molecules), which are in good agreement with the experimental data in the respective pressure range. As expected these isotherms – due to the simulation technique used, merely based on hole-filling in a static host matrix – do not represent the sorption behavior over a broader range of gas pressures which may involve significant structural rearrangements as well as swelling and relaxational phenomena. Nevertheless, a linear combination of the two GCMC-isotherms allows the interpolation in order to describe the nonlinear gas sorption in the glassy polymers under investigation covering the penetrant pressure range between the reference states in good agreement with the experimental results.
Ultra-thin films of polysulfone are prepared by spin coating down to thicknesses below 10 nm on an aluminum support and investigated by broadband dielectric spectroscopy. As a main result is was found that the glass transition temperature Tg does not depend on the film thickness for thicknesses larger than 10 nm. Secondly from the analysis of the dielectric strength it is concluded that the polysulfone segments form an adsorbed layer with a reduced mobility at the Al support having a thickness of ca. 5 nm.
Experimental sorption and dilation data of the polysulfone/CO2 system at 308 K and pressures up to 50 bar were measured utilizing a gravimetric sorption balance and a dilatometer based on a capacitive distance sensor. The data of this glassy polymer/gas system were subjected to a thorough kinetic analysis on the basis of a viscoelastic model, which allows the separation of the diffusive/elastic fraction of the sorption/dilation process from the slower relaxational part. The results were interpreted in terms of the common dual mode sorption model and the site distribution model of Kirchheim. Detailed atomistic packing models of the same polymer/gas system were created for two reference states with regard to concentration and swelling. The CO2 sorption isotherms of the packing models corresponding to these two swelling states, calculated using GCMC simulations, could be combined in order to interpolate the gas uptake over the intermediate pressure range with good agreement to the experimental data. The elastic part of the gas induced dilation is successfully described by MD simulations and derived partial molar volumes are in satisfying agreement with experimental findings. Finally, the free volume of the packing models is probed and the obtained size distribution of the free volume elements is compared to the results of the analysis of experimental data according to the site distribution model.