Calorimetric glass transition temperature and absolute heat capacity of polystyrene ultrathin films

The absolute heat capacity and glass transition temperature (Tg) of unsupported ultrathin films were measured with differential scanning calorimetry with the step‐scan method in an effort to further examine the thermodynamic behavior of glass‐forming materials on the nanoscale. Films were stacked in layers with multiple preparation methods. The absolute heat capacity in both the glass and liquid states decreased with decreasing film thickness, andTgalso decreased with decreasing film thickness. The magnitude of theTgdepression was closer to that observed for films supported on rigid substrates than that observed for freely standing films. The stacked thin films regained bulk behavior after the application of pressure at a high temperature. The effects of various preparation methods were examined, including the use of polyisobutylene as an interleaving layer between the polystyrene films.