Observation of General Entropy–Enthalpy Compensation Effect in the Relaxation of Wrinkled Polymer Nanocomposite Films

Surface-textured polymer nanocomposite (PNC) films are utilized in many device applications, and therefore understanding the relaxation behavior of such films is important. By extending an in situ wrinkle relaxation method, we observed that the thermal stability of wrinkled PNC films, both above and below the glass transition temperature (T g), is proportional to a film’s nanoparticle (polymer grafted and bare) concentration, with a slope that changes sign at a compensation temperature (T comp) that is determined to be in the vicinity of the film’s T g. This provides unambiguous confirmation of entropy–enthalpy compensation (EEC) as a general feature of PNC films, implying that the stability of PNC films changes from being enhanced to becoming diminished by simply passing through this characteristic temperature, a phenomenon having evident practical ramifications. We suggest EEC will also arise in films where residual stresses are associated with the film fabrication process, which is relevant to nanotech device applications.