To treat data from temperature modulated differential scanning calorimetry (TMDSC) in terms of complex or reversing heat capacity
firstly one should pay attention that the response is linear and stationary because this is a prerequisite for data evaluation.
The reason for non-linear and non-stationary thermal response is discussed and its influence on complex (reversing) heat capacity
determination is shown. The criterion for linear and stationary response is proposed. This allows to choose correct experimental
conditions for any complex heat capacity measurement. In the case when these conditions can not be fulfilled because of experimental
restrictions one can estimate the influence of non-linearity and non-stationarity on measured value of complex or reversing
Temperature modulated dynamic mechanical analysis (TMDMA) was performed in the same way as temperature modulated DSC (TMDSC)
measurements. As in TMDSC TMDMA allows the investigation of reversible and non-reversible phenomena during crystallisation
of polymers. The advantage of TMDMA compared to TMDSC is the high sensitivity for small and slow changes in crystallinity,
e.g. during re-crystallisation. The combination of TMDMA and TMDSC yields new information about local processes at the surface
of polymer crystallites. It is shown that during and after isothermal crystallisation the surface of the individual crystallites
is in equilibrium with the surrounding melt.
Quasi-isothermal temperature modulated DSC (TMDSC) were performed during crystallization to determine heat capacity as function of time and frequency. Non-reversible and reversible phenomena in the crystallization region of polymers were distinguished. TMDSC yields new information about the dynamics of local processes at the surface of polymer crystals, like reversible melting. The fraction of material involved in reversible melting, which is established during main crystallization, keeps constant during secondary crystallization for polycaprolactone (PCL). This shows that also after long crystallization times the surfaces of the individual crystallites are in equilibrium with the surrounding melt. Simply speaking, polymer crystals are living crystals. A strong frequency dependence of complex heat capacity can be observed during and after crystallization of polymers.