Frequency and temperature amplitude dependence of complex heat capacity in the melting region of polymers

Amplitude and frequency dependence of reversible melting of polycaprolactone (PCL) and an ethylene octene copolymer (EOM) were studied using temperature-modulated differential scanning calorimetry (TMDSC) (2?10^?1 Hz <f < 0.05 Hz) and shear spectroscopy (dynamic mechanical analysis, DMA) (5?10^?4 Hz < f < 100 Hz). It was found that the excess heat capacity of PCL is constant for temperature amplitudes in the range 5 mK < A_T < 2 K. The excess heat capacity decreases with frequency of temperature perturbation and tends to zero at about 0.1 Hz and 100 Hz for PCL and EOM, respectively. The constant excess heat capacity and the frequency dependence support the idea that reversible melting is related to a relaxation process on the surface of the polymer crystals. The occurrence of such a relaxation process was shown by shear modulus measurements in the same frequency and temperature region. The relaxation process is, in the melting region, much slower than main relaxation (glass transition). At low temperatures, a crossover can be seen, indicating the independence of both processes because of spatial separation. The main relaxation is related to the melt, while the other is related to the crystal surface.