Variation in Activation Energy and Nanoscale Characteristic Length at the Glass Transition

Differential scanning calorimetry has been used to study the α-relaxation (glass transition) in virgin polystyrene (PS), PS-clay nanocomposite, amorphous indomethacin (IM), maltitol (Mt) and glucose (Gl). Variation of the effective activation energy (E) throughout the glass transition has been determined by applying an advanced isoconversional method to DSC data on the glass transition. The relaxations have been characterized by determining the effective activation energies (E) and evaluating the sizes of cooperatively rearranging regions at the glass transition (Vg). The values of Vg have been determined from the heat capacity data. The α-relaxation demonstrates markedly larger values of E (~340 vs ~270 kJ mol-1) for the PS-clay system than for virgin PS. For IM in the glass transition region, the effective activation energy of relaxation decreases with increasing temperature from 320 to 160 kJ mol-1. In the Tg region E decreases (from~250 to ~150 kJ mol-1 in maltitol and from~220 to ~170 kJ mol-1 in glucose) with increasing T as typically found for the α-relaxation. It has been found that in the sub-Tg region E decreases with decreasing T reaching the values ~60 (glucose) and ~70 (maltitol) kJ -1 that are comparable to the literature values of the activation energies for the β-relaxation. Heat capacity measurements have allowed for the evaluation of the cooperatively rearranging region in terms of the linear size The PS-clay system has also been found to have a significantly larger value of Vg, 36.7 nm3 as compared to 20.9 nm3 for PS. Heat capacity measurements of IM have allowed for the evaluation of the cooperatively rearranging region (CRR) in term of linear size (3.4 nm) and the number of molecules (90). The size of CRR have been determined as 3.1 (maltitol) and 3.3 (glucose) nm.