Using standard and temperature‐modulated differential scanning calorimetry, we have studied the segmental relaxation behavior of montmorillonite‐epoxy nanocomposites. The experimental results showed that the incorporation of clay particles caused the epoxy network to exhibit slower relaxation dynamics compared with the neat epoxy resin. Analysis based on the Tool‐Narayanaswamy‐Moynihan (TNM) model indicated that the nanocomposite systems had greater nonlinearity, higher apparent activation energy, and broader relaxation time distribution than the neat epoxy resin. Further analysis based on the Adam‐Gibbs model indicated that the presence of clay nanoparticles decreased the macroscopic configurational entropy of the epoxy network, and increased the size of the cooperative rearrangement region as well as the fundamental energy barrier. The peculiar relaxation behavior observed in the present experiments was attributed to the confinement effect of nanoparticles on molecular entities during the segmental relaxation. This confinement effect led to a stronger temperature dependence of the relaxation behavior near the glass transition temperature, or greater fragility. An inverse correlation between nonexponentiality and fragility was also observed, which is consistent with the results reported in the literature.
The original MDSC curves: complex heat capacity (C_{rm P}^* ) versus temperature; the inset shows the nonexponentiality parameters (β) for all the samples.
