ABSTRACT
A detailed calorimetric study on an epoxy-based nanocomposite system was performed employing bisphenol A diglycidyl ether (DGEBA) cured with diethylenetriamine (DETA) as the polymer matrix and a taurine-modified MgAL layered double hydroxide (T-LDH) as the nanofiller. The -NH2 group of taurine can react with DGEBA improving the interaction of the polymer with the filler. The combined X-ray scattering and electron microscopy data showed that the nanocomposite has a partially exfoliated morphology. Calorimetric studies were performed using conventional DSC, temperature modulated DSC (TMDSC) and fast scanning calorimetry (FSC) in the temperature modulated approach (TMFSC) to investigate the vitrification and molecular mobility dependent on the filler concentration. First, TMDSC and NMR were used to estimate the amount of the rigid amorphous fraction which consists of immobilized polymer segments at the nanoparticle surface. It was found to be 40 wt% for the highest filler concentration, indicating that the interface dominates the overall macroscopic properties and behavior of the material to a great extent. Second, the relaxation rates of the α-relaxation obtained by TMDSC and TMFSC were compared with the thermal and dielectric relaxation rates measured by static FSC. The investigation revealed that the system shows two distinct α-relaxation processes. Furthermore, two separate vitrification mechanisms were also found for a bulk network-former without geometrical confinement as also confirmed by NMR. This was discussed in terms of the intrinsic spatial heterogeneity on a molecular scale, which becomes more pronounced with increasing nanofiller content.
ABSTRACT
The complex effects of nanoparticles on a thermosetting material based on an anhydride cured DGEBA/boehmite nanocomposite with different particle concentrations are considered. A combination of X-ray scattering, calorimetry, including fast scanning calorimetry and temperature modulated calorimetry, and dielectric spectroscopy was employed to study the structure, the vitrification kinetics and the molecular dynamics of the nanocomposites. For the first time in the literature, for an epoxy-based composite, a detailed analysis of the X-ray data was carried out. Moreover, the unfilled polymer was found to be intrinsically heterogeneous, showing regions with different crosslinking densities, indicated by two separate dynamic glass transitions. The glass transition temperature decreases with increasing nanoparticle concentration, resulting from a change in the crosslinking density. Moreover, on the one hand, for the nanocomposites, the incorporation of nanofiller increased the number of mobile segments for low nanoparticle concentrations, due to the altered crosslinking density. On the other hand, for higher loading degrees, the number of mobile segments decreased, resulting from the formation of an immobilized interphase (RAF). The simultaneous mobilization and immobilization of the segmental dynamics cannot be separated unambiguously. By taking the sample with the highest number of mobile segments as a reference state, it was possible to estimate the amount of RAF.
