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The addition of nanofillers can have a significant influence on the resin stoichiometry of thermosetting polymer systems. Based on differential scanning calorimetry (DSC) results, it is estimated that the inclusion of 2 and 5 wt% of silicon nitride nanofiller displaces the resin/hardener stoichiometry of an epoxy/amine network by 6.5 and 18%, respectively. Dielectric spectroscopy results confirm the above findings, in that the spectra of the nanocomposite samples were found to be equivalent to the spectra of unfilled samples when the above stoichiometric effect was taken into account. Therefore, this study provides clear evidence that the presence of a nanofiller can directly and significantly affect the curing process of an epoxy network. Consequently, this should always be considered when introducing nanofillers into thermosetting matrices. These results indicate the presence of covalent bonding between the nanoparticles and the surrounding polymer and, therefore, provide an opportunity to explore the influence of this bonding on the molecular dynamics of the polymer layer around the particles. However, the obtained DSC and dielectric spectroscopy results suggest that, in the system considered here, either the covalent bonding does not have an appreciable influence on the segmental dynamics of the polymer, as revealed by these techniques, or that the thickness of the affected layer is less than 1 nm and therefore too small to be distinguished from experimental uncertainties.

journal of materials science

Influence of filler/matrix interactions on resin/hardener stoichiometry, molecular dynamics, and particle dispersion of silicon nitride/epoxy nanocomposites