Cure behavior of epoxy/MWCNT nanocomposites: The effect of nanotube surface modification

The effect of carboxyl and fluorine modified multi-wall carbon nanotubes (MWCNTs) on the curing behavior of diglycidyl ether of bisphenol A (DGEBA) epoxy resin was studied using differential scanning calorimetry (DSC), rheology and infrared spectroscopy (IR). Activation energy (Ea) and rate constants (k) obtained from isothermal DSC were the same for the neat resin and fluorinated MWCNT system (47.7 and 47.5 kJ/mol, respectively) whereas samples containing carboxylated MWCNTs exhibited a higher activation energy (61.7 kJ/mol) and lower rate constant. Comparison of the activation energies, rate constants, gelation behavior and vitrification times for all of the samples suggests that the cure mechanisms of the neat resin and fluorinated sample are similar but different from the carboxylated sample. This can be explained by the difference in how the fluorinated nanotubes react with the epoxy resin compared to the carboxylated nanotubes. Although the two systems have different reaction mechanisms, both systems have similar degrees of conversion as calculated from the infrared spectroscopic data, glass transition temperature (Tg), and predictions based on DSC data. This difference in reaction mechanism may be attributed to differences in nanotube dispersion; the fluorinated MWCNT system is more uniformly dispersed in the matrix whereas the more heterogeneously dispersed carboxylated MWCNTs can hinder mobility of the reactive species and disrupt the reaction stoichiometry on the local scale.