화학공학소재연구정보센터
Journal of Polymer Science Part B: Polymer Physics, Vol.36, No.13, 2461-2470, 1998
Curing kinetics of phase separating epoxy thermosets studied by dielectric and calorimetric investigations : A simple model for the complex dielectric permittivity
Dielectric relaxation spectroscopy (3 kHz less than or equal to f less than or equal to 3 MHz), differential scanning calorimetry, and temperature-modulated calorimetry have been performed during isothermal curing of an epoxy network (diglycidylether of bisphenol A crosslinked with diaminodiphenyl methane), and of two thermoplast modified epoxy resins (semi-interpenetrating polymer networks) consisting of the epoxy network component and different amounts (10 and 20 wt %) of a linear high T-g polymer (polysulfone or polyethersulfone). During reaction, the homogeneous-mixtures phase separate into an epoxy-rich and a linear polymer-rich phase with different mobilities of the electrical dipoles. The complex dielectric permittivity is composed of a contribution from the ionic de-conductivity and a contribution from relaxations of the permanent electrical dipoles in the two phases. The decrease of the de-conductivity in the initial stage of cure is related to the time for gelation or vitrification. The contribution of the dipole relaxations to the dielectric permittivity reflects an increase of the relaxation times with curing time for both phases. The time-dependent changes in the complex dielectric permittivity are described by a simple two-phase model based on two Havriliak-Negami functions combined with Vogel-Fulcher equations for the description of the curing-time dependence of the relaxation times. The increase of the relaxation times in the phases during isothermal curing is incorporated by time-dependent Vogel temperatures. The latter are related to the time evolution of the glass-transition temperatures in the two phases measured independently by calorimetry.