Dynamics of phase separation in poly(acrylonitrile-butadiene-styrene)-modified epoxy/DDS system: kinetics and...

The dynamics of phase separation and final morphologies of poly(acrylonitrile-butadiene-styrene) (ABS)-modified epoxy system based on diglycidyl ether of bisphenol A (DGEBA) cured with 4,4'-diaminodiphenylsulfone (DDS) have been monitored in situ throughout the entire curing process by using optical microscopy (OM), differential scanning calorimetry (DSC), rheometry, and small-angle laser light scattering (SALLS). The evolution of phase separation and final morphologies with substructures were explored by OM. The final morphologies of the blend cured at 150 and 165 °C are of phase-inverted type and are quite different from the final morphologies of the same blend cured at 180 °C, in which the final morphologies are cocontinuous. AFM observations of the fully cured sample confirmed the existence of three different phases, the epoxy continuous phase, SAN (styrene/acrylonitrile) continuous phase, and PB droplets at the interface, with a strong tendency to stay at SAN continuous phase. Furthermore, the continuous epoxy phase contains SAN particles and the continuous SAN phase contains epoxy particles. Cure kinetics and rheological results correspond well with the viscoelastic phase separation revealed by OM. The SALLS results display clearly that the phase separation takes place according to nucleation and growth mechanism followed by spinodal decomposition. The development of light scattering patterns during the second stage phase separation follows the Cahn-Hilliard model of spinodal demixing. Furthermore, the evolution of the scattering vector follows a Maxwell-type relaxation equation establishing the viscoelastic behavior of phase separation. The relaxation time of phase separation can be described by the Williams-Landel-Ferry equation for viscoelasticity. As a whole, the dependence of phase separation on cure temperature and the development of final morphologies and the associated mechanisms were explored in detail for the complex epoxy/ABS system.