Dielectric and morphological investigations of phase separation and cure in rubber-modified epoxy resins: Comparison between teta- and DDM-based systems

Real-time and equilibrium dielectric measurements, covering the frequency range 10⁻¹–10⁵ Hz, are reported on a series of rubber-modified epoxy resins, based on reaction of the diglycidyl ether of bisphenol A (DGEBA) with either triethylenetetramine (TETA) or diaminodiphenylmethylene (DDM). The rubber modifier used was a carboxyl-terminated butadiene acrylonitrile (CTBN) reactive oligomer and the phase-separated structure, the results of which was examined using both dielectric and electron microscopic techniques. The mixture was initially homogeneous, but after a short period of time, it underwent phase separation and this process was marked by the appearance of a dielectric peak associated with ion-charge migration within the occluded rubbery phase. Analysis of the peak provided information on the morphology of the system and these data were compared with information obtained from scanning electron microscopy. A phase-separated morphology was observed consisting of spherical rubber particles dispersed in an epoxy matrix. For high concentrations of rubber ≥ 10 wt %, precipitation of epoxy domains within the rubbery phase was observed. Detailed dielectric studies of the peak associated with phase separation revealed that in the case of the TETA system the peak continued to shift after vitrification, whereas in the case of DDM, it was invariant with time. The point at which the peak appears was used to determine the time at which phase separation occurred. Differences observed in the lower temperature dielectric spectra were associated with variations in the form of the phase structure and possibly reflect different degrees of densification of the matrix. Good agreement was observed between the predictions of the Maxwell—Wagner—Sillers (MWS) theory and experimental observation for these systems. © 1993 John Wiley & Sons, Inc.