Formation and inhibition of free radicals in electrically stressed and aged insulating polymers

Previous work has shown that prebreakdown, electrical aging, and breakdown phenomena are directly associated with charge carriers injected from electrical contacts and their subsequent dissociative trapping and recombination. In addition, the energy released from each trapping or recombination event is dissipated in the breaking of the bonds of macromolecules, thus forming free radicals and new traps in the electrically stressed insulating polymers, as predicted by Kao's model. It is this gradual degradation process that leads to electrical aging and destructive breakdown. New experimental results are presented to confirm previous findings and a new approach to inhibit the degradation process by the incorporation of suitable dopants into the polymer. The concentration of free radicals in the polymer increases with an increasing electric field at a fixed stress time of 250 h and with increasing stress time at a fixed electric field of 833 kV cm−1. The concentration of free radicals is directly related to the concentration of new traps created by stress. However, when suitable dopants are incorporated, the initiation voltage for the occurrence of electrical treeing and the breakdown strength are both increased. The dopants tend to create shallow traps and have little effect on the deep trap concentration. This implies that the dopants act as free‐radical scavengers that tend to satisfy the unpaired electrons of the broken bonds, which create new acceptor‐like electron traps and new shallow traps. By doing so, the shallow traps screen the deep traps, thereby reducing the energy released during trapping and recombination and the probability of breaking the macromolecular bonds and causing structural degradation. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 3416–3425, 2003