Deep trapping centers in crosslinked polyethylene investigated by molecular modeling and luminescence techniques

Space charge in crosslinked polyethylene (XLPE) has been detected under both ac and dc fields. Its role in electrical aging and breakdown is recognized, but not deeply understood. It is thought that identification of the trapping centers in this material would help improve the modeling of conduction and electrical aging as well as making possible the design of crosslinked materials with improved properties. We have developed theoretical and experimental approaches to this problem which emphasize the role of chemical traps acting as deep trapping centers. Molecular modeling is used to estimate the trap depth for negative and positive charge carriers associated with the main by-products of crosslinking reactions (using dicumyl peroxide as a crosslinking agent) since their aromatic structure makes them candidates for deep traps. Calculations on acetophenone, n-methyl styrene and cumyl alcohol show that they indeed can act as deep traps. Because such deep traps can act as recombination centers, their involvement in charge trapping can be checked in specially designed luminescence experiments. In our experiments, charges of both polarities are generated at the surface of the material under study by using a non-reactive cold plasma in helium. The analysis of the decay kinetics and emission spectrum of the subsequent luminescence allows us to define unambiguously the time range in which charge recombination is the dominant excitation process of the luminescence. The emission spectra obtained within this time range provide the optical fingerprint of chromophores acting as deep traps in the material. The low-density polyethylene (LDPE) doped with crosslinking byproducts and XLPE (film and cable peeling) have been investigated. Their role in charge trapping is apparent in the luminescence experiments and in space charge distribution analysis. In thermally treated XLPE, it is shown that other species strongly bonded to the polymer chain are also able to trap electrical charges.