The influence of high electrical fields (above 20 kV mm−1) on ageing, polarization and morphology of polyethylene (PE) is discussed. Infrared and positron annihilation spectroscopy measurements together with capacitance measurements tend to indicate that polymer morphology is modified by high fields. We show that accelerated electrical ageing characteristics of PE are directly linked to morphology changes induced by the field. Below a so‐called critical field, the activation volume of the ageing process is dependent on field‐induced strain. Above the critical field, the amorphous phase is significantly deformed and weak van der Waals bonds are broken, leading to another faster ageing regime. There is excellent agreement between the proposed model and experimental data obtained with PE‐insulated high voltage cables. The possible relation between the submicrocavity formation proposed in our ageing model and various polarization measurements is discussed. It is our contention that strong charge injection occurs only after submicrocavity formation, ie after weak bonds are broken. As is well known, polarization currents obtained under high fields are controlled by space charges. It seems that wave packets and the negative resistance observed above 100 kV mm−1 in PE are associated with a steady state in field‐induced defect formation. This suggests that space charges are related to the formation of submicrocavities and, therefore, are a consequence and not a cause of high field ageing.
© 2002 Society of Chemical Industry