Lamellae-controlled electrical properties of polyethylene - morphology, oxidation and effects of antioxidant on the DC conductivity.

Destruction of the spherulite structure in low-density polyethylene (LDPE) is shown to result in a more insulating material at low temperatures, while the reverse effect is observed at high temperatures. On average, the change in morphology reduced the conductivity by a factor of 4, but this morphology-related decrease in conductivity was relatively small compared with the conductivity drop of more than 2 decades that was observed after slight oxidation of the LDPE (at 25 °C and 30 kV mm -1 ). The conductivity of LDPE was measured at different temperatures (25-60 °C) and at different electrical field strengths (3.3-30 kV mm -1 ) for multiple samples with a total crystalline content of 51 wt%. The transformation from a 5 μm coherent structure of spherulites in the LDPE to an evenly dispersed random lamellar phase (with retained crystallinity) was achieved by extrusion melt processing. The addition of 50 ppm commercial phenolic antioxidant to the LDPE matrix ( e.g. for the long-term use of polyethylene in high voltage direct current (HVDC) cables) gave a conductivity ca. 3 times higher than that of the same material without antioxidants at 60 °C (the operating temperature for the cables). For larger amounts of antioxidant up to 1000 ppm, the DC conductivity remained stable at ca. 1 × 10 -14 S m -1 . Finite element modeling (FEM) simulations were carried out to model the phenomena observed, and the results suggested that the higher conductivity of the spherulite-containing LDPE stems from the displacement and increased presence of polymeric irregularities (formed during crystallization) in the border regions of the spherulite structures.