Quantitative analysis of the temperature effect on the radiation crosslinking and scission of polyethylene macromolecules

The γ-radiation-induced crosslinking of low-density polyethylene over a wide temperature range was studied with a new log–logarithmic scale method for sol–gel analysis. A straight line was always obtained for the plotting of log (sol fraction) against log (dose). Gel points were accurately obtained from the plot intersects, and scission/crosslinking ratios were obtained from the plot slopes via computer simulations with GelSim6 software. The crosslinking and scission yields were determined to be 0.17 and 0.078 mmol/kJ, respectively, at 30 °C, and they increased to 2.3 and 4.4 mmol/kJ, respectively, at 300 °C. The observed regularities are explained by the fact that enhanced macromolecular motion decreases the cage effect on recombination reactions in the polymer. © 2001 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 39: 1656–1661, 2001