| Abstract: | The complex degradation behavior of a poly(vinyl chloride) (PVC) cable jacketing material in combined radiation/temperature/air aging environments is experimentally separated into two dominant radiation dose-rate effect mechanisms. The first, operative at high dose rates, involves diffusion-limited oxidation, which leads to heterogeneously oxidized samples. The second, important at low dose rates, involves thermally-induced breakdown of intermediate peroxides. In the homogeneous degradation regime, a theoretical kinetic model is derived which, based on experimental evidence, assumes unimolecular termination kinetics and rate-determining, hydroperoxide-mediated branching reactions. Dependent upon the ratio of particular rate constants, the model predicts that dose-rate effects will either continue to increase or eventually disappear as the dose rate is lowered. Theoretical analysis of sequential (radiation followed by temperature exposures) aging experiments allows a time–temperature–dose rate shifting procedure to be developed. Using this procedure, higher temperature combined environment results can be shifted to a lower reference temperature, thereby extending the lower temperature results to lower (and experimentally inaccessible) dose rates. By applying this procedure to experimental PVC data, evidence in support of the theoretical model is obtained. In addition, model predictions are shown to agree with 12-year real-time aging results. |
