Interaction of oxidation and crosslinking in gamma-irradiated ultrahigh molecular-weight polyethylene.

The interaction between oxidation and crosslinking in gamma-irradiated ultrahigh molecular-weight polyethylene with and without artificial aging was studied. The effect of the atmosphere during irradiation (air vs. low oxygen) occurred primarily within about 0.5 mm of the surface, that is, the depth to which oxygen had diffused when the polyethylene specimen was machined and when it was irradiated. Irradiation in the presence of oxygen induced oxidation instead of crosslinking, so that the level of crosslinking achieved was lower than that which normally would occur at the same dose in the absence of oxygen. Subsequent artificial aging reduced the gel content (crosslinking) and had a maximal effect on the surface and subsurface regions for the gamma-air and gamma-low oxygen polyethylenes, respectively. Thus the storage environments and durations prior to irradiation and prior to artificial aging must be taken into account when attempting to duplicate the oxidation-crosslinking profiles that occur with actual implants in clinical use. In addition, the oxidation mechanisms initiated by the artificial aging method used in this study (i.e., heating in air to 80 degrees C) initiated somewhat different oxidative reactions from those that occur during prolonged shelf life at room temperature or in vivo. In particular, the formation of a peak of oxidation below the free surface of the polyethylene is due to the combined effects of the distribution of residual free radicals and the diffusion gradient of the oxygen. The interactive relationship between oxidation and crosslinking characterized in the present study provides a fundamental basis for understanding the wear behavior of gamma-sterilized components in past clinical use. It also provides guidelines for the development of polyethylenes with improved resistance to oxidation and wear, with particular relevance to estimation of the amount of crosslinking need- ed to potentially eliminate the clinical problem of osteolysis. Copyright 2002 Wiley Periodicals, Inc.