Time- and depth-dependent changes in crosslinking and oxidation of shelf-aged polyethylene acetabular liners

Since crosslinking and oxidation of ultrahigh-molecular-weight polyethylene (UHMWPE) have important roles in determining the wear resistance of UHMWPE total joint components, the time and depth dependence of crosslinking and oxidation of new shelf-aged (2-11 years), ready-to-implant acetabular liners were studied by using solvent extraction and Fourier transform infrared spectroscopy. The ultrastructure of these materials also was examined by using low-voltage scanning electron microscopy in an oil-free vacuum. Oxidation levels increased with time and with depth (p < 0.0001) from the surface of the older liners to a maximum value at about 1-2 mm below the surface, then decreased. They were minimal at the midsection of the liners. The crosslinking of these liners decreased with time and depth (p < 0.0001) and was inversely proportional to the level of oxidation. High and depth-dependent oxidation levels were observed in all older liners made from GUR 415 and 412 resins but were distinctly absent from a comparably aged (i.e., 9 years) liner made from 1900 CM-resin. Some liners showed varying degrees of inhomogeneous and discontinuous morphologic ultrastructure in addition to varying amounts of porosity while others had a more homogeneous ultrastructure. Oxidation and crosslinking of polyethylene are time- and depth-dependent processes that are mutually competitive. We suggest that resin choice and perhaps consolidation-related variables lead to differences in polyethylene's ultrastructure. These ultrastructural differences in polyethylene's inhomogeneities, that is, the type (interconnected or closed-cell) or extent may affect the oxidation resistance of polyethylene. While oxygen diffusion to free radicals in polyethylene already is known to explain some of these time- and depth-dependent effects, perhaps such ultrastructural variations also may facilitate or retard oxygen diffusion in this material. Resin-based ultrastructural variability partially may explain the variability in the clinical performance of polyethylene total joint implant components. Thus resin choice or processing modifications related to polyethylene's ultrastructure may increase its oxidation resistance and ultimately improve the clinical wear performance of polyethylene total joint orthopedic implants.