Molecular orientation at the surface layer of cross-linked ultrahigh molecular weight polyethylene (UHMWPE) has been examined. Molecular orientation has been shown to affect the wear resistance and surface mechanical properties of UHMWPE under biomechanical loading conditions. This study utilizes a nondestructive synchrotron based soft x-ray technique; near edge x-ray absorption fine structure at the carbon K-edge to examine the degree of surface molecular orientation of UHMWPE subjected to various cross-linking/sterilization techniques as a function of stress and wear. UHMWPE samples prepared under gamma irradiation, ethylene-oxide (EtO) treatment, and electron beam irradiation were worn in a wear tester systematically. Results suggest that the cross-linking resists surface orientation when the samples were under tensile and biomechanical stresses. The molecular orientation in the C–C chains in the polymer showed a monotonic decrease with an increase in gamma irradiation dosage levels. EtO sterilized samples showed more C–C chain orientation than the electron beam irradiated samples, but lower than the 30kGy gamma irradiated samples. Ordered C–C chains in UHMWPE samples have been associated with more crystallinity or large strain plastic deformation of the polymer. Higher levels of gamma irradiation appear to induce cross-linking of C–C chains and render a polymer with more amorphous phase which resists orientation after wear and imparts wear resistance to the polymer.

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