title: Crosslink density, oxidation and chain scission in retrieved, highly cross-linked UHMWPE tibial bearings.
abstract: Irradiated, thermally stabilized, highly cross-linked UHMWPE bearings have demonstrated superior wear performance and improved in vitro oxidation resistance compared with terminally gamma-sterilized bearings, yet retrieval analysis reveals unanticipated in vivo oxidation in these materials despite fewer or no measurable free radicals. There has been little evidence to date that the oxidation mechanism in thermally stabilized materials is the same as that in conventional materials, and so it is unknown whether oxidation in these materials is leading to chain scission and a degradation of mechanical properties, molecular weight, and crosslink density. The aim of this study was to determine whether measured in vivo oxidation in retrieved, highly cross-linked tibial bearings corresponds with a decreasing crosslink density. Analysis of three tibial bearing materials revealed that crosslink density decreased following in vivo duration, and that the change in crosslink density was strongly correlated with oxidation. The results suggest that oxidation in highly cross-linked materials is causing chain scissions that may, in time, impact the material properties. If in vivo oxidation continues over longer durations, there is potential for a clinically significant degradation of mechanical properties.
authors.affiliation: Thayer School of Engineering, Dartmouth College, 14 Engineering Drive, Hanover, NH 03755, USA. Electronic address: Steven.D.Reinitz.TH@Dartmouth.edu.
authors.forename: Steven D
authors.initials: SD
authors.lastname: Reinitz
authors.affiliation: Thayer School of Engineering, Dartmouth College, 14 Engineering Drive, Hanover, NH 03755, USA.
authors.forename: Barbara H
authors.initials: BH
authors.lastname: Currier
authors.affiliation: Thayer School of Engineering, Dartmouth College, 14 Engineering Drive, Hanover, NH 03755, USA.
authors.forename: Rayna A
authors.initials: RA
authors.lastname: Levine
authors.affiliation: Thayer School of Engineering, Dartmouth College, 14 Engineering Drive, Hanover, NH 03755, USA.
authors.forename: Douglas W
authors.initials: DW
authors.lastname: Van Citters
mesh_terms: D019645:Arthroplasty, Replacement, Knee; D018786:Bone Substitutes / Q000737:chemistry*; D003432:Cross-Linking Reagents / Q000737:chemistry*; D005720:Gamma Rays; D007720:Knee Prosthesis; D010084:Oxidation-Reduction; D011095:Polyethylenes / Q000737:chemistry*; D017550:Spectroscopy, Fourier Transform Infrared; D013242:Sterilization; D013977:Tibia / Q000601:surgery
chemical_list: D018786:Bone Substitutes; D003432:Cross-Linking Reagents; D011095:Polyethylenes; C111601:ultra-high molecular weight polyethylene
keywords: Arthroplasty; Cross-linking; FTIR; Knee replacement; Oxidation; Polyethylene