Successive Self-Nucleation and Annealing for the Characterization of Biomedical Ultra-High-Molecular-Weight PolyEthylene (UHMWPE) Formulations.

The Successive Self-Nucleation and Annealing (SSA) technique is a thermal fractionation method that involves subjecting a polymer sample to sequential self-nucleation and annealing steps at progressively decreasing temperatures, using differential scanning calorimetry (DSC). Since its introduction in the late 1990s, SSA has been widely applied to study the molecular structure of polymers with structural irregularities, including highly branched or crosslinked polyethylenes and random copolymers. However, the use of SSA for medical-grade ultra-high-molecular-weight polyethylene (UHMWPE), a highly linear homopolymer with minimal defects, has not yet been explored. This study aims to evaluate both its applicability to biomedical UHMWPE and its ability to reveal morphological differences among commercially available formulations. Several biomedical UHMWPE formulations, including conventional, highly cross-linked, and α-tocopherol-stabilized materials, were characterized by micro-FTIR, gel fraction and cross-link density measurements and subsequently subjected to SSA thermal fractionation. The results show that ram extrusion induces entanglements that act as interruptions in the otherwise linear chain structure, thereby enabling thermal fractionation: more than 80% of the crystalline fraction of ram-extruded UHMWPE is composed of three crystal populations melting at approximately 135, 132, and 126 °C, accompanied by four additional minor fractions at progressively lower melting temperatures. Gamma irradiation followed by thermal treatments significantly modifies the fractionation behavior, leading to the formation of an additional population of high-melting crystallites as evidenced by an increase in the number of melting peaks from 7 to 8. Oxidative degradation of highly crosslinked and annealed UHMWPE increases crystallinity by approximately 11% relative to its unoxidized counterpart but reduces the ability of the material to undergo thermal fractionation, decreasing the number of melting peaks. In contrast, the addition of low concentrations of α-tocopherol does not significantly influence the fractionation behavior. These findings demonstrate that thermal fractionation of medical-grade UHMWPE is feasible and that SSA is an effective tool for detecting morphological differences among formulations.