Department of Orthopaedic Surgery, Tokyo Medical University, 6-7-1, Nishishinjuku, Shinjuku-ku, 160-0023 Tokyo, Japan.
Ceramic Physics Laboratory and Research Institute for Nanoscience, Kyoto Institute of Technology, Sakyo-ku, Matsugasaki, 606-8585 Kyoto, Japan.
J Mech Behav Biomed Mater. 2014 Mar;31:31-44. doi: 10.1016/j.jmbbm.2012.12.009. Epub 2013 Jan 11.
Infusion of vitamin E (α-tocopherol) in highly crosslinked ultra-high molecular weight polyethylene (UHMWPE) liners has been conceived to achieve superior oxidation stability while preserving enhanced mechanical properties as compared to post-irradiation remelted liners. However, the presence of an antioxidant in the material microstructure brings an issue of concern in whether a "foreign substance" might reduce radiation crosslinking efficiency and/or change microstructural characteristics by diffusing into UHMWPE. The key to clarify this fundamental issue resides in performing a quantitative evaluation of the obtained material structure and its polymeric chain mobility on the molecular scale. In this paper, a Raman spectroscopic examination is presented of molecular orientation and phase fractions in as-processed vitamin E-infused UHMWPE acetabular liners in comparison with a model (undoped and unirradiated/uncrosslinked) and a conventional (undoped and 33kGy-sterilized by gamma-irradiation) UHMWPE liners. The microstructural responses of structurally different liners to externally applied compressive strain were also monitored. The main results of the spectroscopic analyses can be summarized as follows: (i) preliminary gamma irradiation reduced the fraction of amorphous phase and increased the degree of molecular alignment, the vitamin E-infused liner preserving the crystallinity level achieved by the 100-kGy irradiation injected before infusion; (ii) the presence of vitamin E significantly promoted orientational randomness, which increased with increasing compressive strain magnitude, a phenomenon beneficial to minimize strain-softening-assisted wear phenomena.
将维生素 E(α-生育酚)注入高度交联的超高分子量聚乙烯(UHMWPE)衬垫中,旨在实现卓越的氧化稳定性,同时保持增强的机械性能,优于辐照后重熔的衬垫。然而,材料微观结构中抗氧化剂的存在带来了一个问题,即“外来物质”是否可能通过扩散到 UHMWPE 中降低辐射交联效率和/或改变微观结构特征。澄清这个基本问题的关键在于在分子尺度上对获得的材料结构及其聚合物链迁移率进行定量评估。本文通过拉曼光谱检查了加工过程中的维生素 E 注入 UHMWPE 髋臼衬垫中的分子取向和相分数,与模型(未掺杂和未辐照/未交联)和传统(未掺杂和 33kGy-γ 辐照灭菌)UHMWPE 衬垫进行了比较。还监测了结构不同的衬垫对外部施加压缩应变的微观结构响应。光谱分析的主要结果可以总结如下:(i)初步的伽马辐照降低了非晶相分数并增加了分子取向度,维生素 E 注入衬垫保留了注入前 100kGy 辐照所达到的结晶度水平;(ii)维生素 E 的存在显著促进了取向随机性,随着压缩应变幅度的增加而增加,这一现象有利于最小化应变软化辅助磨损现象。