Europium stearate additives delay oxidation of UHMWPE for orthopaedic applications: a pilot study.

BACKGROUND: Ultrahigh-molecular-weight polyethylene (UHMWPE) is used as an articulating surface in prosthetic devices. Its failure under various mechanisms after oxidation is of utmost concern. Free radicals formed during the sterilization process using high-energy irradiation result in oxidation. Europium, an element of the lanthanide family, has a unique electron configuration with an unusual lack of preference for directional bonding and notable bonding to oxygen. Because of this, it currently is used in studies for stabilization of polymers such as polyvinyl chloride. QUESTIONS/PURPOSES: We asked whether europium stearate could enhance the oxidation resistance after irradiation in nitrogen of UHMWPE. METHODS: Conventional nonirradiated and gamma-irradiated in nitrogen UHMWPE were compared with polyethylene doped with 375 ppm and 3750 ppm europium(III) stearate under the same treatment conditions. Chemical characterization was performed by Fourier transform infrared (FTIR) microspectroscopy using 200-µm thin films. The oxidation of doped samples with time was compared with that of conventional samples using accelerated oven aging. The types of oxidation products were identified by FTIR and quantified per material and treatment condition as indications of the oxidation level and mechanism. RESULTS: The generation rate of hydroperoxides and ketones was decelerated proportionally with concentration of europium stearates. The oxidative mechanism appeared similar to that of conventional polyethylene with the same types of measurable end products as ketones and hydroperoxides. Yet, the rate of generation of the latter appeared to be slowed down by the action of europium stearate. CONCLUSIONS: Europium stearate mixed in UHMWPE decelerated the oxidation reactions triggered by gamma irradiation in nitrogen, seemingly without major alteration of the oxidation mechanism.

Wear measurement of highly cross-linked UHMWPE using a 7Be tracer implantation technique.

The very low wear rates achieved with the current highly cross-linked ultrahigh molecular weight polyethylenes (UHMWPE) used in joint prostheses have proven to be difficult to measure accurately by gravimetry. Tracer methods are therefore being explored. The purpose of this study was to perform a proof-of-concept experiment on the use of the radioactive tracer beryllium-7 ((7)Be) for the determination of in vitro wear in a highly cross-linked orthopedic UHMWPE. Three cross-linked and four conventional UHMWPE pins made from compression-molded GUR 1050, were activated with 10(9) to 10(10) (7)Be nuclei using a new implantation setup that produced a homogenous distribution of implanted nuclei up to 8.5 µm below the surface. The pins were tested for wear in a six-station pin-on-flat apparatus for up to 7.1 million cycles (178 km). A Germanium gamma detector was employed to determine activity loss of the UHMWPE pins at preset intervals during the wear test. The wear of the cross-linked UHMWPE pins was readily detected and estimated to be 17 ± 3 µg per million cycles. The conventional-to-cross-linked ratio of the wear rates was 13.1 ± 0.8, in the expected range for these materials. Oxidative degradation damage from implantation was negligible; however, a weak dependence of wear on implantation dose was observed limiting the number of radioactive tracer atoms that can be introduced. Future applications of this tracer technology may include the analysis of location-specific wear, such as loss of material in the post or backside of a tibial insert.

Effect of europium(II) stearate on the mechanical properties and the oxidation resistance of UHMWPE.

The objective of this pilot study is to investigate the effect of europium(II) stearate additive on the mechanical properties and oxidation resistance of an ultra-high molecular weight polyethylene (UHMWPE), which has been used as an articulating surface in prosthetic devices for many years. It is hypothesized in this study that combining the UHMWPE with lanthanide stearates could enhance oxidation resistance, leading to better preservation of the material's mechanical integrity. Compression molded UHMWPE was doped at 0, 375 and 750 ppm of europium(II) stearate, γ-irradiated to 35 kGy in a nitrogen atmosphere, and accelerated aged in accordance with the ASTM standard F2003-02. Non-irradiated and nonaged samples were used as controls. Miniature samples were comparatively tested for mechanical properties using the small punch test. Oxidation indices (OIs) were obtained through the FTIR spectroscopy on thin film sections of all irradiated samples. The UHMWPE doped with the europium(II) stearate had the same small punch test curve shape as the conventional UHMWPE control; the ultimate displacement remained unchanged (approximately 4.33±0.02 mm), while the ultimate load and work-to-failure exhibited only small changes (<7.5% and <5.0%, respectively). The doped material was more resistant to oxidation than the control material, retaining 83% of its as-irradiated work-to-failure after irradiation and accelerated aging, versus only 53% for the control. Accelerated aging changed the average oxidation index of the control group from 0.07 to 0.40; whereas the average oxidation indices changed from 0.03 to 0.15 and from 0.05 to 0.13 for the 375 ppm and the 750 ppm doped condition, respectively.