Introduction. Oxidation of ultrahigh molecular weight polyethylene (UHMWPE) can lead to failure of implants used in total joints. Cyclic loading is postulated to be one mechanism of in vivo oxidation in UHMWPE components as one previous study has shown [1]. We developed an accelerated aging test that incorporated compressive cyclic loading that the UHMWPE components would be exposed to in vivo. Surgeons are moving towards larger femoral heads in hip arthroplasty and removing less bone in knee arthroplasty necessitating thinner UHMWPE components. We hypothesized that, in this accelerated aging test, thinner UHMWPE components would be more susceptible to oxidation caused by the cyclic loading due to higher stresses in the material. Materials and Methods. All samples tested in this study were Conventional PE: GUR1050 was machined into test specimens, vacuum packaged and gamma sterilized. Test samples were blocks 100 mm × 89 mm in cross-section with 3 different thicknesses: 1 mm, 3 mm, and 10 mm (n=3 each). Three cylinders were cored out of each test sample to serve as controls (Fig 1a) that were physically separated and thereby isolating the oxidation attributable to an applied compressive cyclic load. The controls were placed back into the holes from where they were cored during testing. Compressive loading was administered by a 12.5 mm diameter applicator affixed to a hydraulic test frame (Fig 1b), and all testing was done at 80°C in air. A sinusoidal compressive cyclic stress between 1 and 10 MPa was applied at 5 Hz for 7 days. Microtomed thin films from all samples were analyzed via Fourier Transform Infrared Spectroscopy (FTIR) to quantify oxidation [2] after testing. Oxidation was measured through the thickness of the sample at targeted points along the length from directly underneath the center of the load applicator to 10mm away (Fig 1a). Oxidation was also measured through the thickness of the cylindrical controls. Results. The oxidation profiles of each sample at 0.0mm (Fig 2a) and 3.0mm (Fig 2b) from the center point of load application showed that as one decreases the thickness of the test sample the oxidation levels of the sample increase. Both locations showed increased oxidation over the control samples. Discussion. Cyclic loading increased the rate of oxidation of gamma sterilized UHMWPE. The oxidation also increased with decreasing thickness of the UHMWPE samples. This oxidation could potentially accelerate the long term oxidative instability and could contribute to the delamination failure of tibial inserts. For figures/tables, please contact authors directly.

Background. Sequentially annealed, highly crosslinked polyethylene (HXLPE) has been used clinically in total knee arthroplasty (TKA) for over a decade[1]. However, little is known about the reasons for HXLPE revision, its surface damage mechanisms, or its in vivo oxidative stability relative to conventional polyethylene. We asked whether retrieved sequentially annealed HLXPE tibial inserts exhibited: (1) similar reasons for revision; (2) enhanced resistance to surface damage; and (3) enhanced oxidative stability, when compared with tibial inserts fabricated from conventional gamma inert sterilized polyethylene (control). Methods. Four hundred and fifty-six revised tibial inserts in two cohorts (sequentially annealed and conventional UHMWPE control) were collected in a multicenter retrieval program between 2000 and 2016. We controlled for implantation time between the two cohorts by excluding tibial inserts with a greater implantation time than the longest term sequentially annealed retrieval (9.5 years). The mean implantation time (± standard deviation) for the sequentially annealed components was 1.9 ± 1.7 years, and for the control inserts, 3.4 ± 2.7 years (Figure 1). Reasons for HXLPE revision were assessed based on medical records, radiographs, and examinations of the retrieved components. Surface damage mechanisms were assessed using the Hood method[2]. Oxidation was measured at the bearing surface, the backside surface, the anterior and posterior faces, as well as the post (when available) using FTIR (ASTM F2102). Surface damage and oxidation analyses were available for 338 of the components. We used nonparametric statistical testing to analyze for differences in oxidation and surface damage when adjusting for polyethylene formulation as a function of implantation time. Results. The tibial inserts in both cohorts were revised most frequently for loosening, infection, and instability. Instability was observed more frequently in inserts without a stabilizing post. In both cohorts, the most commonly observed surface damage mechanisms were burnishing, pitting, and scratching. Delamination was rare and only observed in 2 sequentially annealed inserts and 7 inserts in the control cohort. We observed six cases of posterior condyle fracture, which was always associated with instability (Figure 2). 5/6 of the fracture cases did not have a stabilizing post. Oxidation indices of the sequentially annealed inserts were, on average, low (ASTM oxidation index < 1) and not significantly different than the control inserts on the bearing surface and anterior/posterior face (Figure 3). Discussion. The findings of this study document the reasons for revision, surface damage mechanisms, and oxidative behavior of sequentially annealed HXLPE for TKA. We observed evidence of low in vivo oxidation in both retrieved sequentially annealed HXLPE and control tibial inserts. We found no association between the levels of oxidation and clinical performance of the HXLPE tibial components. However, because of the short-term follow-up, analysis of longer-term retrievals may be appropriate

Introduction. Inradiation cross-linked and melted ultrahigh molecular weight polyethylene (UHMWPE) total joint implants, the oxidation potential is afforded to the material by by post-irradiation melting. The resulting cross-linked UHMWPE does not contain detectable free radicals at the time of implantation and was expected to be resistant against oxidation for the lifetime of the implants. Recently, analysis of long-term retrievals revealed detectable oxidation in irradiated and melted UHMWPEs, suggesting the presence of oxidation mechanisms initiated by mechanisms other than those involving the free radicals at the time of implantation. However, the effect of oxidation on these materials was not well studied. We determined the effects of in vitro oxidation on the wear and mechanical properties of irradiated and melted UHMWPEs. Materials and Methods. Medical grade slab compression molded UHMWPE (GUR1050) was irradiated using 10, 50, 75, 100, 120 or 150 kGy. The irradiated and melted UHMWPEs were accelerated aged at 70°C for 2, 3, 4, 6 and 8 weeks at 5 atm of oxygen. Oxidation profiles were determined by first microtoming 150 μm cross sections; these were then extracted by boiling hexane for 16 hours and vacuum dried for 24 hours. They were then analyzed on an infrared microscope as a function of depth away from the surface. An oxidation index was calculated per ASTM 2102 as the ratio of the area under the carbonyl peak at 1740 cm-1 to the area under the crystalline polyethylene 1895 cm-1 peak. The cross-link density was calculated as previously described (Oral 2010). The wear rate was determined using a custom-designed pin-on-disc wear tester against CoCr polished discs at 2 Hz and a rectangular path of 5 × 10 mm in undiluted bovine serum (Bragdon 2001). Tensile mechanical properties were determined using Type V dogbones according to ASTM D638. Results and Discussion. Oxidation increased as a function of aging duration for all UHMWPE samples. The cross-link density decreased non-linearly with increasing oxidation and the wear rate increased non-linearly. The dependence of wear on cross-link density was different for freshly irradiated, unoxidized samples in contrast to aged and oxidized samples (Figure 1). The elongation at break and the ultimate tensile strength decreased with increasing oxidation (Figure 2) and the modulus increased with increasing oxidation. There was an increase in the oxidation rates and oxidation levels of irradiated and melted UHMWPEs with increasing radiation dose (Figure 1), which suggested that regardless of the presence of residual free radicals, increased cross-linking made the material more prone to oxidation and oxidative degradation. The wear rate was not very sensitive to oxidation with an increase only observed at an oxidation index of 1 (Figure 3), suggesting a significant level of degradation and oxidative damage only at this level of oxidation. In contrast, the tensile strength and elongation-at-break were very sensitive to oxidation, showing severe degradation at low oxidation levels. Significance. This is the first study exploring the effects of simulated oxidation in irradiated and melted UHMWPEs without detectable free radicals known to cause oxidation. We have shown that when oxidation occurs, severe degradation may occur in irradiated and melted UHMWPEs

Introduction. The purpose of this multicenter study was to assess the oxidative stability, mechanical behavior, wear and reasons for revision of 2nd generation sequentially annealed HXLPE, X3, and compare it to 1. st. generation XLPE, Crossfire. We hypothesized that X3 would exhibit similar wear rates but lower oxidation than Crossfire. Methods. 182 hip liners were consecutively retrieved during revision surgeries at 7 surgical centers and continuously analyzed over the past 12 years in a prospective, multicenter study. 90 were highly crosslinked and annealed (Crossfire; Implanted 4.2±3.4 years, max: 11 years), and 92 were highly crosslinked and annealed in 3 sequential steps (X3; Implanted 1.2±1.5 years; max: 5 years). Oxidation was characterized in accordance with ASTM 2102 using transmission FTIR performed on thin sections (∼200μm) from the superior/inferior axis. Mechanical behavior was assessed via the small punch test (ASTM 2183). Results. The liners were revised predominantly for loosening, instability, and infection. No differences were detected in linear penetration rates rates between the X3 and Crossfire liners (p=0.40), independent of head size. Oxidation was comparable between the Crossfire and X3 cohorts at the bearing surface, backside, and locking mechanism (p>0.05). At the rim, X3 liners exhibited lower oxidation than Crossfire (p<0.001). Ultimate strength of the HLXPE was not significantly different between X3 and Crossfire (p=0.996). Discussion. This ongoing study continues to evaluate the polyethylene properties and reasons for revision among clinically relevant HXLPEs used in total hip replacement. Both Crossfire retrievals, implanted for up to 11 years, and X3 retrievals, implanted up to 5 years, have thus far proven effective at reducing wear rates. Mechanical behavior oxidative stability has been preserved at the bearing surface of the retrievals for both materials. The oxidative stability of Crossfire and X3 at the rim face of the liners, however, is formulation dependent. With respect to oxidation, it is clear that sequential annealing reduced rim oxidation when compared with first-generation annealing

One of serious issues in total hip arthroplasty (THA) is the osteolysis which results in aseptic loosening caused by the wear particles from a polyethylene (PE) acetabular cup. In addition, oxidation degradation of PE cup resulting in the fracture or the severe wear caused by the reduction of mechanical properties in vivo is also the issue. The oxidation degradation is considered to be induced by residual free radicals generated by gamma-ray irradiation for cross-linking to reduce wear or for sterilization. In this study, (1) wear property, (2) oxidation degradation of retrieved PE and highly cross-linked PE (CLPE) cups against alumina ceramic femoral heads, and (3) the correlation between those properties were evaluated. The radiographic wear of six conventional PE cups with the mean follow-up of 19.1–23.3 years and 60 CLPE cups with the mean follow-up of 3.1–9.1 years were measured by a non-radiostereometric analysis method (Vectorworks. ®. 10.5 software package). As a retrieval analysis, 26 retrieved acetabular cups were evaluated; 16 cups were ethylene oxide gas-sterilized conventional PE cups with clinical use for 16.0–24.9 years and 10 cups were gamma-ray-sterilized CLPE cups with clinical use for 0.9–6.7 years. The linear and the volumetric wear were measured using a three-dimensional (3D) coordinate measurement machine. The shapes of unworn and worn surfaces with 15- and 30-point intervals, respectively, were measured. Oxidation degradation of the surface, sub-surface and inner for both worn and unworn parts of the retrieved cups was measured using a Fourier-transform infrared (FT-IR) spectroscopy. Oxidation indices were calculated using the peak at 1740 cm. −1. and 1370 cm. −1. according to ASTM F2012. In the radiographic analysis, the linear wear rate of CLPE cups was significantly lower than that of conventional PE cups [Fig. 1]. In the retrieval analysis, the linear wear rate of CLPE cups (mean: 0.07 mm/year) showed a 51% reduction (p = 0.002) compared to conventional PE cups (mean: 0.14 mm/year) [Fig. 2]. The retrieval and the radiographic analysis for both conventional PE and CLPE cups showed similar results (p = 0.7 and 0.1, respectively). Maximum oxidation indices for CLPE cups were similar to those of conventional PE cups regardless of the difference of clinical duration [Fig. 3]. This result is different from in vivo wear, which increases as the clinical duration. For both conventional PE and CLPE cups, the oxidation indices of subsurface were higher than those for surface. The worn parts showed higher oxidation indices than those for unworn parts. From the results, even when the free radicals were so few or absent, the oxidation degradation would be induced in vivo. In conclusion, the wear resistance for CLPE cups was greater than that for conventional PE cups from both radiographic and retrieval analyses. The in vivo oxidation degradation might not be caused by only residual free radicals. It was found that oxidation degradation of PE cups when used with alumina ceramic femoral heads is not correlated to their wear properties

INTRODUCTION. Multiple sources have consistently reported oxidation indices less than 0.1 with Marathon® inserts implanted up to 10 years. Understanding effects of oxidation level on UHMWPE wear in vivo is of great value. The objective of this study is to characterize the wear performance of Marathon® acetabular inserts at various levels of artificially induced oxidation, quantified using Bulk Oxidation Index (BOI) as determined per ASTM F2102, and to ascertain if wear rate is affected by progressive polyethylene oxidation. METHODS. GUR 1050 UHMWPE acetabular inserts, re-melted and cross-linked at 5.0Mrad (Marathon®, DePuy Synthes Joint Reconstruction, Warsaw, IN), were artificially aged per ASTM F-2003 in a stainless steel chamber at 5 atm. oxygen pressure and 70°C. Samples were maintained at temperature for 9, 10.4 and 11 weeks. After aging was completed, Fourier Transform Infra-Red (FTIR) spectroscopy was employed on one insert from each time point to evaluate the induced oxidation as a result of artificial aging. Resulting induced BOI values measured by FTIR were 0.195, 0.528 and 1.184. UHMWPE inserts had an inner diameter of 28mm and an outer diameter of 48mm and were articulated against 28mm diameter M-Spec® metal femoral heads (DePuy Synthes Joint Reconstruction, Warsaw, IN). Testing was conducted on a 12-station AMTI ADL hip simulator (AMTI, Watertown, MA) with load soak controls per ISO 14242-1:2014(E) in bovine serum (18mg/mL total protein concentration) supplemented with 0.056% sodium azide (preservative) and 5.56mM EDTA (calcium stabilizer). The UHMWPE inserts were removed from the machine, cleaned, and gravimetric wear determined per ISO 14242-2:2000(E) every 0.5 million cycles (MCyc) for 4.0 MCyc total. A two-tailed student's t-test was used (variance determined by F-test results) to analyze differences in wear rates between the three test groups. RESULTS. After 4.0 MCyc of wear testing, the average wear rate of the Marathon® UHMWPE acetabular inserts with OI levels of 0.195, 0.528 and 1.184 articulated against the CoCrMo femoral heads were 6.0 ± 4.2 mg/MCyc (±95% confidence interval), 8.7 ± 0.4 mg/MCyc and 15.3 ± 2.2 mg/MCyc, respectively (Figure 1). As BOI level increased, the wear rate also increased. Wear rates of inserts with BOI of 0.195 compared to 0.528 were not significantly different (p=0.11). Wear rates of inserts with BOI of 0.195 were significantly lower (p=0.00) compared to 1.184. Wear rates of inserts with BOI levels of 0.528 were significantly lower (p=0.00) compared to 1.184. DISCUSSION. This study aimed to characterize the wear performance of Marathon® acetabular inserts at three levels of oxidation created by accelerated aging. Artificially aged inserts with a BOI level similar to those reported from clinically retrieved Marathon® inserts (0.195) had a wear rate equivalent to non-aged inserts previously tested (data not shown), indicating the in vivo oxidation of this highly cross-linked UHMWPE has no effect on wear rate. Although not measured clinically, higher levels of oxidation may result in significantly higher wear rates in vivo

Introduction. Highly crosslinked polyethylene (HXLPE) was clinically introduced approximately a decade and a half ago to reduce polyethylene wear rates and subsequent osteolysis. Clinical and radiographic studies have repeatedly shown increased wear resistance, however concerns of rim oxidation and fatigue fracture remain. Although short to intermediate term retrieval studies of these materials are available, the long-term behavior of these materials remains unclear. Methods. Between 2000 and 2015, 115 1st generation HXLPE acetabular liners implanted for 5 or more years were collected and analyzed as part of an ongoing, multi-institutional orthopaedic implant retrieval program. There were two material cohorts based on thermal processing (annealed (n=45) and remelted (n=70)). Each cohort was stratified into two more cohorts based on implantation time (5 – 10 years and >10 years). For annealed components, the intermediate-term liners (n=30) were implanted on average (±SD) for 7.3 ± 1.7 years while the long-term liners (n=15) were implanted for 11.3 ± 1.8 years. For remelted components, the intermediate-term liners (n=59) were implanted on average (±SD) for 7.2 ± 1.3 years while the long-term liners (n=11) were implanted for 11.3 ± 1.2 years. For each cohort, the predominant revision reasons were loosening, instability, and infection (Figure 1). Short-term liners (in-vivo <5ys) from previous studies were analyzed using the same protocol for use as a reference. For oxidation analysis, thin slices (∼200 μm) were taken from the superior/inferior axis and subsequently boiled in heptane for 6 hours to remove absorbed lipids that may interfere with the oxidation analysis. 3mm line profiles (in 100μm increments) were taken perpendicular to the surface at each region of interest. Oxidation indices were calculated according to ASTM 2102. Penetration was measured directly using a calibrated micrometer (accuracy=0.001mm). Results. The penetration rates for both the annealed and remelted cohorts were low and similar between the two material cohorts (Figure 2). There were several cases of fractured zirconia heads associated with a manufacturer recall that resulted in higher penetration rates. At the bearing and rim surfaces, the annealed liners had higher oxidation indices than the remelted components (p<0.001). For the remelted components, the intermediate-term liners had higher oxidation indices than the short-term liners (p=0.001). For the annealed liners, both the long-term and intermediate-term liners had higher oxidation indices compared with the short-term liners (p=0.007 and 0.001, respectively). Discussion. Thermally treated first generation HXLPEs were introduced to reduce polyethylene wear and prevent oxidative degradation. The results of this study suggest that both thermally treated HXLPEs demonstrate lower penetration rates than conventional polyethylene, however, the resistance to oxidation was formulation dependent. Specifically, the remelted components were more effective at preventing oxidation than the annealed liners. However, despite the lack of measurable free radicals, we were able to observe temporal changes in the oxidation of the remelted liners. Future work will include analysis of long-term 1stgeneration annealed HXLPE to fully assess its performance in the second decade of service

Introduction. First-generation annealed HXLPE has been clinically successful at reducing both clinical wear rates and the incidence of osteolysis in total hip arthroplasty. However, studies have observed oxidative and mechanical degradation occurring in annealed HXLPE. Thus, it is unclear whether the favorable clinical performance of 1st generation HXLPE is due to the preservation of bearing surface tribological properties or, at least partially, to the reduction in patient activity. The purpose of this study was to evaluate the in vitro wear performance (assessed using multidirectional pin-on-disk (POD) testing) of 1. st. -generation annealed HXLPE with respect to in vivo duration, clinical wear rates, oxidation, and mechanical properties. Materials and Methods. 103 1. st. -generation annealed HXLPE liners were collected at revision surgery. 39 annealed HXLPE liners were selected based on their implantation time and assigned to three equally sized cohorts (n=13 per group); short-term (1.4–2.7y), intermediate term (5.2–8.0y) and long-term (8.3–12.5y). From each retrieved liner, two 9-mm cores were obtained (one from the superior region and one from the inferior region). Sixteen cores were fabricated from unimplanted HXLPE liners that were removed from their packaging and six pins from unirradiated GUR 1050 resin served as positive controls. Multidirectional POD wear testing was conducted against wrought CoCr disks in a physiologically relevant lubricant (20 g/L protein concentration) using a 100-station SuperPOD (Phoenix Tribology, UK). Each pin had its own chamber with 15mL lubricant maintained at 37±1°C. An elliptical wear pattern with a static contact stress of 2.0 MPa was employed. Testing was carried out to 1.75 million cycles at 1.0 Hz and wear was assessed gravimetrically. POD wear rates were calculated using a linear regression of volumetric losses. In vivo penetration was measured directly using a calibrated micrometer. Oxidation was assessed on thin films obtained from superior and inferior regions of the liners (ASTM 2102). Mechanical properties were assessed using the small punch test (ASTM 2183). Results. In vitro wear rates from the SuperPOD were positively correlated with implantation time (Rho=0.27; p=0.015) and average oxidation (Rho=0.36; p=0.004) at the bearing surface of the retrieved HXLPE liners. All retrieved HXLPE cohorts had lower in vitro wear rates than uncrosslinked positive control (p≤0.03) and higher wear rates than the never-implanted HXLPE cohort (p <0.001). POD wear rates were negatively correlated with small punch ultimate load (p<0.01). However, the in vitro wear rates were not correlated with clinical penetration rates (p=0.71). Discussion. This study investigated the effects of in vivo degradation on 1. st. -generation annealed HXLPE liners. The data in this study suggest that the tribological properties degrade due to in vivo oxidation as the liner is exposed to the in vivo environment. The clinical implications of these findings, however, are not clear as the clinical penetration rates were not correlated with the in vitro POD wear rates. This may be partially due, to decreasing patient activity as they age. These findings will be useful for comparison for evaluating the in vitro wear properties of other HXLPEs, including 2nd generation HXLPE. Acknowledgements. This study was supported by the NIH(NIAMS) R01AR47904

Introduction

Cobalt chrome femoral head has been used widely in total hip arthroplasty and has shown favorable outcome. However, there is still of concern of potential metal toxicity from the wear debris. In the other hand, titanium is well known for its biocompatibility but it is not used in bearing surface of arthroplasty due to its brittleness. Recently, coating of the prosthesis using plasma electrolytic oxidation (PEO) has shown favorable surface protection. Thus, in this study, we tried to find out whether the PEO coating on the titanium surface would provide surface protection.

Introduction

The longevity of highly cross-linked polyethylene (XLPE) bearings is primarily determined by its resistance to long-term oxidative degradation. Addition of vitamin E to XLPE is designed to extend in vivo life, although it has unintended consequences of inducing higher frictional torque and increased wear when articulating against metallic femoral heads.^1–3 Conversely, lower friction was observed when oxide ceramic heads were utilized.³ Previous studies suggest that oxide ceramics may contribute to XLPE oxidation, whereas a non-oxide ceramic, silicon nitride (Si₃N₄), might limit XLPE's degradation.⁴ To corroborate this observation, an accelerated hydrothermal ageing experiment was conducted using static hydrothermal contact between XLPE and commercially-available ceramic femoral heads.

Introduction

Micro-arc oxidation (MAO) is an electrochemical method used to treat metal surfaces. It provides nanoporous pits, and thick oxide layers, and incorporates calcium and phosphorus into the coating layer of titanium alloy. This modification on the surface of titanium alloy by MAO coating would improve the ability of cementless stems to osseointegrate. In spite of these structural and chemical advantages, clinical study of total hip arthroplasty (THA) using MAO coated stem has not yet been reported. In this study, we evaluated the clinical and radiographic results associated with cementless grit-blasted tapered-wedge stems that were identical in geometry but differed with regard to surface treatment with or without MAO coating.

Introduction:

The solvent extraction step applied in conventional oxidation measurement protocols for UHMWPE retrievals resulted in an elevated oxidation index (OI) in remelted highly cross-linked UHMWPE (RM-HXLPE). The present study seeks to confirm the effect of solvent extraction on OI measurement and to understand the relationships among soak-aging, fluid uptake, and resulting OI from various test protocols.

Introduction

In total hip arthroplasty (THA), polyethylene (PE) liner oxidation leads to material degradation and increased wear, with many strategies targeting its delay or prevention. However, the effect of femoral head material composition on PE degradation for ceramic-PE articulation is yet unknown. Therefore, using two different ceramic materials, we compared PE surface alterations occurring during a series of standard ceramic-PE articulation tests.

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. There has been little evidence to date that oxidation in these materials is leading to degradation of mechanical properties, but since oxidation has previously been shown to cause chain scission in other materials, there is the potential for oxidation to cause decreased molecular weight and crosslink density. The aim of this study was to determine whether measured in vivo oxidation in highly cross-linked tibial bearings corresponds with a decreasing crosslink density. Retrieval analysis for three tibial bearing materials reveals that crosslink density is decreasing following in vivo duration, and that the change in crosslink density is strongly correlated with oxidation. The results suggest that oxidation in highly cross-linked materials is causing chain scissions that may impact the material properties. If the correlation between oxidation and duration continues, then as longer duration, more oxidized devices are retrieved there is a potential for measurable mechanical property changes.

Introduction. While advances in joint-replacement technology have made total ankle arthroplasty a viable treatment for end-stage arthritis, revision rates for ankle replacements are higher than in hip or knee replacements [1]. The questions asked in this study were (1) what retrieved ankle devices demonstrate about ankle arthroplasty failures, and (2) how do these failures compare to those seen in the hip and the knee?. Materials and Methods. An IRB-approved retrieval laboratory received retrieved polyethylene inserts and surgeon-supplied reason for revision from 70 total-ankles (7 designs, including five currently-marketed designs) from 2002 to the present. All retrievals were rated for clinical damage. Polyethylene inserts received six months or less after retrieval (n=45) were analyzed for oxidation using Fourier Transform Infrared (FTIR) spectroscopy, reported as maximum ketone oxidation index [2]. Insert sterilization method was verified using trans-vinylene index [3]. Oxidation measured in the 45 ankle inserts versus their time in vivo was compared to oxidation rates previously published for gamma-sterilized hip and knee polyethylene retrievals [6]. Statistical analysis was performed using IBM SPSS v.22. Results. The ankle devices were retrieved most commonly for loosening (n=22) followed by polyethylene fracture (n=9). These failure modes occurred after statistically different in vivo time (loosening: mean=4.4±3.6 years; polyethylene insert fracture: mean=9.5±4.1 years; p=0.002). Presence of clinical fatigue (cracking and/or delamination) was identified in 24 of the 70 retrieved inserts, and its presence correlated with in vivo time (Spearman's rho =0.449, p<0.001). Thirteen of these fatigued inserts were analyzed by FTIR. TVI analysis confirmed the sterilization method of the fatigued inserts: 12 gamma, 1 non-gamma sterilized. All 13 fatigued inserts had maximum ketone oxidation index (KOI) of 1.2 or higher. Presence of fatigue correlated with measured oxidation (Spearman's rho =0.685, p<0.001). Six of the 9 inserts that fractured in vivo were analyzed by FTIR. All were gamma-sterilized, and all had oxidation of 1.2 or higher. Oxidation rate determined for most of the 45 ankle inserts was at or above oxidation rates previously published for gamma-sterilized hip and knee polyethylene retrievals [6]. Discussion. This retrieval study concurs with the ankle arthroplasty literature that loosening is the most common reason for ankle revision [4]. Ankle inserts retrieved as a result of implant loosening had lower oxidation and no fatigue damage resulting from their shorter in vivo time. Fatigued and/or fractured inserts were in vivo for longer times, allowing more oxidation to occur. The effect of oxidation on polyethylene tensile strength and ductility has been reported for tibial inserts [5]. Oxidation above the critical value [5] has a dramatic effect on the ability of the polyethylene to resist fatigue damage and fracture, since the toughness of the polyethylene drops to near zero. All fatigued and fractured ankle inserts had oxidation that exceeded this critical oxidation. Most ankle inserts, whether gamma or non-gamma sterilized, oxidized at or above the oxidation rates previously published for gamma-sterilized hip and knee polyethylene retrievals [6]

Introduction. Sequentially annealed highly crosslinked polyethylenes (HXLPEs) were introduced in total knee replacement (TKR) starting in 2005 to reduce wear and particle-induced osteolysis. Few studies have reported on the clinical performance of HXLPE knees. In this study, we hypothesized that due to the reduced free radicals, sequentially annealed HXLPE would have lower oxidation levels than gamma inert-sterilized controls. Methods. 145 tibial components were retrieved at consecutive revision surgeries at 7 different surgical centers. 74 components were identified as sequentially annealed HXLPE (X3, Stryker) while the remainder (n = 71) were conventional gamma inert sterilized polyethylene. The sterilization method was confirmed by tracing the lot numbers by the manufacturer. The conventional inserts were implanted for 1.7 years (Range: 0.0–9.3 years), while the X3 components were implanted 1.1 years (Range: 0.0–4.5 years). Surface damage was assessed using the Hood method. Oxidation analysis was performed in accordance with ASTM 2102 following submersion in boiling heptane for 6 hours to remove absorbed lipids. 30 of the conventional and 29 of the HXLPE inserts were available for oxidation analysis. Results. The predominant reasons for revision were loosening, instability, and infection for both material cohorts. None of the highly crosslinked tibial inserts were revised for osteolysis. Pitting, scratching, and burnishing were the predominant damage mechanisms within both material groups. Delamination was not present within the highly crosslinked inserts. Oxidation indices were similar between the two cohorts at the bearing surface, AP face, and the post (p>0.30). Oxidation was lower at the backside surface in the HXLPE group when compared to the gamma inert group (p=0.04). In the HXLPE group, the backside surface had lower oxidation indices than the bearing surface (p = 0.02), post (p < 0.02), and AP Face (p = 0.001). In the HXLPE cohort, only the bearing surface was positively correlated with implantation time (Rho = 0.51; p = 0.01); whereas, the oxidation indices in the gamma inert cohort were not correlated with implantation time. Discussion. This study evaluated the surface damage mechanisms and oxidative stability of 2nd generation HXLPE in total knee replacement. Sequentially annealed HXLPE inserts exhibited comparable surface damage mechanisms and oxidation indices as compared with conventional inserts. Additional, longer-term HXLPE retrievals are necessary to ascertain the long term in vivo stability of these materials in total knee replacement

To prevent aseptic loosening resulting from osteolysis induced by polyethylene (PE) wear particles in THA, it is necessary to develop a high wear-resistance bearing material. We have investigated the bearing surface mimicking the articular cartilage; grafting a biocompatible polymer, poly(2-methacryloyloxyethyl phosphorylcholine) (PMPC), onto the PE surface. High wear-resistance of PMPC-grafted surface has been revealed in the hip simulator wear test of 20 million cycles. Additionaly, in THA, oxidation degradation induced by residual free radicals resulting from gamma-ray irradiation for cross-linking or sterilization is also regarded as serious issue. Recently, gas plasma (GP) sterilization has been used as a less residual radical sterilization method. In this study, we ask a question: the GP sterilization would affect to PMPC surface and/or PE substrate? Hence, we investigated surface chemical, wear, mechanical, physical and oxidation properties of GP sterilized PMPC-grafted highly cross-linked PE (CLPE). GP-sterilized CLPE and PMPC-grafted CLPE (CLPE (GP) and PMPC-CLPE (GP), respectively; GUR 1020 resin, 75 kGy irradiation), and 25 kGy-gamma-sterilized PMPC-grafted CLPE (PMPC-CLPE (g); GUR 1020 resin, 50 kGy irradiation) were evaluated. Surface property of PMPC layer was evaluated by X-ray photoelectron spectroscopy (XPS), fourier-transform infrared (FT-IR) spectroscopy, fluorescence microscope and cross-sectional transmission electron microscope (TEM) observations. Wettability and lubrication of the PMPC-CLPE surface were evaluated by static water contact angle measurement and ball-on-plate friction test, respectively. Wear properties of the acetabular cups were examined by using hip simulator in the combination with Co-Cr-Mo femoral heads. To evaluate the GP sterilization effect to the CLPE substrate, tensile test, izod impact test, small punch test, gel content, residual radical concentration and oxidation degradation were conducted. Oxidation degradation was evaluated as oxidation index by using a FT-IR spectroscopy. By the XPS and FT-IR measurements, phosphorus peak and P-O peak attributed to grafted PMPC were observed, respectively. Uniform PMPC layer (100–200 nm thick) was observed on both surfaces of PMPC-CLPE (g) and PMPC-CLPE (GP) [Fig. 1]. Water contact angle of CLPE (GP) was almost 100 degree, while those for PMPC-CLPE (g) and PMPC-CLPE (GP) decreased dramatically to almost 10 degree. Dynamic coefficient of friction of PMPC-CLPE (g) and PMPC-CLPE (GP) was lower than that for CLPE (GP). In the hip simulator wear test, PMPC-CLPE (g) and PMPC-CLPE (GP) cups showed significantly lower amount of wear than that of CLPE (GP) [Fig. 2]. The number of the wear particles was extremely less in PMPC-CLPE (g) and PMPC-CLPE (GP), though the size was not different of all cases. Water thin film might be formed at the grafted PMPC layer, which acted as significantly efficient lubricant. There was no difference in the mechanical and physical properties among three groups. Oxidation index for PMPC-CLPE (GP) after acceleration of aging was lower than that of PMPC-CLPE (g). The GP sterilization might affect only to the PMPC-grafted surface, whereas gamma irradiation affects also to the PE substrate. From these results, the PMPC-CLPE (GP) is expected to be one of the great bearing materials having not only high-wear resistance but also high-oxidation resistance, which could give further longevity of implantation

HXLPE acetabular liners were introduced to reduce wear-related complications in THA. However, post-irradiation thermal free radical stabilization can compromise mechanical properties, leave oxidation-prone residual free radicals, or both. Reports of mechanical failure of HXLPE acetabular liner rims raise concerns about thermal free radical stabilization and in vivo oxidization on implant properties. The purpose of this study is to explore the differences in the mechanical, physical and chemical properties of HXLPE acetabular liner rims after extended time in vivo between liners manufactured with different thermal free radical stabilization techniques. Remelted, single annealed and sequentially annealed retrieved HXLPE acetabular liners with in vivo times greater than 4.5 years were obtained from our implant retrieval laboratory. All retrieved liners underwent an identical sanitation and storage protocol. For mechanical testing, a total of 55 explants and 13 control liners were tested. Explant in vivo time ranged from 4.6 – 14 years and ex vivo time ranged from 0 – 11.6 years. Rim mechanical properties were tested by microindentation hardness testing using a Micromet II Vickers microhardness tester following ASTM standards. A subset of 16 explants with ex vivo time under one year along with five control liners were assessed for oxidation by FTIR, crystallinity by Raman spectroscopy, and evidence of microcracking by SEM. No significant difference in in vivo or ex vivo was found between thermal stabilization groups in either set of explants studied. In the mechanically tested explants, there was no significant correlation between in vivo time and Vickers hardness in any thermal stabilization group. A significant correlation was found between ex vivo time and hardness in remelted liners (r=.520, p = .011), but not in either annealed cohort. ANCOVA with ex vivo time as a covariate found a significant difference in hardness between the thermal free radical stabilization groups (p 0.1) was found in retrieved remelted (25%), single annealed (100%) and sequentially annealed (75%) liner rims. Crystallinity was increased in the subsurface region relative to control liners for both annealed, but not remelted, liner rims. Hardness was increased in oxidized rims for both annealed cohorts but not in the remelted cohort. Microcracking was only found along the surface of one unoxidized remelted liner rim. Mechanical properties were reduced at baseline and worsened after in vivo time for remelted HXLPE liner rims. Rim oxidation was detected in all groups. Oxidation was associated with increased crystallinity and hardness in annealed cohorts, but not remelted liners. Increased crystallinity and oxidation do not appear to be directly causing the worsened mechanical behavior of remelted HXLPE liner rims after extended in vivo time

Alpha Lipoic Acid (L.A.) is an effective natural antioxidant discovered in the human body in 1951 from L.J. Reed and I.C. Gunslaus from liver. It is inside broccoli, spinach and red meats, especially liver and spleen. Actually it is largely used as antioxidant in antiaging products according to the low toxicity level of the product. The present study take into consideration the possibility to reduce oxidation of medical irradiated UHMWPE GUR 1050, mixing together polyethylene powder and Alpha Lipoic Acid powder. The study is composed of two parts. Part 1 Thermostability of alpha lipoic acid during polyethylene fusion Part 2 detection of oxygen level in artificially aged irradiated polyethylene. Solid pieces were made with Gur 1050 powder (Ticona Inc., Bayport, Tex, USA) and mixed with Alpha Lipoic Acid (Talamonti, Italy, Stock 1050919074) 0,1%-­‐0,3%-­‐0,5%-­‐1%-­‐2% and gamma ray irradiated with 30 kGy (Isomedix, Northborough, MA). An owen (80° Celsius) was used to produce an aging effect for 35 days in the doped and control samples (Conventional not doped polyethylene). This process simulate an aging effect of 10 years into the human body. Part 1 : THERMAL STABILITY : a Fourier Transfer Infra Red (FTIR) test was made in pieces molded in a cell at 150° and 200°Celsius and pressure of 200 MPa comparing to the UHMWPE powder mixed with alpha lipoic acid. The presence of Alpha Lipoic Acid in the polyethylene was found at any depth in the manufacts. Part 2 : OXIDATION OF THE SURFACE : After 5 weeks at 80° Celsius in a owen (ASTM standard F-­‐2003-­‐02)A FOURIER TRANSFER INFRA RED TEST (FTIR) was made in the superficial layer and deeper on the undersurface of doped 0,1% and conventional UHMWPE. The antioxidation limit is defined as the ratio of the area under 1740cm/−­‐1 carbonyl and 1370 cm/−­‐1 Methylene absorbance peaks. In conventional UHMWPE oxidation is detected on the surface and decreases in the deeper layers down to zero under 1500 Micron. In the doped UHMWPE, FTIR demonstrate a very low oxidation limit on the surface and at any depth, comparing to conventional UHMWPE. The examples show that Lipoic Acid is effective as antioxidant in irradiated UHMWPE and it is stable with respect to thermal treatment. For any figures or tables, please contact authors directly

Introduction:. First generation highly crosslinked polyethylenes (HXPLEs) have proven successful in lowering both penetration and osteolysis rates. However, 1. st. generation annealing and remelting thermal stabilization have been associated with in vivo oxidation or reduced mechanical properties. Thus, 2. nd. generation HXLPEs were developed to improve oxidative stability while still maintaining material properties. Little is known about the in vivo clinical failure modes of these 2. nd. generation HLXPEs. The purpose of this study was to assess the revision reasons, wear, oxidative stability, and mechanical behavior of retrieved sequentially annealed Vitamin E diffused HXLPE in THA and TKA. Methods:. 251 2. nd. Generation HXLPE hip and knee components were consecutively retrieved during revision surgeries and continuously analyzed in a prospective, IRB approved, multicenter study. 123 acetabular liners (Implanted 1.2y; Range 0–5.0y) and 117 tibial inserts (Implanted 1.6y; Range 0–5.8y) were highly crosslinked and annealed in 3 sequential steps (X3). Five acetabular liners (Implanted 0.6y; Range 0–2.0y) and six tibial inserts (Implanted 1.3y; Range 0.5–1.8y) were diffused with Vitamin E (E1). Patient information was collected from medical records (Table 1). Linear penetration of liners was measured using a calibrated digital micrometer (accuracy: 0.001 mm). Surface damage of tibial components was assessed using the Hood method. Thin sections were taken from the acetabular liners (along the superior/inferior axis) and the tibial components (along the medial condyle and central spine) for oxidation analysis and analyzed according to ASTM 2102. Mechanical behavior was assessed via the small punch test (ASTM 2183). Results:. The liners and tibial components fabricated from both HXLPEs were revised predominantly for loosening, instability, and infection (Figure 1). The average penetration rate for the Sequentially Annealed group was low (PR = 0.045 mm/yr). Pitting, scratching and burnishing were the predominant damage mechanisms of the tibial inserts within both material groups, with no evidence of delamination. Oxidation indices were low (Mean OI≤0.3) and similar between liners and inserts of the Sequentially Annealed components at the bearing and backside surface (Figure 2, p ≥ 0.15). Oxidation was positively correlated with implantation time at the bearing surface of the Sequentially Annealed groups (Rho > 0.29, p < 0.005). The Ultimate Load of the Sequentially Annealed acetabular liners was statistically higher than the tibial components (p < 0.001), however the mean difference was minimal (∼6N). Discussion:. This study evaluated the properties of 2. nd. generation HXLPEs used in THA and TKA. Sequentially Annealed liners had penetration rates comparable with 1. st. generation HXLPEs. While oxidation was low for both sequentially annealed and Vitamin E HXLPEs, we were able to detect regional variations in the oxidative in the sequentially annealed cohort. Longer-term retrievals are necessary to fully assess the oxidative stability of Vitamin E diffused HXLPE used in TKA and THA