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

Introduction. 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. Material and Methods. 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 – 14.0 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. Results. No significant difference in in vivo or ex vivo time 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<.0005, η. 2. = 0.322). Post hoc analysis revealed hardness was significantly lower in the retrieved remelted group compared to both the single annealed (p=.001) and sequentially annealed (p<.0005) cohorts. Hardness was significantly higher in the retrieved remelted liners compared to controls (p=.007), with no different in either annealed cohort. Detectable subsurface oxidation (OI > 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. Conclusion. 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. For any figures or tables, please contact authors directly

Radiation cross-linked ultrahigh molecular weight polyethylene (UHMWPE) is the bearing of choice in joint arthroplasty. The demands on the longevity of this polymer are likely to increase with the recently advancing deterioration of the performance of alternative metal-on-metal implants. Vitamin E-stabilized, cross-linked UHMWPEs are considered the next generation of improved UHMWPE bearing surfaces for improving the oxidation resistance of the polymer. It was recently discovered that in the absence of radiation-induced free radicals, lipids absorbed into UHMWPE from the synovial fluid can initiate oxidation and result in new free radical-mediated oxidation mechanisms. In the presence of radiation-induced free radicals, it is possible for the polymer to oxidize through both existing free radicals at the time of implantation and through newly formed free radicals in vivo. Thus, we showed that reducing the radiation-induced free radicals in vitamin E-stabilized UHMWPE would increase its oxidative stability and presumably lead to improved longevity. We describe mechanical annealing, low pressure annealing, and warm irradiation of irradiated vitamin E blends as novel methods to eliminate 99% of radiation-induced free radicals without sacrificing crystallinity. These are significant improvements in the processing of highly cross-linked UHMWPE for joint implants with improved longevity

Since its introduction in total hip replacements in the 1960's, Ultra High Molecular Weight Polyethylene (UHMWPE) has played a major role as a bearing component material for joint arthroplasty. Concerns were raised when issues of wear resistance became apparent, and therefore Highly Crosslinked Polyethylenes were introduced. Such materials undergo a thermal treatment to quench the free radicals and reduce progressive oxidation. However, said thermal treatment weakens the material mechanical properties and hence the use of antioxidants has been proposed and implemented in clinical use, mainly Vitamin-E. This can be added to the material before or after irradiation. If it is done before, part of the anti-oxydant is consumed during irradiation and so will not be available for its main purpose, and part reacts before irradiation with the free radicals thus reducing the crosslinking effect. If it is added after irradiation, high temperatures are required in order to diffuse it in the bulk material, and anyway the surface will be mainly rich in antioxidant. However, Vitamin-E tends to neutralize the free radicals on the oxidized lipid chain present in our body fluids and so in direct contact with the prosthetic components: such mechanism reduces the Vitamin-E quantity available for anti-oxidation purposes in the long run. A UHMWPE doped with Hindered Amine Light Stabilizer (HALS) has been developed and tested for applications in large joint replacements where highest resistance to wear and tough mechanical properties are simultaneously required, such as tibial inserts for knee joints or acetabular inserts for large diameter heads. Mechanical and biocompatibility tests were run in accordance with ASTM F 2565-06 and ISO 10993-1 with successful results and good reproducibility. In particular, electro spin resonance exhibited a very high level of free radicals in the three samples, which confirms the properties of this new material. Free radicals are the result of the activation of the HALS molecules during irradiation, creating nitroxide radicals that will destroy the residual alkyl radicals responsible for the oxidation before and after implantation. Biocompatibility tests proved absence of cytotoxicity, sensitization, irritation, genotoxicity or pyrogenic reactions. The possible future applications for this new material in the arthroplasty field will be discussed along with the expected advances and advantages

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. In vivo, UHMWPE bearing surfaces are subject to wear and oxidation that can lead to bearing fatigue or fracture. A prior study in our laboratory of early antioxidant (AO) polyethylene retrievals, compared to gamma-sterilized and highly cross-linked (HXL) retrievals, showed them to be more effective at preventing in vivo oxidation. The current analysis expands that early study, addressing the effect of:. manufacturing-variables on as-manufactured UHMWPE;. in vivo time on these initial properties;. identifying important factors in selecting UHMWPE for the hip or knee. Methods. After our prior report, our IRB-approved retrieval laboratory received an additional 96 consecutive AO-retrievals (19 hips, 77 knees: in vivo time 0–6.7 years) of three currently-marketed AO-polyethylenes. These retrievals represented two different antioxidants (Vitamin E and Covernox) and two different delivery methods: blending-prior-to and diffusing-after irradiation cross-linking. Consecutive HXL acetabular and tibial inserts, received at retrieval, with in vivo time of 0–6.7 years (260 remelted, 170 annealed) were used for comparison with AO-retrievals. All retrievals were analyzed for oxidation and trans-vinylene index (TVI) using a Thermo-Scientific iN10 FTIR microscope. Mechanical properties were evaluated for 35 tibial inserts by uniaxial tensile testing using an INSTRON load frame. Cross-link density (n=289) was measured using a previously published gravimetric gel swell technique. Oxidation was reported as maximum ketone oxidation index (KOI) measured for each bearing. TVI was reported as the average of all scans for each material. Cross-link density and mechanical properties were evaluated as a function of both TVI and oxidation. Results. Minimal increase in oxidation was seen in these AO-retrievals, out to almost 7 years in vivo. In contrast, HXL-retrievals showed increasing KOI with time in vivo (annealed-HXL = 0.127/year, remelted-HXL = 0.036/year, p<0.001). HXL oxidation rate was higher in knees (0.091/year) than in hips (0.048/year), p<0.001. Cross-link density (XLD) correlated positively with TVI for both HXL (Pearson's correlation=0.591, p<0.001) and AO (Pearson's correlation=0.598, p<0.001) retrievals. AO-materials had higher TVI for the same or similar XLD than did HXL polyethylene. XLD correlated negatively with KOI for HXL retrievals (Pearson's correlation=−0.447, p<0.001). Mechanical properties varied by material across all materials evaluated, with tensile toughness correlating negatively with increasing TVI (Pearson Correlation=−0.795, p<0.001). Discussion. Irradiation cross-linking has been used effectively to improve wear resistance. Residual free radicals from irradiation are the target of AO-polyethylene, to prevent loss of UHMWPE XLD, resulting from in vivo oxidation of free radicals as seen in HXL retrievals, and toughness, resulting from oxidation or initial remelting. Despite different manufacturing variables, AO-polyethylene retrievals in this cohort had minimal oxidation and no change in XLD or toughness due to oxidation. However, toughness did vary with irradiation dose as did cross-link density. To achieve the same level of cross-linking as HXL-polyethylene required a higher irradiation dose in blended AO-polyethylene. AO-polyethylenes evaluated in this study had toughness that decreased with irradiation dose, but avoided loss of toughness due to remelting. Because AO-polyethylenes did not oxidize, they did not show the decrease of cross-link density, and potential loss of wear resistance, seen in HXL-polyethylene. For any figures or tables, please contact authors directly

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. The optimum UHMWPE orthopaedic implant bearing surface must balance wear, oxidation and fatigue resistance. Antioxidant polyethylene addresses free radicals, resulting from irradiation used in cross-linking, that could oxidize and potentially lead to fatigue damage under cycles of in vivo use. Assessing the effectiveness of antioxidant (AO) polyethylene compared to conventional gamma-sterilized or remelted highly cross-linked (HXL) polyethylene is necessary to set realistic expectations of the service lifetime of AO polyethylene in the knee. This study evaluates what short-term antioxidant UHMWPE retrievals can reveal about: (1) oxidation-resistance, and (2) fatigue-resistance of these new materials. Methods. An IRB-approved retrieval laboratory received 25 AO polyethylene tibial insert retrievals from three manufacturers with in vivo time of 0–3 years. These were compared with 20 conventional gamma-inert sterilized and 30 HXL (65-kGray, remelted) tibial inserts of the same in vivo duration range. The retrievals were. (1) analyzed for oxidation and trans-vinylene index (TVI) using an FTIR microscope, and (2) inserts of sufficient size and thickness were evaluated for mechanical properties by uniaxial tensile testing using an INSTRON load frame. Oxidation was reported as maximum oxidation measured in the scan from the articular surface to the backside of each bearing. TVI was reported as the average of all scans for each material. Average ultimate tensile strength (UTS), ultimate elongation (UE), and toughness were the reported mechanical properties for each material. Results. Maximum oxidation values differed significantly across material types (p=0.018, Figure 1). No antioxidant retrieval exhibited a subsurface oxidation peak, in contrast to conventional gamma-sterilized (55%) and highly cross-linked (37%) retrievals that exhibited subsurface oxidation peaks over the same in vivo time (Figure 2). Trans-vinylene index (TVI) correlated positively with nominal irradiation dose (p<0.001). Mechanical properties varied by material, with tensile toughness correlating negatively with increasing TVI (p<0.001, Figure 3). Discussion. AO polyethylene was developed to address the problem of free radicals in polyethylene resulting from irradiation used in cross-linking or sterilization. Each manufacturer used a different antioxidant or method of supplying the antioxidant. However, all of the antioxidant materials appeared to be effective at minimizing oxidation over the in vivo period of this study. The antioxidant materials prevented in vivo oxidation more effectively than both conventional gamma-sterilized and remelted HXL polyethylene, at least over the in vivo period represented. The toughness, or ability of the material to resist fatigue damage, decreased with increasing irradiation cross-linking dose (increasing TVI). The AO polyethylenes evaluated in this study had lower toughness than conventional gamma-sterilized polyethylene, but they avoided the loss of toughness due to remelting. Clinical relevance. Antioxidant polyethylene tibial retrievals showed superior oxidation resistance to conventional gamma-inert and remelted HXL inserts. Material toughness varied with the irradiation dose used to produce the material. Comparison of antioxidant retrieval tensile properties can be used as a guide for clinicians in choosing appropriate materials for the applications represented by their patients

INTRODUCTION. Ultra-High Molecular Weight Polyethylene (UHMWPE) wear debris is thought to be a main factor in the development of osteolysis (1). However, the method for the evaluation of the biological response to UHMWPE particles has not yet been standardized. In this study, four different types of UHMWPE particles were generated using a mechanized pulverizing method and the biological responses of macrophages to the particles were investigated using an inverted cell culturing process (2). MATERIALS & METHODS. Virgin samples were manufactured via Direct Compression Molding (DCM) technique from UHMWPE GUR1050 resin powder (Ticona, USA). For vitamin E (VE)-blended sample, the resin was mixed with VE at 0.3 wt% and the mixture was then molded using DCM. The crosslinked virgin samples were made by gamma ray irradiation to UHMWPE GUR1020 resin sheet (Meditech, USA) with doses of 95kGy ±10% and annealed. The VE-blended crosslinked samples were made by electron beam irradiation to VE-blended samples with doses of 300kGy and annealed. The material conditions were summarized in Figure 1. To pulverize the samples, the Multi-Beads Shocker (Yasui Kikai, Japan) was used. After pulverization, samples were dispersed in an ethanol solution and sequentially filtered through polycarbonate filters. Over 100 sections of the filter were selected randomly and images of the particles were analyzed using scanning electron microscope (SEM). To analyze the macrophage biological response, an inverted cell culturing process was used (2). The mouse macrophage-like cells were seeded at densities of 4×105cells per well in a 96-well culture plate and incubated for 1h. UHMWPE particles suspended in the culture medium were then added to each well in the appropriate amount. After that, fresh medium was added to fill the wells, and a sealing film was used to cover the culture plate. The culture plate was then inverted to cause the UHMWPE particles interact with the adhered macrophages. The inverted culture plate was incubated for 8h. The amount of TNF-α was measured by enzyme-linked immunosorbent assay (ELISA). RESULTS & DISCUSSION. Geometric measurements showed no significant difference in the UHMWPE particles (Figure 2). The amount of TNF-α released stimulated by the crosslinked virgin particles showed significantly higher relative to the other UHMWPE particles (Figure 3). During crosslinking irradiation, the carbon free radicals are generated in the main chain (3). In the presence of oxygen, these radicals can react to form peroxy radicals and when the peroxy free radicals react with hydrogen they form hydroperoxides, which can further degrade into other oxidation products (4). It has been reported that VE hinders this cascading in UHMWPE (5). Therefore, it is possible that oxidation of the crosslinked virgin UHMWPE was involved in the cytokine response observed in this study. However resin material, molding technique and the irradiation method were different between crosslinked virgin and VE-blended crosslinked samples. Further consideration will be needed to examine the relationship between residual radicals, hydroperoxides and biological response

Introduction. Osteolysis caused by wear of the ultrahigh molecular weight polyethylene (UHMWPE) often leads to failure. Cross-linking improves wear, but also produces residual free radicals that decrease oxidative stability. In vitro studies have shown that the anti-oxidative properties of vitamin E UHMWPE stabilize free radicals while retaining the physical and chemical properties of UHMWPE. The porous surface of the Regenerex™ shell was developed for improved bone in-growth fixation. The increased porosity of the Regenerex™ shell promotes early bony in-growth with the goal of greater long-term stability. The purpose of this study was to evaluate vitamin E infused polyethylene (VEPE) wear and stability of acetabular and femoral components using RSA. Methods. 58 patients (64 observed hips), all with osteoarthritis, gave informed consent to participate in a 5 year RSA study. Each patient received a VEPE liner, a Regenerex™ acetabular shell, and an uncemented stem with either a 32mm or 36 mm cobalt chrome femoral head. Tantalum beads were inserted into the VEPE, the pelvic and the femoral bone to measure head penetration into the polyethylene, and shell and stem stability over time, using RSA. RSA radiographs were scheduled immediately postoperatively (up to 6 weeks) and 6 months, 1, 2, 3, and 5 years after surgery. The Wilcoxon signed-ranks nonparametric test was used to determine if changes in penetration or migration were significant over time at p≤0.05. Results. 58 hips have been followed for 6 months, 55 at 1 year, 52 at 2 years, 47 at 3 years and 18 at 5 years. The 36mm cohort data is not reported at this time due to insufficient follow-up. The median± standard error (SE) superior head penetration into the polyethylene was 0.05±0.01mm at 2 years, 0.05±0.01mm at 3 years, and 0.05±0.02 mm at 5 years. The acetabular components had a median± SE cup translation in the proximal direction of 0.09±0.03mm at 2 years, 0.04±0.04mm at 3 years, and 0.06±0.06mm at 5 years. The median± SE cup rotation was −0.09±0.16 degrees at 2 years, −0.02±0.15 degrees at 3 years, and 0.30±0.20 degrees at 5 years. There was a statistically significant difference in cup rotation between the 6 month and 1 year intervals (p=0.007), but no significant differences in translation or head penetration. The median± SE stem distal migration was 0.08±0.07mm at 2 years, 0.05±0.23mm at 3 years, and 0.02±0.17mm at 5 years, with a significant difference between the 6 month and 3 year intervals (p=0.029). Discussion. The VEPE liners show low head penetration at 5 years. The early head penetration, probably due to creep, is substantially lower relative to that reported for non-vitamin E stabilized UHMWPE measured by similar techniques. At 5 years, all acetabular components were stable, with the early significant difference in rotation at 1 year likely due to early settling of the cup. This study documents the longest-term evaluation of in vivo wear performance of vitamin E stabilized UHMWPE. The stability of the Regenerex™ shell and femoral stem shows promise for long-term survivorship

Introduction. Radiation cross-linked UHMWPEs were developed to address osteolysis-induced joint arthroplasty failure by improving wear resistance and reducing associated particulate debris. Introduced clinically fifteen years ago, they are the primary bearing surface in use with excellent clinical outcomes and wear resistance. First generation materials sought to maintain oxidative stability by reducing or eliminating free radicals through thermal treatments, while second generation aimed to further balance oxidation resistance and improve mechanical properties through sequential irradiation and annealing or the incorporation of an antioxidant. Recent reports have identified lipid absorption and cyclic loading as potential in vivo oxidation-inducing mechanisms. In this on-going retrieval study, we report on the current status of oxidative stability in these two generations of UHMWPE bearings. Materials & Methods. Six types of highly cross-linked UHMWPE hip and knee bearings (Table 1) were surgically-retrieved and collected under IRB approval. Standard material analysis was performed on cross-sections of loaded and unloaded bearing surfaces of the components. Thin sections (150 µm thickness) were extracted in boiling hexanes under reflux for 16 hours followed by vacuum drying for 24 hours. FTIR was used to evaluate oxidation and calculated from post-hexane absorbance spectra by normalizing the area under 1740 cm. −1. (1680–1780 cm. −1. ) to the area under 1370 cm. −1. (1330–1390 cm. −1. ), per ASTM F2102-13. Gravimetric swelling of regional cross-sectional blocks (1–2 mm. 3. ) for 2 hours in 130°C boiling xylenes was used to assess cross-link density, per ASTM 2214. Results. Irradiated and melted retrievals all showed detectable (OI>0.1) subsurface oxidation in the articular surface of retrievals (Fig 1). Behavior between materials types differed: 47% of Longevity acetabular liners (MOI=0.14±0.19; Table 2) showed detectable oxidation as opposed to 19% in Marathon retrievals (MOI=0.07±0.08), both with comparable sample sizes and in vivo durations. We saw no concomitant change in the cross-link density, except in one case where OI>1.0. Sequentially irradiated and annealed (X3) retrievals showed the highest incidence of detectable oxidation (76%), highest average maximum oxidation (0.35±0.39), signs of oxidative embrittlement and a loss of cross-link density which correlated with decreasing oxidation (R. 2. =0.30; p-value=0.000016). Oxidation was in both loading regions of X3 knees, while Prolong knees were observed to have oxidation solely at the articular surface. Antioxidant-stabilized E1 retrievals showed low detectable oxidation values (MOI=0.11±0.03) in both regions without change in cross-link density. Discussion. Throughout the first decade of service, irradiated and melted UHMWPE retrievals showed subsurface oxidation, but with little to no impact on material properties. Detectable oxidation and embrittlement were identified in sequentially irradiated and annealed retrievals at shorter time points. Residual free radicals and pre-implantation shelf oxidation, as a result of air permeable packaging, are potential factors behind the higher oxidation at earlier time points. Antioxidant-stabilized retrievals showed no change in their oxidative behavior with the lowest oxidation and variability in this very short 0–3 year follow-up. Continued analysis is needed to understand the second decade of behavior along with longer-term follow-up with patients to understand if these changes could affect clinical outcomes through oxidation-induced changes in material or mechanical properties

Introduction:. Moderately crosslinked polyethylene maintains a balance of wear resistance and mechanical properties. The GVF poly was manufactured from GUR1020 UHMWPE bars, sealed in vacuumed foil package, and gamma sterilized at 4 Mrads. The MARATHON® polyethylene inserts were manufactured from GUR1050 UHMWPE bars, crosslinked by gamma irradiation at 5 Mrad, and followed by a remelting process that eliminates free radicals. The final sterilization method is gas plasma (GP) or ethylene oxide (EtO). Both methods will not introduce free radicals. Previous studies have shown MARATHON polyethylene (GP sterilized) with 83% lower wear than conventional polyethylene in a simulation test [1], compared to a 10-year clinical study that showed 77% wear reduction [2]. There is no study to compare the wear performance of MARATHON (EtO sterilized) and conventional poly. Materials and Methods:. Four groups of polyethylene inserts (Table 1) were paired with matching femoral heads that were manufactured from CoCrMo (ASTM F1537) with diameters of 28, 32, and 36 mm. The inserts were chosen to have similar thickness at the dome for MARATHON, while for GVF it was the largest head size available. Wear testing was performed on an AMTI Hip Simulator per the ISO 14242-1 standard [3] at 1 Hz using the described inputs (Table 2), which provide a larger range of motion than the ISO standard. The cups were mounted in accordance with ISO 14242-1 using custom fixturing and secured with cement while the femoral heads were mounted on a vertical taper support. Testing was performed in 25% bovine calf serum at 37 ± 2°C. Wear of the inserts was determined gravimetrically. Finally, wear rates were calculated by linear regression and then compared between the groups using ANOVA analysis (α = 0.05). Results:. The total wear over 5-million cycles and the wear rate of each group is in Figure 1. The wear of GVF (Group A) was the highest over that of the MARATHON (Groups B, C and D), with a wear reduction of 53%, 61%, and 74%, respectively. For MARATHON, there was a 7% wear increase per mm increase in head size (p < 0.01). Discussion:. The fact that the wear of MARATHON was at least 53% lower than that of GVF suggested that the poly wear was primarily affected by gamma-irradiation dose and process used for crosslinking of the polyethylene. In addition, the lower wear of MARATHON provides an option of using large head size which has the dual benefits of increased joint stability and improved head/shell ratio for better range of motion

Contemporary crosslinked polymers didn't just happen. The material was, has, and continues to be studied more than any other bearing surface material used in the total hip and total knee replacement construct. Historical failures and successes provided the information needed to make it the success that it is today as we approach the end of the second decade of extensive use. Recognition that wear particles, not cement, was the major cause of osteolysis was important. Next, understanding that oxidation from free radical formation was deleterious to wear resistant polyethylene was understood and finally, that crosslinking was responsible for magnitude increases in wear resistance. Although manufacturers have developed multiple processes to develop their crosslinked polymers (gamma and e beam radiation, melting and annealing, and most recently the addition of antioxidants) there are excellent 10-year results demonstrating head penetration rates (indicative of wear and creep) in the 0.02 to 0.04 mm/year range for many materials with minimal if any detection of osteolysis on radiographs and close to 0% revised for wear at 10+ years. Are there any cautions? Recently, at 10- to 15-year follow up, some clinically insignificant osteolysis has been noted in one study and in that same study, 36 mm heads had twice the volumetric wear as 32 mm heads, but it was still a relatively low volume compared to the previous generation polyethylenes. We need further follow up, but at two decades of use, crosslinked polymers have dramatically reduced the osteolysis problem

Aim. Photodynamic therapy (PDT) requires a photosensitiser, a light source of an appropriate wavelength, and the presence of molecular oxygen. Once stimulated to its excited phase by the light, the photosensitiser reacts with oxygen to form free radicals of ‘singlet oxygen’ which is cytotoxic to microorganisms. We aim to demonstrate the effectiveness of PDT as an in-vitro antimicrobial technique against Staphylococcus aureus, Methicillin resistant Staphylococcus aureus, Staphylococcus epidermidis, Pseudomonas aeruginosa and Acinetobacter bauminii. This will form the scientific basis for further animal and human studies assessing PDT for treatment of periprosthetic infections, septic arthritis, and open fractures. Method. A PDT treatment protocol was devised using lawns of bacteria on agar plates. PDT was targeted towards the bacteria and the remaining microorganisms were quantified using a serial dilution technique. In order to assess the ability of photodynamic therapy to target biofilms on metallic implants, biofilms were cultured on polished titanium and hydroxyapatite-coated titanium discs and subjected to PDT. Results. Reductions in bacterial colony forming units of up to 7 log were achieved using PDT. The figure is a box plot representing a comparison of the amount of biofilm Pseudomonas aeruginosa (cfu/ml) remaining on the polished titanium disc and hydroxyapatite-coated titanium disc following treatment with photodynamic therapy. (MB+/-: photosensitizer present/absent; L+/-: laser present/absent). Conclusions. PDT has long been used in dermatology and dentistry as an antimicrobial technique. Its potential for treating orthopaedic infections has not yet been investigated. This study demonstrates potential for PDT as an antimicrobial technique in the treatment of bacteria commonly found in periprosthetic infections, septic arthritis, and open fractures. This in-vitro work lays the foundations for future animal and clinical studies. We envision PDT being used as an adjunct to antibiotics in treatment of these conditions, helping prevent ongoing infection, and the development of resistance

Introduction. In vitro studies showed that the anti-oxidative properties of vitamin E stabilize free radicals while retaining the mechanical strength of UHMWPE. The purpose was to evaluate vitamin E diffused polyethylene (VEPE) wear and stability of femoral components using RSA. Patient reported outcome measures (PROMs) were evaluated to determine the clinical outcome at 5 years. Methods. 48 patients (52 hips), with osteoarthritis, participated in a 5 year RSA study. Each patient received a VEPE liner, a porous titanium coated shell, and an uncemented stem with a 32mm head. Tantalum beads were inserted into the VEPE and the femur to measure head wear and stem stability using RSA. RSA and PROM follow-up was obtained postoperatively, 6 months, 1, 2, 3, and 5 years after surgery. The Wilcoxon signed-ranks test determined if changes in penetration or migration were significant (p≤0.05). Results. 47 hips were followed at 3 years, and 35 at 5 years. The median± standard error (SE) superior head penetration into the polyethylene was 0.05±0.01mm at 3 years and 0.06±0.01 mm at 5 years. There was no difference after 2 years. The median± SE distal stem migration was 0.06±0.21mm at 3 years, and 0.06±0.29mm at 5 years with no significant differences over time. All PROMs improved significantly from the preoperative to all other intervals (p<0.001 for all). Discussion. The VEPE liners show low head penetration at 5 years. The early head penetration, probably due to creep, is lower relative to that reported for non-VEPE measured by RSA. While most stems were stable, the high standard error results from one stem that migrated substantially by 6 months (9.4mm), which has since stabilized. This study documents the longest-term evaluation of in vivo wear performance of vitamin E stabilized UHMWPE. The low wear and the stability of the femoral stem shows promise for long-term survivorship

Wear of the tibial polyethylene liner of total knee arthroplasty (TKA) is complex and multifactorial. The issues involved include those of implant design and locking mechanism, surgical-technical variability, and patient weight and activity level. However, tibial polyethylene fabrication, including bar stock, amount of irradiation, quenching of free radicals, and sterilization may also be factors in the long-term survival of TKA. Highly crosslinked polyethylene is now widely used in total hip arthroplasty, but its value and use in TKA is a subject of great controversy. In making a decision to use these products, the surgeon should consider multiple sources of evidence: in-vitro wear testing; clinical cohort studies; randomised controlled trials; registry survival data; and retrieval analyses. The two questions to be asked are: is there a value or benefit in the use of these new polyethylenes, and what are the risks involved with the use of these products?. Laboratory testing, generally to 5 million cycles, has shown a significant decrease in tibial polyethylene wear of several products, with both cruciate-retaining and substituting designs, and under adverse conditions. Retrospective cohort studies and RCTs comparing conventional and highly crosslinked polyethylene have shown little difference between the two products at mean follow-up times of 5 years. One registry study showed no difference in the rate of revision at short-term follow-up, but the Australian Joint Replacement Registry in 2014 did report a decreased rate of revision for loosening and osteolysis in “young patients” with one particular tibial polyethylene. The risks of the use of highly crosslinked polyethylene include fracture (the tibial liner, PS post, and patella pegs), and particle size-reactivity. However, these risks appear to be quite low. Retrieval data shows lower damage scores with certain polyethylenes, and variable changes in the oxidation score. At present, the data does not support the widespread or routine use of highly crosslinked or antioxidant polyethylene in TKA. However, consideration should be given for use of certain products in young and active patients. Longer-term follow-up will ultimately determine the role of highly crosslinked polyethylene in TKA

Background. A first generation once annealed highly crosslinked polyethylene (HXLPE) was introduced in 1998. At 8 years it was reported to have a 78% reduction in wear compared with conventional polyethylene and no osteolysis. However, concerns regarding the long-term performance and oxidative resistance of this annealed material exist because of the presence of free radicals. Questions/purposes. We therefore addressed the following questions: (1) Does the improvement in wear observed at earlier follow-up continue out to 15 years? (2) What is the incidence of osteolysis in this group of patients?. Methods. We retrospectively reviewed 48 prospectively followed patients who had 50 hips with a once annealed HXLPE and were followed an average of 12 years (15 years maximum). Linear head penetration and cup position were measured from AP radiographs at early, 1-year, 5-year, and most recent follow-ups. There were 26 females, 22 males, with an average age of 61 years. Results. At average 12 years follow-up, annual linear wear was 0.018 mm (SD = 0.024). Average cup inclination was 50.2 degrees (SD = 5.1 range 48 to 64) and anteversion was 18.6 (SD = 8.3, range 3 to 35). No mechanical failure or osteolysis has been found on routine x-rays to date. Conclusions. At 8 year follow this once annealed material had a reported linear wear rate of 0.031mm /year. We now report, at a 12 years average 15 years maximum follow-up, a further reduction in linear wear of 0.018mm/yr. and no mechanical failures or osteolysis (Figure-1)

Artificial knee joints are continuously loaded by higher contact stress than artificial hip joints due to a less conformity and much smaller contact area between the femoral and tibial surfaces. The higher contact stress causes severe surface damage such as pitting or delamination of polyethylene (PE) tibial inserts. To decrease the risks of these surface damages, the oxidation degradation of cross-linked polyethylene (PE) induced by residual free radicals resulting from gamma-ray irradiation for cross-linking or sterilization should be prevented. Vitamin E (VE), as an antioxidant, blended PE (PE(VE)) has been used to solve the problems. In addition, osteolysis induced by PE wear particles, bone cement and metallic debris is recognized as one of the important problems for total knee arthroplasty (TKA). To decrease the generation of PE wear particles, we have developed the bearing surface mimicking the articular cartilage; grafting a biocompatible polymer, poly(2-methacryloyloxyethyl phosphorylcholine) (PMPC), onto the PE surface having high wear resistance. In this study, we have evaluated the surface, mechanical under severe oxidative condition, and wear properties of PMPC-grafted cross-linked PE(VE) (PMPC-CLPE(VE)) material for artificial knee joints. Untreated and PMPC-grafted 0.1 mass% VE-blended PE (GUR1020E resin) with a gamma-ray irradiation of 100 kGy for cross-linking and 25 kGy for sterilization were prepared (CLPE(VE) and PMPC-CLPE(VE), respectively). Surface properties were evaluated by Fourier-transform infrared (FT-IR) spectroscopy and transmission electron microscope (TEM) observations. Surface wettability and frictional property were measured by static water contact angle measurement and ball-on-plate friction test. To evaluate the oxidation degradation resistance, mechanical and physical properties such tensile test, izod impact test, small punch test and cross-link density measurement before and after accelerated aging were measured. Wear properties of the tibial inserts were examined by using knee simulator in the combination of Co-Cr-Mo femoral components according to ISO14243-3. Gravimetric wear, volumetric penetration and the number of generated wear particles were measured. By the FT-IR measurements and TEM observation, P–O peaks attributed to MPC unit and uniform PMPC layer with 100–200 nm thick was observed only on PMPC-CLPE(VE) surface. Static water contact angle of CLPE(VE) was almost 100 degree, while that of PMPC-CLPE(VE) decreased significantly to almost 35 degree. There was no significant difference in the mechanical and physical properties between CLPE(VE) and PMPC-CLPE(VE). Moreover, both the CLPE(VE) and PMPC-CLPE(VE) maintained these properties even after the accelerated aging of 12 weeks [Fig. 1]. Blended VE in CLPE would act as radical scavengers to prevent oxidation degradation. In the knee simulator wear test, the PMPC-CLPE(VE) tibial inserts showed about a half gravimetric wear compared to the CLPE(VE) tibial inserts [Fig. 2]. This would be due to the significant differences observed in wettability of the surface. Water thin film formed on the hydrated PMPC graft layer, would act as significantly efficient lubricant. From these results, the PMPC-CLPE(VE) is expected to be one of the great bearing materials not only preventing surface damages due to higher contact stress and oxidation degradation but also improving wear resistance, and to provide much more lifelong artificial knee joints. For any figures or tables, please contact authors directly (see Info & Metrics tab above).

Implant wear and osteolysis have been a major cause of failure of total knee implants. In the mid-1990s, manufacturers recognised the impact of oxidation on wear with implants sterilised by gamma irradiation in air and changed their methods of sterilisation. This has resulted in a dramatic reduction in wear. In retrieval studies, non-irradiated polyethylene has not shown the fatigue type of failure associated with oxidation. The percentage of revisions done at the Anderson Clinic for polyethylene wear for osteolysis has dropped from 44% in the late 1990s to 4% in the past decade. With the continued use of polyethylene free of oxidation, we anticipate a further reduction in the need for revision surgery secondary to wear and osteolysis. Highly cross-linked polyethylene was introduced to further reduce wear with total knee implants. Higher levels of irradiation used increases crosslinking in the polyethylene but the material strength is reduced. Although volumetric wear is reduced, the wear particles are smaller in size and potentially more bio-reactive. The Manufacturer And User Device Experience Database (MAUDE) reports describe early implant breakage and osteolysis of highly cross-linked polyethylene inserts. Implants that were highly crosslinked with quenched free radicals demonstrate increased levels of oxidation after retrieval unlike, never implanted components “off-the-shelf”. Backside wear remains a concern as non-modular implants have better long-term survivorship compared to their modular counterparts. These reports should temper enthusiasm for using highly cross-linked material in knees or modular tibial components until longer term clinical and retrieval studies have been completed

Introduction. Moderately crosslinked, thermally treated ultrahigh molecular weight polyethylene (UHMWPE) has to date demonstrated a good balance of wear resistance and mechanical properties. MARATHON™ Polyethylene (DePuySynthes Joint Reconstruction, Warsaw, IN) is made from polyethylene resin GUR 1050, gamma-irradiated at a dose of 5.0 Mrads to create crosslinking of polyethylene, and followed by a remelting process to eliminate free radicals for oxidative stability. 10-year clinical study [1] and laboratory wear simulation tests [2–3] have reported excellent wear performance of the MARATHON poly. There continues to be demand for improved head-to-shell ratio acetabular systems because larger head sizes have the benefits of increased stability and range of motion. The increased head-to-shell ratio is often times achieved by using a reduced liner thickness. One of the clinical concerns of thinner poly liners is the potential for rim fracture, particularly in the occurrences of rim loading or impingement at high cup angles [4–7]. This study investigated the performance of thinner poly liners to the challenge of high angle rim loading and neck-to-liner impingement. Materials and Methods. Three groups of ETO sterilized MARATHON polyethylene liners (ID/OD: 28/44, 32/48, and 36/52 mm) were paired with matching CoCrMo heads (n=6 each group). To simulate rim loading, liners were assembled in the metal shells tilted at 64° (Figure 1) with sinusoidal loading (0 to 5000N at 3Hz) in a 37°C water bath for 5-million cycles or until component failure, whichever occurred first. For neck-liner impingement testing, metal shells were potted at 54º (in the abduction/adduction plane with a ±10° of motion per ISO 14242–1 [8]) on a hip simulator (n=4 each group) using a physiological loading (max 3000N at 1Hz) for 3-million cycles (Figure 2). The impingement occurred at 64º during the simulated gait cycle (Figure 3). The liners were inspected every million cycles, using a high intensity light to search for signs of crack initiation and/or fractures. Both test methods were validated to be able to replicate liner fractures. Results. All MARATHON ETO liners passed 5-million cycles of high angle fatigue testing. All liners passed 3-million cycles of impingement testing. Discussion. Causes of liner fractures can be multi-factorial. Examples of influencing factors are: poly material, component designs, patient activity level, implant orientations, and neck-liner impingement. Improved head-to-shell ratio design requires reduction of the liner thickness, which raises the concern of liner fracture. In this study, we investigated adverse testing conditions of rim-loading and neck-liner impingement, in order to evaluate the mechanical performance of thin polyethylene liner