We have assessed the different adhesive properties of some of the most common bacteria associated with periprosthetic joint infection on various types of ultra high molecular Weight Polyethylene (UHMWPE). Quantitative in vitro analysis of the adhesion of biofilm producing strains of Staphylococcus aureus and Escherichia coli to physically and chemically characterised standard UHMWPE (PE), vitamin E blended UHMWPE (VE-PE) and oxidised UHMWPE (OX-PE) was performed using a sonication protocol. A significant decreased bacterial adhesion was registered for both strains on VE-PE, in comparison with that observed on PE, within 48 hours of observation (S. aureus p = 0.024 and E. coli p = 0.008). Since Vitamin E reduces bacterial adhesive ability, VE-stabilised UHMWPE could be valuable in joint replacement by presenting excellent mechanical properties, while reducing bacterial adhesiveness. Cite this article: Bone Joint J 2014;96-B:497–501

Summary Statement. In the most recent type of highly cross-linked UHMWPE, stabilised by vitamin E, the majority of this anti-oxidant cannot be leached out. Even more, the vitamin E molecules are grafted to the UHMWPE polymer backbone by an ether bond. Introduction. Today, highly cross-linked, vitamin E stabilised UHMWPE is clinically accepted as bearing material in joint replacements. Little is known about the chemistry of this antioxidant in the polymer after irradiation. The present investigation presents a model for the chemical nature of the trapping of vitamin E in PE. Method. UHMWPE type GUR 1020 (Ticona GmbH, Kelsterbach/Germany) was blended with 0.1 % vitamin E (Merck KGaA, Darmstadt/Germany), compression moulded at Mathys Ltd Bettlach in-house and cross-linked with γ-irradiation dose of nominally 100 kGy. To assess the extent of vitamin E leachable out, three 0.3 mm sections were cut from the centre of the samples. By extraction in heptane for 48 h at 98 °C, this amount of vitamin E trapped in the polymer was determined by Fourier transform infrared spectroscopy (FTIR) as relative vitamin E index (RVEI). The nature of the extracted substances was analysed by GC-MS. For solids, many of modern spectroscopic methods are not applicable. Therefore, 0.1 % vitamin E were dissolved in two model hydrocarbons (cyclohexane and n-octane) and irradiated at the same 100 kGy γ-dose. In order to determine the chemical bond vitamin E – hydrocarbon after irradiation, these liquid solution samples were analysed by different spectroscopic methods, such as GC-MS, MALDI-TOF-SIMS, HPLC and NMR. Results. Extraction experiments showed that only 23 % of the vitamin E could be extracted by heptane after irradiation whereas from a non-irradiated control sample, all vitamin E was extracted. GC-MS confirmed that the extracted vitamin E was chemically unchanged. Analysing the model hydrocarbons after irradiation, the GC-MS-chromatogram of the cyclohexane solution showed a single peak of the formal cyclohexene adduct of vitamin E. Illustrates this adduct, cyclohexyl-6-O-α-tocopherolether. Contrariwise, the same analysis of the n-octane solution revealed three formal octane adducts. By preparing references substances these three peaks could be attributed to ethers of vitamin E bonded at three different, but chemically equivalent CH. 2. positions on the eight carbon atom chain of n-octane. The single mass peak of the cyclohexane solution arises from the six chemically equivalent carbon atoms in this cyclic hydrocarbon. The 100 kGy γ-dose transformed 76 % of the vitamin E in the n-octane solution to the corresponding ethers and 68 % of the vitamin E in the cyclohexane to cyclohexyl ether. Therefore we postulate that in highly cross-linked, vitamin E stabilised UHMWPE the vitamin E is grafted to the polymer carbon backbone by an ether bond at the phenolic OH group of the vitamin E molecule. Conclusion. Upon irradiation, vitamin E is grafted to the UHMWPE polymer backbone to a large amount. This portion of antioxidant cannot leach out. Therefore, vitamin E stabilised HXLPE is protected from oxidation and ageing by a chemically grafted, quasi internal antioxidant

Introduction. Highly cross-linked ultrahigh molecular weight polyethylene (UHMWPE) is the most common bearing surface used in total joint arthroplasty due to its excellent wear resistance. While radiation cross-linking is currently used, cross-linking using a cross-linking agent such as a peroxide can also be effective with improved oxidative stability, which can be achived by an antioxidant such as vitamin E. The peroxide cross-linking behavior of UHMWPE in the presence of vitamin E was unknown. We investigated the cross-linking behavior and the clinically relevant mechanical and wear properties of peroxide cross-linked, vitamin E-blended UHMWPE. Materials and Methods. Medical grade UHMWPE (GUR1050) was blended with vitamin E and the peroxide (2,5-Dimethyl-2,5-di(t-butylperoxy)hexyne-3 or P130) before compression molding. Various vitamin E (0.1, 0.2, 0.3, 0.5, 0.6, 0.8 and 1.0 wt%) and peroxide concentrations (0.5, 1 and 1.5 wt%) were studied. 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. Oxidative stability was determined using oxidation induction testing (Braithwaite 2010). Double-notching and IZOD impact testing was performed according to ASTM D256. Samples prepared with vitamin E concentrations of 0.3 wt% and above and P130 concentrations of 0.5 and 1 wt% were also terminally gamma sterilized. Controls were 150-kGy irradiated vitamin E blends of UHMWPE. Results and Discussion. The cross-link density of peroxide cross-linked UHMWPEs were higher than the irradiated controls at a given vitamin E concentration (For example 250, 301 and 355 mol/dm3 for 0.5, 1 and 1.5 wt% peroxide cross-linked UHMWPE compared to 217 mol/dm3 for 150 kGy irradiated UHMWPE; Figure 1). The cross-link density dependence of wear was similar to radiation cross-linked UHMWPE, resulting in clinically relevant wear rates of 0.5 to 1.5 mg/MC. While the cross-link density of radiation cross-linked UHMWPE became saturated at vitamin E concentrations above 0.3 wt% (Oral 2008), this was not observed in peroxide cross-linked UHMWPE (Figure 2), suggesting more efficient cross-linking in the presence of the antioxidant. The impact strength was 30% higher for the peroxide cross-linked UHMWPEs at the comparable wear rate compared to irradiated controls (72 vs. 56 kJ/m2). The oxidation induction time of all peroxide cross-linked UHMWPEs (up to 57 min) was higher than that of the 0.1 wt% vitamin E-blended, 150-kGy irradiated UHMWPE (6 min). Gamma sterilization of peroxide cross-linked vitamin E blends decreased wear (0.5 wt% peroxide in Figure 3). Thus, peroxide concentration for cross-linking can be reduced if terminal sterilization is used. The mechanical properties and the oxidative stability of the material were not significantly affected by gamma sterilization. Significance. Peroxide cross-linking enabled good wear resistance for high vitamin E concentration blends of UHMWPE (>0.3 wt%), previously not possible by irradiation. Peroxide cross-linking of vitamin E-blended UHMWPE can provide a one-step, cost-effective method to manufacture wear resistant total joint implants with improved oxidative stability

Ultra-high molecular weight polyethylene (UHMWPE) has been successfully used as a bearing material in total joint arthroplasty. However, longevity of these implants has been compromised by wear and fatigue damage of the polyethylene. The addition of vitamin E to the polyethylene is a process recently introduced in the market to stabilize free radicals produced during radiation crosslinking. The objective of the present study is to investigate the effect of the addition of vitamin E on the wear characteristics of UHMWPE. Sequentially cross-linked and annealed UHMWPE material (X3™, Stryker Orthopaedics, Mahwah, NJ) was used as a control. Trident™ acetabular cups (Stryker Orthopaedics, Mahwah, NJ) with inner diameters of 36 mm and 44 mm and a wall thickness of 3.8 mm were tested on a 12 station MTS hip joint simulator. The simulator used a physiologic loading pattern with a maximum load of 2450N. The test was conducted under standard clean conditions with alpha calf fraction serum diluted to a protein concentration of 20 g/l for a total of three million cycles. All cups ran against CoCr femoral heads, and gravimetric measurements were taken every half-million cycles. Results show that sequentially crosslinked components, size 3 6mm, had an average volume loss of 9.4 ± 2.5 mm3, while vitamin E components of the same size had an average of 16.5 ± 3.1 mm3. This represents a 75% increase for vitamin E components that is statistically significant (p = 0.039). Size 44 mm sequentially crosslinked components had an average volume loss of 6.8 ± 3.7 mm3, while vitamin E components had an average of 19.7 ± 3.2 mm3. This denotes a statistically significant increase of 192% for material with vitamin E (p = 0.011). Linear regression analysis yielded wear rates of 4.1 ± 0.9 mm3/mc and 6.1 ± 1.3 mm3/mc for size 36 mm sequentially crosslinked and vitamin E components, respectively, which represents a non-significant increase of 49% for vitamin E components. Size 44 mm sequentially crosslinked components had a wear rate of 3.8 ± 1.3mm3/mc, while vitamin E components had a wear rate of 8.1 ± 0.7 mm3/mc. This represents a statistically significant increase of 117% in wear rate for vitamin E components (p = 0.013). The results of this testing indicate that the addition of vitamin E degrades wear performance relative to sequentially crosslinked material. Research shows that the introduction of Vitamin E affects the ability to create crosslinks during irradiation by reacting with some of the free radicals. Oral et al have shown that the crosslink density decreases when Vitamin E is blended into UHMWPE. Their research has also shown that a decrease in crosslink density causes an increase in wear rate. The results of the current testing show that the addition of vitamin E to polyethylene reduces the wear resistance of highly crosslinked polyethylene

Aim: Wear of the UHMWPE component is responsible for many TJR failures. It is now well known that oxidation of UHMWPE, induced by radiation sterilisation in the presence of oxygen, dramatically increases the wear rate. Vitamin E is already used as biocompatible antioxidant in a number of applications, thus it has been suggested as a suitable stabiliser for orthopaedic UHMWPE. This work investigates the role of the vitamin E on the oxidation process of a gamma-sterilized material. Methods: GUR 1050 (Meditech, Fort Wayne, IN) resins were blended with 0.05 wt% to 0.5wt% vitamin E and compression molded into billets. Gamma irradiation to 30 and 100 kGy was carried out in an industrial plant. This material was then sectioned using a microtome into 180 micron-thick specimens in preparation for the accelerated ageing. The samples were treated in an air circulating oven at 90°C. Every 20 hours they were analyzed with FTIR and the carbonyl concentration was recorded. The CL-imaging measurements were run at 180°C under oxygen in a Differential Scanning Calorimetry (DSC) coupled to a CCD camera. The Oxidation Induction Time (OIT) has been measured as the starting time of oxidation, extrapolated from the CL curve in the function of time. Results: The results obtained from both techniques clearly evidence that 0.05 wt % of Vitamin E it is enough to stabilize even the material irradiated to the highest dose (100 kGy). Irradiation of UHMWPE leads to the formation of alkyl radicals. When irradiation is carried out in air, macroalkyl radicals can react with oxygen to form hydroperoxides, which in turn decompose giving other oxidation species, mainly ketones and acids. The overall result of irradiation in air is the formation of oxidation products and a decrease in the molecular mass, due to chain fragmentation. The ability of α-tocopherol as a free radicals scavenger during gamma irradiation prevents the reaction of polymer radicals with oxygen. While performing this role, α-tocopherol is consumed and transformed into a variety of by-products. Nevertheless, higher OIT for the doped and irradiated specimens compared to the control (0% Vit.E, 0 kGy) suggest even a stabilising effect of these by-products. Conclusions: Vitamin E has been shown to be highly efficient against radiation-induced oxidation and therefore it should be recommended as biocompatible stabilizer for orthopaedic UHMWPE, in order to preserve good mechanical properties

Introduction. Vitamin E stabilization of radiation crosslinked UHMWPE is done by (1) blending into the resin powder, consolidating and irradiating or (2) diffusing into already consolidated and irradiated UHMWPE and terminally gamma sterilizing. With blending, a higher radiation dose is required for crosslinking to the same level as virgin UHMWPE. With diffusion, the vitamin E amount used is not limited by the crosslink density, but, vitamin E is exposed to terminal sterilization dose of 25–40 kGy, less than the 100–150 kGy used with blending, which may decrease the grafting of the antioxidant onto the polymer. We investigated the efficiency of grafted vitamin E against squlene-initiated accelerated aging. Methods. Medical grade GUR1050 UHMWPE with vitamin E (0.1 wt%) was irradiated to 150 kGy. Tibial knee insert preforms were irradiated to 100 kGy, diffused with vitamin E using a doping and homogenization procedure. This UHMWPE was used either before or after gamma sterilization. One set of machined blocks (10 × 10 × 6 mm; n = 6) were extracted in boiling hexane for 4 days, then dried. The extracted blocks were doped with squalene at 120°C for 2 hours. One block each was analyzed after doping. The rest were accelerated aged at 70°C and 5 atm. of oxygen for 6 (n = 2) and 14 days (n = 3). Thin sections (150 micron thick) were microtomed and analyzed by Fourier Transform Infrared Spectroscopy to determine a vitamin E index (1245–1275 cm. −1. normalized to 1850–1985 cm. −1. ) and an oxidation index (1700 cm. −1. normalized to 1370 cm. −1. ) after extraction with boiling hexane for 16 hours and drying. Results. After extraction, 92% of the original vitamin E was removed from diffused and sterilized UHMWPE and 99% of the vitamin E was removed from the diffused and unsterilized UHMWPE. Vitamin E content of the blended, irradiated UHMWPEs could not be detected. As a result of accelerated aging in the presence of squalene, all extracted vitamin E-stabilized UHMWPEs showed increased oxidation except diffused, sterilized UHMWPE. The small amount grafted vitamin E in these samples (8%, ∼0.02 wt%) protected irradiated UHMWPE under these conditions. All vitamin E-stabilized, extracted UHMWPEs showed higher oxidative stability than irradiated and melted virgin UHMWPE in the presence of squalene. In the blended, irradiated UHMWPE, there was less effective vitamin E compared to the diffused, sterilized UHMWPE due to the high dose irradiation. Conclusions. Radiation grafting of vitamin E onto UHMWPE was effective against squalene initiated oxidation in accelerated aging. Vitamin E-diffused, sterilized UHMWPE showed no oxidation and diffused, unsterilized UHMWPE and blended, irradiated UHMWPE showed higher oxidative resistance than irradiated/melted UHMWPE

Aims. The objective of this five-year prospective, blinded, randomised controlled trial (RCT) was to compare femoral head penetration into a vitamin E diffused highly cross-linked polyethylene (HXLPE) liner with penetration into a medium cross-linked polyethylene control liner using radiostereometric analysis. . Patients and Methods. Patients scheduled for total hip arthroplasty (THA) were randomised to receive either the study E1 (32 patients) or the control ArComXL polyethylene (35 patients). The median age (range) of the overall cohort was 66 years (40 to 76). Results. The five-year median (interquartile range) proximal femoral head penetration into the E1 was -0.05 mm (-0.13 to -0.02) and 0.07 mm (-0.03 to 0.16) for ArComXL. At three and five years, the penetration was significantly greater in the ArComXL group compared with the E1 group (p = 0.029 and p = 0.019, respectively). All patient-reported outcomes (PROs) improved significantly from the pre-operative interval compared with those at one year, and remained favourable at five years. There were no differences between the two groups at any interval. Conclusion. The five-year results showed that E1 polyethylene does not wear more than the control, ArComXL. This is the longest-term RCT comparing the wear performance and clinical outcome of vitamin E diffused HXLPE with a previous generation of medium cross-linked polyethylene. Cite this article: Bone Joint J 2017;99-B:577–84.

Introduction. Wear of the UHMWPE component is responsible for many TJR failures. It is now well known that oxidation of UHMWPE, induced by radiation sterilisation in air, dramatically increases the wear rate. ASTM regulations for orthopaedic UHMWPE forbids the addiction of any antioxidant to the polymer powder or to fabricated forms. Vitamin E is widely employed as a biocompatible stabiliser in the food and cosmetic industry. Aim of the present study is to evaluate the efficiency of Vitamin E as a stabiliser for prosthetic UHMWPE. Materials. Virgin UHMWPE samples were obtained from compression moulded slabs (GUR 1020, Perplas). In addiction, compression moulded slabs of GUR 1020 mixed with 500 and 1000 ppm of Vitamin E respectively were also studied. Electron beam irradiation was performed with doses ranging from 50 to 225 kGy, in air, at room temperature. Slices of controlled thickness (0,1–0,3 mm) were microtomed from the blocks and accelerated ageing was carried out in a ventilated oven at 90°C. FTIR spectroscopy were used to monitor changes in the polymer structure after irradiation and ageing. Mechanical properties were evaluated using the small punch test, as described in ASTM F2183-02. Results. FTIR measurements on the aged samples showed that the addiction of Vitamin E induces a substantial increase in the oxidative stability of UHMWPE. The overall work to failure of original UHMWPE irradiated at 100 kGy was halved after 160 hours of accelerated ageing, due to the developed oxidation. On the other hand, the work to failure of samples with Vitamin E was constant up to 1800 hours of ageing under the same conditions. Discussion Irradiation of UHMWPE induces C-C and C-H bond scissions, leading to the formation of alkyl radicals. When irradiation is carried out in air, macroal-kyl radicals can react with oxygen to form hydroperox-ides, which in turn decompose giving other oxidation species, mainly ketones and acids, which decrease the molecular mass. Oxidation of the polymer has been found to cause a dramatic deterioration of its mechanical properties. Vitamin E has been shown to be highly efficient against radiation-induced oxidation and therefore it should be recommended as biocompatible stabilizer for orthopaedic UHMWPE, in order to preserve good mechanical properties

Concerns about reduced strength, fatigue resistance, and oxidative stability of highly crosslinked UHMWPE have limited the acceptance of these materials for TKR. It was hypothesized that a new crosslinked UHMWPE stabilized with vitamin E would substantially improve wear performance and resistance to oxidative degradation without compromising mechanical properties. The purpose of this study was to comprehensively test this hypothesis in vitro. GUR1020 was machined from isostatic molded bar-stock, crosslinked with 100 kGy, and then doped with vitamin E. This material was compared to direct molded GUR1050 UHMWPE. Both materials were gamma irradiation sterilized as for clinical use. Small punch testing, crack growth rate fatigue testing and oxidation index measurements were performed on each material before and after accelerated aging. Knee simulator testing evaluated wear of each material for 5-million walking cycles. CR knees were tested on a 6-station AMTI knee simulator; PS knees were tested on two 4-station Instron-Stan-more knee simulators. Statistical differences in all metrics were evaluated for significance with ANOVA (p < 0.05). After 4-week accelerated aging, the control material showed elevated oxidation, loss of small punch mechanical properties and decreased fatigue crack growth resistance. In contrast, the vitamin E stabilized material had minimal changes in these properties. Further, the vitamin E stabilized material exhibited 85% reduction in wear for both the CR and PS designs. Highly crosslinked UHMWPE stabilized with vitamin E appears to be promising for use as a bearing surface in TKA

INTRODUCTION. Electron-beam-irradiated dl-α-Tocopherol (Vitamin E)-blended UHMWPE is now being considered as a potential new bearing surface material for hip prosthesis [1]. However, Vitamin E stabilizes some of the primary free-radicals required for crosslinking, thereby reducing the material's crosslink density [2]. Additionally, some biological-stabilization effects of Vitamin E may also be reduced by oxidation. In this study, Vitamin E radicals in electron-beam-irradiated UHMWPE were measured and identified using Electron Spin Resonance (ESR), and the effects of annealing on radical stabilization and crosslink density were examined. MATERIALS & METHODS. Both pure UHMWPE and Vitamin E added (0.3% w/w) resin was used to produce bulk specimens via vacuum direct compression molding at 220°C under 25 MPa for 30 min. Cylindrical pins (3.5 mm diameter, 40 mm length) for ESR measurement were then machined and placed in vacuum packaging. The pins were irradiated at 300 kGy, with half of each test group annealed at 80°C for 24 hours. Free radical measurements were made using a high-sensitive X-band ESR operating at 9.44 GHz. Detection of Vitamin E radicals was performed by comparing the characteristic symmetrical spectrum of oxidized Vitamin E to the spectra observed for the pins using both g-value and linewidth as references. Crosslink density was measured via gel fraction analysis and was performed in accordance with ASTM D2765. Thin sections (20 × 40 mm. 2. , 200 μm) were machined from the bulk specimens, which were then placed in vacuum packaging, irradiated and annealed at the same conditions as those for the ESR measurements. Two of these thin sections were then placed in a stainless-steel cage (200 µm pore diameter) and were immersed in decahydronaphtalene at 200°C for 24 hours. These specimens were then extracted using soxhlet extractor at 100°C for 24 hours and dried in vacuum at 150°C for 12 hours. RESULTS. The characteristic symmetrical spectrum of oxidized Vitamin E was measured and identified in the electron-beam-irradiated Vitamin E-blended specimens [Fig. 1]. For the annealed samples, this spectrum was reduced [Fig. 2]. The annealing treatments increased gel fraction [Fig. 3] and decreased the total amount of primary free-radicals [Fig. 4] in the electron-beam-irradiated Vitamin E-blended specimens at the same rate as that for the Virgin specimens. DISCUSSION & CONCLUSIONS. Electron-beam-irradiated Vitamin E-blended specimens showed the same characteristic symmetrical spectrum as that of oxidized Vitamin E. Thus, measurement and identification of Vitamin E radicals in electron-beam-irradiated UHMWPE was confirmed. Also, annealing treatment at 80°C for 24 hours was effective in stabilizing Vitamin E radicals. The results showed in [Fig. 3] and [Fig. 4] suggest that the treatments increased gel fraction by accelerating the reaction between primary free-radicals. The results also suggest that Vitamin E radical stabilization was achieved through the interaction of Vitamin E radicals amongst themselves, and not through the interchange between Vitamin E radicals and primary free-radicals

The addition of vitamin E has been shown to improve wear performance in highly crosslinked (HXL) ultra high molecular weight polyethylene (UHMWPE) total knee replacements (TKR) [1]. We set-out to verify if a new type of vitamin E stabilized HXL UHMWPE would substantially improve wear performance, and we present our new results together with our previous ones to tell a fuller story. This paper therefore reports in vitro wear of tibial bearings of both conventional and HXL UHMWPE (with vitamin E) for a total of 16 specimens covering both ends of the TKR size spectrum, very large and very small. Different designs, sizes and four material types/processes of UHMWPE were tested. In material type 1, tested previously, the polyethylene was machined from isostatic molded GUR1020 bar stock, crosslinked with 10 Mrad, and then doped with vitamin E. From this material, 4 samples of large posterior stabilized (LPS1) TKRs were tested. Material type 2 was HXL where vitamin E was blended into the polyethylene (GUR1020) at the powder stage and the final irradiation was to 9 Mrad. From this material, 2 large cruciate retaining (LCR2) samples and 2 small cruciate retaining (SCR2) samples were tested. The above sample groups from both material types 1 and 2 were compared in the same simulator testing to corresponding identical design, size and sample numbers of conventional UHMWPE not highly crosslinked and with no vitamin E (material types 3 & 4 respectively). Each test was run on a significantly upgraded (in house) 4-station Instron-Stanmore force-controlled knee simulator. The machine simulated flexion with anatomically realistic joint reaction forces and torques between tibia and femur, and included a spring-based system to simulate soft-tissue restraining forces and torques. The force-control waveforms of the walking cycle specified in ISO-14243-1 were applied for 5 million cycles (Mc) at 1Hz, with bovine serum lubrication with 20g/l protein concentration at 37°C). The tibial bearing inserts were weighed at various intervals standardized between all tests. No gross delamination or fracture of the tibial inserts was observed in any tests, but all inserts showed measurable wear. The vitamin E stabilized material exhibited an 85% reduction in wear for the LPS1 designs (p < 0.05, ANOVA) compared to its corresponding conventional poly control material. The LCR2 and SCR2 designs with the new vitamin E material exhibited wear reductions of 61% and 77%, respectively when compared to their corresponding conventional bearings (p < 0.05, ANOVA). The vitamin E highly crosslinked UHMWPE tibial bearings significantly reduced overall wear when compared to conventional tibial bearings of the same design. Such level of wear reduction should translate to worthy clinical significance in preventing osteolysis. Highly crosslinked UHMWPE stabilized with vitamin E appears to be promising for use as a bearing surface in TKR, from at least two different technologies/processes

Summary Statement. In the present hip simulator studies, bearings with the newest generation of HXLPE, stabilised with vitamin E, did not show increased wear under severe conditions, such as accelerated ageing, component mal-orientation and third body wear. Introduction. Unfortunately, acetabular hip components cannot always be implanted in optimal condition. Therefore, we performed hip simulator studies with cups made from highly cross-linked, vitamin E stabilised UHMWPE in i) artificially aged condition, ii) with an inclination angle corresponding to 80 ° in vivo and iii) with third bodies coming from the Ti coating of the acetabular cup. Methods. For these hip simulator studies, seleXys cup inlays, size 28/EE, and RM Pressfit samples 50/28 (Mathys Ltd Bettlach, Switzerland) were used. Standard PE parts and vitamys® inlays (highly cross-linked, vitamin E stabilised UHMWPE) were tested in the same series. PE cups were machined out of sintered GUR 1020 slabs, packaged and gamma-sterilised in inert atmosphere at 30 kGy. The vitamys® material was made in-house by adding 0.1 wt.-% of vitamin E (Merck KGaA, Darmstadt/Germany) to GUR 1020 powder from Ticona GmbH, Kelsterbach/Germany. Cross-linking used 100 kGy gamma-irradiation and the final sterilisation was gas plasma. Artificial ageing was done under pressurised oxygen at 70 °C according to ASTM F2003 for 14 days (standard PE) and 60 days (vitamys®), respectively. The hip simulator test protocol of ISO 14242 was kept for the artificially aged cups, but the inclination angle altered to 80 ° for the test with the steep cup position. In the third test, the test fluid (diluted bovine serum stabilised with sodium azide and EDTA) was altered by adding about 10 Ti particles to the bearing for the first million cycles. This test condition imitates third body wear by particles shed from the coating of the RM cups. All testing was conducted at the RMS Foundation (Bettlach / Switzerland) on a servo-hydraulic six-station hip simulator (Endolab, Thansau/Rosenheim, Germany) at a temperature of 37±1°C. At lubricant change interval of 500’000 cycles, the inlays were measured gravimetrically with an accuracy of 0.01 mg. Results. The wear rate of the standard UHMWPE in the condition aged for 14 days reached 45 mg/Mcycle, corresponding to a 57 % increase over non-aged cups. For the vitamys® cups, the wear rate was virtually unchanged even after 60 days ageing (5.8 mg/Mcycle vs. 5.9 mg/Mcycle). For standard UHMWPE tested with an inclination of 80°, wear was 16% lower than those of the inlays with 45° inclination. Whereas for the vitamys® inlays, the wear rate was about the same for both inclination angles (5.4 mg/Mcycle vs. 5.9 mg/Mcycle,). The addition of Ti particles increased the wear rate of standard UHMWPE to 35 mg/Mcycle. However, vitamys® was hardly affected by the third bodies: the wear rate stood at 7.8 mg/Mcycle. Conclusions. Based on the present simulator study, it seems that hip bearings with the newest generation of HXLPE, stabilised with vitamin E, are exempt from increased wear rate when subjected to severe conditions, such as accelerated ageing, component mal-orientation and third body wear

INTRODUCTION. Highly cross-linked polyethylene (XLPE) inserts have shown significant improvements in decreasing wear and osteolysis in total hip arthroplasty [1]. In contrast to that, XLPE has not shown to reduce wear or aseptic loosening in total knee arthroplasty [2,3,4]. One major limitation is that current wear testing in vitro is mainly focused on abrasive-adhesive wear due to level walking test conditions and does not reflect “delamination” as an essential clinical failure mode [5,6]. The objective of our study was to use a highly demanding daily activities wear simulation to evaluate the delamination risk of polyethylene materials with and without vitamin E stabilisation. MATERIALS & METHODS. A cruciate retaining fixed bearing TKA design (Columbus® CR) with artificially aged polyethylene knee bearings (irradiation 30 & 50 kGy) blended with and without 0.1% vitamin E was used under medio-lateral load distribution and soft tissue restrain simulation. Daily patient activities measured by Bergmann et al. [7] in vivo, were applied for 5 million knee wear cycles in a combination of 40% stairs up, 40 % stairs down, 10% level walking, 8% chair raising and 2% deep squatting with up to 100° flexion [8] (Fig. 1). The specimens were evaluated for gravimetric wear and analysed for abrasive-adhesive and delamination wear modes. RESULTS. The total amount of gliding surface wear was 28.7±1.9 mg for the vitamin E stabilised polyethylene irradiated with 30 kGy and 26.5±5.7 mg with 50 kGy irradiation, compared to 355.9±119.8 mg for the standard material. The combination of artificial ageing and high demanding knee wear simulation leads to visible signs of delamination in the articulating standard polyethylene bearing areas in vitro. Delamination began after 2 million test cycles for the standard polyethylene, indicated by the transition between linear and exponential slope in Fig. 2. Delamination was not found in the Vitamin E blended gliding surfaces. CONCLUSION. To evaluate moderately or highly cross-linked polyethylenes in regard to ageing and wear behaviour in vitro, conditions are simulated to create clinical relevant failure modes given in total knee arthroplasty. With the applied test protocol it is possible to discriminate between the polyethylene bearing materials with and without Vitamin E stabilisation. To view tables/figures, please contact authors directly

Recent findings about UHMWPE oxidation from in vivo stresses lead to the need of a better understanding of which anti-oxidant additivation method is the best option for the use in orthopaedic field. A GUR 1050 crosslinked Vitamin E - blended UHMWPE has been investigated, to provide an accurate outline of its properties. DSC and FTIR measurements, together with ageing and tensile tests were performed on compression moulded blocks, as well as biocompatibility tests, including implantation on rabbits. Moreover, wear simulations on finished components (Delta acetabular liners) have been completed. All the test procedures have been repeated for a reference material, a GUR 1050 crosslinked and remelted standard UHMWPE (commercial name UHMWPE X-Lima), and the outcomes have been compared to the crosslinked Vitamin E - blended UHMWPE ones. On the additivated UHMWPE, we found a ultimate tensile strength of 43 MPa, a yield strength value of 25 MPa, and an elongation to breakage equal to 320%. The degree of cristallinity was 45 ± 2%, and no signal of creation of oxidation products was detected up to 2000 h of permanence in oxidant ambient after the ageing test. The reference material showed comparable mechanical resistance values (∗ = 40 MPa, y = 20 MPa, 350% elongation), a cristallinity of 46 ± 2%, and the creation of oxidation products starting from 700 h in oxidant ambient. The biocompatibility tests indicate that the additivated material is biocompatible, as the reference X-Lima UHMWPE. Wear tests gave a wear rate of 5,09 mg/million cycles against 6,13 mg/million cycles of the reference material, and no sign of run in wear rate. Our results indicate that there is no change in mechanical properties in respect to the reference material. This is confirmed by DSC measurements, that show no change in cristallinity. The blend between polymer and additive assures an uniform concentration of Vitamin E across the whole thickness of the moulded block, and ageing test results on additivated UHMWPE have shown that the material possess a superior resistance to degradation phenomena. Biocompatibility assess that the presence of Vitamin E is not detrimental for the in vivo use of the material, and wear results indicate a better wear resistance of the material, especially in the first stages of the wear process. From these considerations, it can be concluded that the material, in respect to the standard UHMWPE, is highly resistant to oxidation phenomena, therefore it is expected to have superior in vivo endurance performance

Vitamin E stabilized highly crosslinked UHMWPE (E-Poly. ™. ) was developed to improve upon the properties of first generation highly crosslinked UHMWPE’s. The post-crosslinking processing for E-Poly. ™. maximizes the strength of the material while at the same time stabilizing residual free radicals that remain after irradiation. E-Poly. ™. is crosslinked with 100 kGy gamma irradiation prior to infusion of vitamin E. The infusion process involves diffusing vitamin E into the crosslinked material at temperatures beneath the melt temperature. Small punch testing (ASTM F2183-02) was completed to evaluate strength of E-Poly. ™. compared to gamma-inert sterilized UHMWPE. The results showed that the E-Poly. ™. material had equivalent or better properties before and after accelerated aging than the gamma-inert sterilized UHMWPE (96–105 N vs. 75–88 N unaged; 100–115 N vs. 42–56 N 2-week aged). Environmental stress crack testing evaluated the resistance to oxidation while the material was subjected to fatigue testing. A constant stress beam was tested for 5 weeks at 80C. Failure was defined as the appearance of cracks or fracture of the specimen. All 4 specimens of gamma sterilized components showed evidence of cracking prior to the completion of the test. 2 of 4 sequentially crosslinked and annealed specimens fractured prior to completion. None of the E-Poly. ™. specimens showed cracks during testing. An examination of the amount of oxidation induced during this testing showed that the addition of fatigue loading increased the oxidation index for UHWMPE’s that had unstabilized free radicals. The surface oxidation index for gamma sterilized UHWMPE increased from ~0.3 to 1.1 and for sequentially crosslinked UHMWPE from ~0.3 to 0.7; the oxidation index for E-Poly. ™. was negligible for all test condition. Hip simulator testing (ISO 14242-1) showed that the volumetric wear rates for E-Poly. ™. were 95–99 % less than that of ArCom. For 28mm head diameters the rates were 53.3 mm3/Mc for ArCom and 0.24 mm3/Mc for E-Poly. ™. Wear particle morphology analysis showed that the E-Poly. ™. wear particles were similar to ArCom. Qualitatively, there appeared to be fewer E-Poly. ™. particles. Knee simulator testing (ISO14243-1) was performed on both cruciate retaining and posterior stabilized Vanguard. ®. knees. The E-Poly. ™. tibial bearing, CR and PS, showed 86% less wear than direct compression molded UHMWPE, the current gold standard. Fatigue testing of the PS post before and after accelerated aging (ASTM F2003) loaded to 1300lbs showed no degradation or failure of the post following 3 million cycles. Vitamin E stabilized highly crosslinked UHMWPE has demonstrated excellent material properties, wear properties, and resistance to oxidation. These properties have been optimized through the combination of cross-linking, processing below the melt temperature subsequent to crosslinking, and the stabilization effect of vitamin E. These properties provide rational support to the utilization of vitamin E stabilized highly crosslinked UHMWPE for hip and knee applications

The aim of this study was to report a 3 year follow up of vitamin E add polyethylene in total knee arthroplasty. UHMWPE powder (GUR1050) was mixed with 0.3% of vitamin E before consolidation by direct compression molding. The vitamin E added UHMWPE was applied to the articular surface and patella in 65 patients (mean age, 69.6 years). Joint fluid concentrations of tocopherol and matrix metalloproteinase 9 were measured in vitamin E added UHMWPE cases one year after surgery, and were compared to those of conventional UHMWPE cases and osteoarthritis patients. Concentrations of α-tocopherol and γ-tocopherol were measured by using HPLC with ultraviolet-visible wavelength detection. Concentrations of matrix metalloproteinase 9 were detected by using enzyme immunoassay. The Average Knee Society score were 91.7(clinical) and 76.7(functional). There were three failures (1 supracondylar fracture, and 2 skin necrosis). The average concentrations of α-tocopherol were 281.8μg/dL (10 cases) in the vitamin E group, 371.8μg/dL (15 cases) in the conventional group, and 317.8μg/dL (46 cases) in the osteoarthritis group. There were no significant differences among three groups. The average concentrations of γ-tocopherol were 43.4μg/dL in the vitamin E group, 52.3μg/dL in the conventional group, and 49.8μg/dL in the osteoarthritis group. There were no significant differences among three groups. The average concentrations of matrix metalloproteinase 9 were 83.2 ng/mL in the vitamin E group, 78.4 ng/mL in the conventional group, and 17.4 ng/mL in the osteoarthritis group. There was no significant difference between the vitamin E group and the conventional group. However, The matrix metalloproteinase 9 concentrations of the osteoarthritis group were significantly lower than others. No cases exhibited measurable polyethylene wear or osteolysis and also no abnormal values relating to vitamin E on joint fluid examinations. At three year follow-up, vitamin E added polyethylene demonstrated the safe use for the human body

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

Ultra-high molecular weight polyethylene (UHMWPE) has been the gold standard material of choice for the load-bearing articulating surface in knee joint prostheses. However, the application of joint replacements to younger (aged < 64 years) and more active people plus the general increase in life expectancy results in an urgent need for a longer lasting material with better in-use performance. There are three major material related causes that can lead to joint failure in UHMWPE knee joint replacements: free radical induced chemical degradation; mechanical degradation through wear and delamination; and UHMWPE micron and submicron wear debris induced osteolysis. As a potential solution to these problems, highly crosslinked UHMWPE stabilised with infused antioxidant vitamin E (α-Tocopherol), which is abbreviated as E-Poly, has been of great interest. In the current work, the wear performance and mechanical properties of Vanguard cruciate retaining (CR) E-Poly tibial inserts were assessed and compared with Vanguard CR Arcom tibial inserts. Also E-Poly plates were compared with direct compression moulded UHMWPE wear plates. Both a multi-directional pin-on-plate tester and a six-station Prosim (Manchester, UK) knee wear simulator were used to assess wear properties of E-Poly plates and E-Poly tibial inserts respectively. All E-Poly plates and tibial inserts were sterilised and vacuum packed in the same way as Vanguard implants before wear testing. The wear knee simulator test was conducted in accordance with ISO 14243-3:2004 with the exception that a more aggressive Tibial Rotation and Anterior/Posterior displacement profiles, based on the kinematics of the natural knee were incorporated. Under the same aggressive pre-clinical wear testing condition, compared with Vanguard Arcom CR tibial inserts, Vanguard E-Poly CR tibial inserts experienced an 85% reduction in the mean wear rate. The former had a mean wear rate of 6.51±1.75 mm. 3. per million cycles (MC) and the latter had a mean wear rate of 0.96±0.11 mm. 3. /MC over the 7 million cycle testing period. A similar reduction (80%±8.5) in the mean wear factor was also observed on E-Poly plates compared with a series of direct compression moulded GUR1050 UHMWPE plates processed under a range of manufacturing processing conditions. Wear testing was conducted with a configuration of flat-ended stainless steel indenters multi-directionally sliding against the UHMWPE plates. Mechanical properties on Vanguard Arcom UHMWPE and E-Polys were evaluated using the small punch test. All tests were carried out using an Instron 5565 Universal Testing System at a constant crosshead speed of 0.5mm/min. With regard to work-to-failure, no statistical difference was observed, with the former being 254.2±4.1 mJ and the latter 255.6±28.2 mJ. However, all E-Polys exhibited strain stiffening due to the stretch of crosslinks. This resulted in a ca 12% reduction in elongation to break observed for E-Polys compared with that of Arcom UHMWPE. The former had an elongation to break of 4.1±0.2 mm and the latter of 4.7±0.3 mm. In conclusion, we have found that Vitamin E Stabilised UHMWPE tibial inserts are promising for knee joint prostheses. However, further investigations are needed to address potential issues such as the particle size and size distribution of E-Poly wear debris and the associated reactivity

Introduction. Ultra high molecular weight polyethylene (UHMWPE) has been used successfully as a bearing material in hip, knee, and shoulder joint replacements. However, there are problems to cause a failure in UHMWPE component, which are wear behavior and creep deformation. Continuous bearing motion and dynamic load have occurred to UHMWPE wear debris caused osteolysis in periprosthetic tissue and to plastic deformation of joint component, and subsequent aseptic loosening of components. Therefore, many studies have being carried out in order to reduce wear debris and to improve mechanical strength from UHMWPE, and there is tremendous improvement of mechanical property in UHMWPE from gamma irradiated conventional UHMWPE (GIPE), highly crosslinked PE (XLPE), and XLPE with vitamin E1, 2. Friction has a significant one of the factors effect on the wear and creep deformation. In this study, the short-term frictional behaviors of three typical types of GIPE, remelted XLPE (R-XLPE), and s annealed XLPE (A-XLPE), and XLPE with Vitamin E against Co-Cr alloy were compared under three levels of contact pressures which occured in hip, knee, and shoulder joints. Methods. Friction tests were conducted with UHMWPE against Co-Cr alloy by using pin-on-disk type triboteter. For test, tribotester performed in a repeat pass rotational slidintg motion with a velocity of 60rpm. Applied contact pressure selected three kinds of levels, 5, 10, and 20MPa which were within the range of maximum contact pressures for total hip, knee, and shoulder joint replacements. To analyze the frictional effect of UHMWPE type, it conducted t-test and p-values less than 0.05 were used to determine the statistically significant difference. Results. In this study, it was observed that coefficients of friction (COF) were affected by various conditions, kinds of materials and applied load. We can reveal the frictional behavior of UHMWPE in various contact pressures. The average of the COF measured that GIPE was 0.029∼0.0423, R-XLPE was 0.018∼0.031, A-XLPE was 0.023∼0.038, and XLPE with Vitamin E was 0.013∼0.027 under 5, 10, and 20MPa. Discussion. COF of R-XLPE, A-XLPE, and XPLE with Vitamin E were lower than GIPE for all levels of contact pressures. This study showed the trend that COF decreased as contact pressure increased. Also, XPLE with Vitamin E has lowest frictional values among UHMWPEs. In the viewpoint of applied load, it was decreased as a contact pressure increased for COF of GIPE, RXLPE, and AXLPE against Co-Cr alloy. COF of GIPE, XLPEs, and XLPE with Vitamin E against Co-Cr alloy were as low as using bio materials compared with the COF of cartilage to cartilage, which was about 0.024. Conclusions. In conclusion, average COF of XLPE with Vitamin E was significantly lower than those of R-XLPE and A-XLPE. XLPEs showed much lower COF than GIPE

Introduction. Increased oxidative stability of orthopedic implants can be achieved by adding an antioxidant, such as Vitamin E (VE) to UHMWPE[1]. The effect of shelf live and accelaterated aging in combination with shelf live on antioxidative effectiveness of VE needs to be investigated to better understand the long-time behavior of VE-blended UHMWPE in an oxidative environment. Currently, IR techniques provide detection limits as low as 0.05 %w/w[2], also it is known that thermo analytical techniques can push the limit of detection down to 10 ppm[3]. The goal of this study was to quantify VE in UHMWPE powder and compression molded UHMWPE with 11 different VE concentrations using FTIR and DSC techniques and to establish respective regression curves. Methods & Materials. GUR 1050 UHMWPE resin (Ticona, Germany) was blended with VE (DSM, Netherlands) to the following target concentrations (%w/w): 0.01, 0.02, 0.05, 0.1, 0.25, 0.35. Concentrations of 0.001, 0.002, 0.003, 0.004, 0.005 were obtained by mixing of the 0.1 powder with virgin GUR 1050 powder. VE-free GUR 1050 was used as reference. Samples of blended resin were compression molded in a low oxygen environment atmosphere at Zimmer Inc. (Warsaw, IN). Subsequently the blocks were microtomed, creating films with a thickness of 200µm for each concentration. The VE concentration was measured using infrared (IR) spectroscopy (BioRad FT6000). The ratios were calculated by normalizing the integrated ether C-O(R) signal (1232cm. −1. to 1275cm. −1. ) and the integrated hydroxyl C-O(H) signal (1190cm. −1. to 1228cm. −1. ) using the twisting CH bond (1980cm. ∗∗∗∗∗. to 2100cm. −1. ) as reference peak area. Oxidative induction time (OIT) at 200°C was measured according to ASTM D 3895–98 using blended and mixed powder samples. Results. Infrared spectroscopy. A strong positive linear correlation between the normalized peak areas and the effectively blended VE content was detected for both ether (Figure 1) and hydroxyl ratios. Figure 1: Normalized ether signal plotted over blended VE sample (928 IR spectra / 7 VE concentrations). Samples below 0.01 %w/w were not FTIR tested as they fell below the detection limits of 0.0074 and 0.0092 %w/w[4] based on ether and hydroxyl ratios. Oxidative-induction time. A logarithmic correlation between oxidation time and the effectively blended VE content was detected (Figure 2). Figure 2: OIT over effectively blended VE concentration (36 data points / 12 VE concentrations). Using OIT, VE concentrations down to 0.001 and 0.002 %w/w VE were quantified with D. absolute. of below 0.0002 %w/w and D. relative. of below 20% to the regression (Figure 3). Figure 3: Relative differences of quantification of VE over blended VE to regression via OIT and IR. Discussion. This study proves detectability of VE concentrations of 0.01 %w/w via calibrated IR absorbance and 0.001 %w/w using a calibrated OIT method at 200°C. Thus, mapping of VE chemical moities within UHMWPE samples below 0.05 %w/w VE by IR and detection of antioxidative stabilization in UHMWPE samples containing less than 0.002 %w/w VE can be achieved. Based on these findings, highly accurate VE measurements for aged, unaged, retrieved and differently processed materials shall be enabled