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

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

The purpose of the study was to compare the mechanical properties, oxidation and wear resistance of a vitamin E blended and moderately crosslinked polyethylene for total knee arthroplasty (MXE) in comparison with clinically established polyethylene materials. The following polyethylene materials were tested: CPE (30 kGy e-beam sterilized), XLPE (75 kGy gamma crosslinked @ 100°C), ViXLPE (0.1 % vitamin E blended, 80 kGy e-beam crosslinked @ 100°C), and MXE (0.1 % vitamin E blended polyethylene, 30 kGy gamma sterilized). For the different tests, the polyethylene materials were either unaged or artificially aged for two or six weeks according to ASTM F2003-02. The oxidation index was measured based on ASTM F2102 at a 1 mm depth. Small punch testing was performed based on ASTM F2977. Mechanical properties were measured on unaged materials according to ASTM D638. Wear simulation was performed on a load controlled 3 + 1 station knee wear simulator (EndoLab GmbH, Thansau, Germany) capable of reproducing loads and movement of highly demanding activities (HDA) as well as ISO 14243-1 load profiles. The load profiles were applied for 5 million cycles (mc) or delamination of the polyethylene components. Medium size AS e.motion. ®. PS Pro (Aesculap AG, Tuttlingen, Germany) femoral and tibial components with a ZrN-multilayer surface, as well as Columbus. ®. CR cobalt-chrome alloy femoral and tibial components were tested. Particle analysis was performed on the serum samples of the ISO 14243-1 wear simulations based on ISO 17853:2011 and ASTM F1877. The analysis of the mechanical properties show that moderately crosslinked polyethylene (MXE) might be a superior material for total knee arthroplasty applications [Schwiesau et al. 2021]. The addition of vitamin E in a moderately crosslinked polyethylene prevented its oxidation, kept its mechanical characteristics, and maintained a low wear, even under a HDA knee wear simulation

Abstract. Objectives. Ultra-High Molecular Weight Polyethylene (UHMWPE) can be made radiopaque through the diffusion of an oil-based contrast agent (Lipiodol Ultra-fluid). A similar process is used for Vitamin E incorporated polyethylene, which has a well-established clinical history. This study aimed to quantify the leaching of Lipiodol and compare to vitamin E polyethylene. Method. GUR 1050 polyethylene (4 mm thickness) was cut into squares, 10 mm. 2. Samples (n=5) were immersed in 25 ml Lipiodol (Guerbet, France), or 15 ml Vitamin E (L-atocopherol, Sigma-Aldrich, UK). To facilitate diffusion, samples were held at 105°C for 18 hours. After treatment, all samples were immersed in DMEM (Sigma-Aldrich, UK) with Penicillin Streptomycin (Sigma-Aldrich, Kent, UK) at 4%v/v and held at 37°C in an incubator. Untreated polyethylene samples were included as controls. Leaching was quantified gravimetrically at weeks 2, 4 and 8. The radiopacity of the Lipiodol-diffused samples was investigated from µCT images (162kV, resolution 0.2 mm, X Tec, XT H 225 ST, Nikon Metrology, UK). Results. The leaching of Lipiodol and Vitamin E followed the same trend and reached a steady state after week 2. At this point there was a 20% decrease in the Hounsfield Unit and droplets of radiopaque oil were visible in the DMEM solution; these were not evident in subsequent scans. Over 8 weeks of 20% Lipiodol leached out of the polyethylene, which was greater than of 10% Vitamin E. Conclusion. After 8 weeks the radiopaque polyethylene was still identifiable in CT scan images, even though 20% of leaching occurred. The leaching of Lipiodol may be mitigated through cross-linking, which has been shown to reduce leaching of Vitamin E; this will be investigated as future work. Declaration of Interest. (b) declare that there is no conflict of interest that could be perceived as prejudicing the impartiality of the research reported:I declare that there is no conflict of interest that could be perceived as prejudicing the impartiality of the research project

Summary. Low energy irradiation of vitamin E blended UHMWPE is feasible to fabricate total joint implants with high wear resistance and impact strength. Introduction. Irradiated ultra-high molecular weight polyethylene (UHMWPE), used in the fabrication of joint implants, has increased wear resistance. But, increased crosslinking decreases the mechanical strength of the polymer, thus limiting the crosslinking to the surface is desirable. Here, we used electron beam irradiation with low energy electrons to limit the penetration of the radiation exposure and achieve surface cross-linking. Methods. Medical grade 0.1wt% vitamin E blended UHMWPE (GUR1050) was consolidated and irradiated using an electron beam at 0.8 and 3 MeV to 150 kGy. Fourier Transform Infrared Spectroscopy (FTIR) was used from the surface along the depth at an average of 32 scans and a resolution of 4 cm. −1. A transvinylene index (TVI) was calculated by normalizing the absorbance at 965 cm. −1. (950–980cm. −1. ) against 1895 cm. −1. (1850 – 1985 cm. −1. ). TVI in irradiated UHMWPE is linearly correlated with the radiation received [3]. Vitamin E indices were calculated as the ratio of the area under 1265 cm. −1. (1245–1275 cm. −1. ) normalized by the same. Pin-on-disc (POD) wear testing was conducted on cylindrical pins (9 mm dia., 13 mm length, n=3) as previously described at 2 Hz [4] for 1.2 million cycles (MC). Wear rate was measured as the linear regression of gravimetric weight change vs. number of cycles from 0.5 to 1.2 MC. Double notched IZOD impact testing was performed (63.5 × 12.7 × 6.35mm) in accordance with ASTM F648. Cubes (1 cm) from 0.1wt% blended and 150 kGy irradiated pucks (0.8 MeV) were soaked in vitamin E at 110°C for 1 hour followed by homogenization at 130°C for 48 hours. Results. The penetration of the electron beam for cross-linking was limited at low beam energy and cross-linking of the surface 2 mm was achieved. The wear rate of samples irradiated at 0.8 and 3 MeV was 1.12±0.15, and 0.98±0.11, respectively (p»0.5). In addition, the wear rate of the surface (0.8 MeV) irradiated UHMWPE was 0.33±0.02 mg/MC 1 mm below the surface. The impact strength of UHMWPE irradiated at 0.8 MeV was 73 kJ/m. 2. and 54.2 kJ/m. 2. for that irradiated at 3 MeV (p=0.001). Doping with vitamin E and homogenization increased the surface vitamin E concentration from undetectable levels to 0.11±0.01. Discussion. The wear rate of this surface cross-linked UHMWPE was comparable to uniformly cross-linked UHMWPEs irradiated at higher electron beam energies. Even lower wear rate subsurface suggested the feasibility of machining 1 mm from the surface in implant fabrication. Limiting cross-linking to the surface resulted in higher impact strength compared to a uniformly cross-linked UHMWPE. Vitamin E was optionally replenished by additional doping after cross-linking; an advantage of this method may be increased oxidation resistance

Background. Wear simulation in total knee arthroplasty (TKA) is currently based on the most frequent activity – level walking. A decade ago multi-station knee wear simulators were introduced leading to optimisations of TKA designs, component surface finish and bearing materials. One major limitation is that current wear testing is mainly focused on abrasive-adhesive wear and in vitro testing does not reflect “delamination” as an essential clinical failure mode. 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. Methods. A cruciate retaining fixed bearing TKA design (Columbus CR) with artificially aged polyethylene knee bearings (irradiation 30±2 kGy) blended with and without 0.1% vitamin E was used under medio-lateral load distribution and soft tissue restrain simulation. Daily patient activities with high flexion (2×40% stairs up and down, 10% level walking, 8% chair raising, 2% deep squatting) were applied for 5 million cycles. 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 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 bearing areas in vitro. Conclusion. To evaluate Vitamin E stabilised polyethylenes in regard to ageing and wear behaviour in vitro, conditions are simulated to create clinical relevant failure modes in the reference material

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

Introduction. Recently, oxidative stress has been implicated in the development of osteonecrosis. Here we focused on vitamins with marked antioxidant potency to see whether their use might prevent the development of osteonecrosis associated with corticosteroid administration. Methods. Fifteen male Japanese white rabbits weighing about 3.5 kg were injected once into the right gluteal muscle with methylprednisolone (MPSL) 40 mg/kg (S Group). Ten other rabbits, in addition, received consecutive daily intravenous injections of vitamin E 50 mg/kg starting from the day of MPSL administration (E Group), and 10 other animals similarly received consecutive daily intravenous injections of vitamin C 30 mg/kg (C Group). All animals were euthanized 2 weeks after MPSL administration, and femurs were extracted, and stained with hematoxylin-eosin. Blood levels of glutathione (GSH) were also measured. Results. In S Group, the osteonecrosis development rate was 93%, in contrast to 60% in C Group, and none in E Group (P<0.05). Also, GSH levels in both S and C Groups abruptly decreased from the 1st day after MPSL administration, whereas, in E Group, the decline in GSH levels was significantly suppressed on days 1 and 3 after MPSL administration (P<0.05). Conclusion. Vitamin E significantly inhibited the decrease in blood GSH levels noted in the groups not receiving it. Since GSH reflects oxidative stress in vivo, vitamin E administration may be preventative in the setting of this kind of corticosteroid-induced osteonecrosis rabbit model

INTRODUCTION. Highly cross linked polyethylenes (HXPE) have to be treated thermally after irradiation to eliminate residual free radicals. By adding vitamin E in the polyethylene powder a post-irradiation thermal treatment is not necessary. In this review the correlation between the intrinsic properties and the long-term stability of Vitelene® as a high performance material for artificial hip articulation will be displayed. MATERIALS & METHODS. Three different types of polyethylene (UHMWPE; GUR1020) were analyzed to compare mechanical properties as well as oxidative stability: PE. STD. (γ, 30 kGy, N. 2. ), HXPE. REM. (γ, 75 kGy, remelted, EO), Vitelene® (β, 80 kGy, 0.1% Vitamin E, EO). Artificial aging (ASTM F2003 − 70 °C, O. 2. at 5 bar) was used to simulate environmental damage. To evaluate the oxidation stability the Oxidation-Induction-Time (OIT) was measured by Differential Scanning Calorimetry (DSC - ASTM D3895) and the Oxidation Index (OI) was determined by Fourier-Transformation-Infrared-Spectroscopy (FTIR - ASTM F2102). The mechanical properties were analyzed by tensile- and impact investigations (ASTM D638 and ISO 11542-2) as well as by Small Punch Testing (SPT - ASTM F2183). The amount of wear was measured gravimetrically (ISO 14242-2). RESULTS. OIT [minutes], after 0, 14, 28, 42, 56 and 70 days aging, respectively 0.47, 0.41, 0.45, 0.42, 0.42 and not determined (nd) for PE. STD,. 0.46, 0.46, 0.47, 0.41, 0.41 and nd for HXPE. REM,. 12.09±0.50, 11.67±0.54, 10.78±0.25, 10.42±0.36, nd and 9.25±0.19 for Vitelene®. Cristallinity [%], after 0, 14, 28 and 42 days aging, respectively 55±2, 63±2, 79±4, 88±3 for PE. STD. , 47±2, 48±0, 50±1, 57±1 for HXPE. REM. , 52±1, 51±1, 53±14, 53±2 for Vitelene®. OI, after 0, 14, 28, 35 and 42 days aging, respectively 0.11±0.03, 0.67±0.15, 4.48±1.17 for PE. STD. , 0.07±0.05, 0.06±0.02, 0.09±0.02, 0.24±0.05, 0.69±0.36 for HXPE. REM. , 0.06±0.01, 0.08±0.01, 0.08±0.01, 0.09±0.01, 0.09±0.01 for Vitelene®. Tensile Strength [MPa], after 0 and 42 days aging, respectively 47.9±10, 0.7±0 for PE. STD. , 56.0±4.0, 25.0±2.0 for HXPE. REM. , 53.1±1.0, 52.0±4.3 for Vitelene®. Elongation [%], after 0 and 42 days aging, respectively 469±69 and 0 for PE. STD. , 343±14, 7±3 for HXPE. REM. , 372±11, 380±15 for Vitelene®. Impact Strength [kJ/m²], after 0 and 42 days aging, respectively 149±6, 4±1 for PE. STD. , 95±1, 5±1 for HXPE. REM. , 86±10, 91±7 for Vitelene®. SPT - Average Ultimate Load [N], after 0, 14 and 28 days aging, respectively 61.5±4.0, 56.3±5.3, 8.2±0.2 for PE. STD. , 71.4±2.2, 68.0±9.9, 64.4±8.2 for Vitelene®. Wear [mg/Mio cycles] (Ø36 mm Biolox® delta), after 0, 14 and 42 days aging, respectively 19.0±0.6, 30.3±3.1 and 365.8±37,2 for PE. STD. , 2.0±0.3, nd and 52.0±16.4 for HXPE. REM. , 2.5±0.5, nd and 2.3±0.7 for Vitelene®. CONCLUSION. The mechanical properties of Vitelene® are unchanged even after 42 days of artificial aging which is correlated to low wear in total hip arthroplasty. Vitamin E stabilization is effective in preventing oxidation and aging of the polyethylene after irradiation cross linking

Summary. Fifteen irradiated, vitamin E-diffused UHMWPE retrievals with up to three years in vivo service showed no appreciable oxidation, nor change in material properties from a never-implanted liner, and showed a 94% decrease in free radical content. Introduction. Radiation cross-linking, used to improve wear resistance of ultra-high molecular weight polyethylene (UHMWPE) bearings used in total joint arthroplasty, generates residual free radicals which are the precursors to oxidative embrittlement. First generation materials adopted thermal treatments to eliminate or reduce free radical content, but came with compromises in reduced mechanical properties or insufficient stabilization. A second generation alternative method infuses an antioxidant, vitamin E, into irradiated UHMWPE to stabilise free radicals while maintaining fatigue strength. In vitro studies predict excellent oxidation and wear resistance in vitamin E-stabilised bearings, but the long-term in vivo oxidation behavior, influenced by lipid absorption and cyclic loading, remains largely unknown. Our aim was to investigate in vivo changes in UHMWPE surgically-retrieved explants that were radiation cross-linked and stabilised by vitamin E. Patients & Methods. Fifteen surgically-retrieved irradiated, vitamin E-diffused and inert-gamma sterilised bearings (E1™, Biomet, Inc., Warsaw IN) with in vivo durations ranging from 3 days to 36.6 months were analyzed at unloaded rim/eminence and the articular surface along with one never-implanted component. Total lifetime of components was summed as shelf storage prior to implantation, in vivo duration and ex vivo duration in air. Fourier Transform Infrared Spectroscopy (FTIR) was used to measure carbonyl index (CI; per ASTM F2102-01ε1) both before and after 16 hour hexane extraction to. Extracted thin films were also reacted with nitric oxide to quantify hydroperoxides, an intermediate oxidation product associated with oxidation potential. Cross-link density was calculated from gravimetric swelling analysis per ASTM F2214. Crystallinity measurements were performed regionally using differential scanning calorimetry (DSC). Free radical content was measured by electron spin resonance (Memphis, TN). Results. Irradiated and vitamin E-diffused retrievals showed scratching at the articular surface, but retained machining marks up to three years in vivo, indicative of no measurable wear. Retrievals showed no significant oxidation at the time of surgical removal with maximum post-hexane carbonyl indices in the barely detectable range (MCI=0.029–0.154), located at the surface of retrievals. Ex vivo oxidation was not observed after 18 months of aging in air at room temperature. There was no increase in hydroperoxides (never-implanted HI=0.62±0.04; retrieval HI= 0.62±0.04), nor change in cross-link density (never-implanted: 0.275±0.015 mol/dm. 3. ; retrieval: 0.295±0.016 mol/dm. 3. ) or crystallinity (never-implanted: 58.3±1.4%; retrievals: 60.0±3.5%). Lipid penetration increased with time, showing a higher rate of diffusion in loaded regions. Free radical content was observed to decay with increasing in vivo duration (R. 2. =0.44; p<0.05), and by one order of magnitude (94%) by 36.6 months. A stronger negative correlation (R. 2. =0.65) was observed between the total lifetime of the liner and free radical content. Discussion/Conclusion. The free-radical scavenging activity of the vitamin E appears to successfully prevent both in vivo and ex vivo oxidation for short durations. Without an increase in hydroperoxides, the oxidation cascade initiated by radiation-induced and lipid-derived free radicals appears to have been halted. Retrievals also gave no indication of wear in this timeframe, similar to improved wear resistance seen in first generation materials. Continued monitoring will be necessary at longer implant durations

Abstract. Objectives. Oil-based fluids can be used to enhance the properties of polyethylene materials. For example, vitamin E infused polyethylene has a superior oxidation resistance and Lipiodol infused polyethylene has an enhanced X-ray attenuation. The aim of this study was to evaluate the long-term influence of oily fluid on the chemical, physical and tensile properties of polyethylene. Methods. An accelerated ageing procedure (an elevated temperature (80. °. C) for four weeks in air. 1. ) was used to investigate the oxidative stability (ASTM F2012-17). 2. , tensile (ISO 527). 3. and thermal properties. 4. of oil treated polyethylene (n=5, GUR 1050, Celanese, Germany)and compared with clinically used polyethylene controls (oil-free standard and thermally treated polyethylene). All the experiments were performed on aged and unaged specimens in accordance to international standards and compared to currently available literature. A Kruskal-Wallis test was performed using a custom MATLAB code (R2017a, USA); with p < 0.05 considered statistically significant. Results. Samples treated with an oil (Vitamin E or Lipiodol) had a higher oxidation stability than currently used medical grade polyethylene, indicated by a smaller increase in oxidation index after ageing (Vitamin E 36%, Lipiodol 40%, untreated 136 %, thermally treated 164%). The mechanical degradation of oil treated polyethylene was also less significant than the untreated controls, as all the tensile properties of oil treated polyethylene after ageing were significantly higher than the standard controls (p>0.05). There was also no alteration in the percentage crystallinity of oil treated samples after ageing. Conclusion. The result of this study indicate that the presence of an oily fluid in polyethylene does not reduce its oxidative stability or tensile properties, providing improved material properties for long term implant applications. Declaration of Interest. (b) declare that there is no conflict of interest that could be perceived as prejudicing the impartiality of the research reported:I declare that there is no conflict of interest that could be perceived as prejudicing the impartiality of the research project

Summary. Prosthetic UHMWPE added with vitamin E and crosslinked UHMWPE are able to decrease significantly the adhesion of various bacterial and fungal strains limiting biomaterial associated infection and consequent implant failure. Introduction. Polyethylene abrasive and oxidative wear induces overtime in vivo a foreign-body response and consequently osteolysis, pain and need of implant revision. To solve these problems the orthopaedic research has been addressed to develop new biomaterials such as a crosslinked polyethylene with a higher molecular mass than standard Ultra High Molecular Weight Polyethylene (UHMWPE), and consequently a higher abrasive wear resistance and an antioxidant (vitamin E)-added UHMWPE to avoid oxidative wear. Nevertheless a feared complication of implant surgery is bacterial or fungal infection, initiated by microbial adhesion and biofilm formation, and related to the biomaterial surface characteristics. Staphylococci are the most common microorganisms causing biomaterial associated infection (BAI), followed by streptococci, Gram-negative bacilli and yeasts. With the aim to prevent BAI, the purpose of this study was to evaluate the adhesion of various microbial strains on different prosthetic materials with specific surface chemical characteristics, used in orthopaedic surgery. Methods. We compared the effects of vitamin E-added UHMWPE and crosslinked UHMWPE with that of standard GUR 1020 UHMWPE, upon the adhesion of ATCC biofilm-producing strains of Staphylococcus epidermidis, S. aureus, Escherichia coli and Candida albicans. After different incubation times the samples were sonicated to release the attached microorganisms and spread onto agar to quantify colony forming units (UFC)/ml. The biomaterials were physico-chemically characterised by means of scanning electron microscopy (SEM), water contact angle (CA) measurements and attenuated total reflectance (ATR)-fourier transform infrared (FTIR) spectroscopy, before and after adhesion assays. The experiments were assayed in triplicate and repeated a minimum of three times. A statistical analysis on results was conducted. Results. No significant difference of the surface roughness, CA and ATR-FTIR spectroscopy was found among the different biomaterials. After 3 and 7 h of incubation microbial adhesion rates were similar with no statistically relevant differences among the samples assayed. On the contrary, after 24 and 48 h of incubation a significantly (p<0.05 and p<0.01) different adhesion trend was achieved on the three biomaterials, highlighting a microbial adhesion significantly lower on vitamin E-added UHMWPE and crosslinked UHMWPE compared with that on standard UHMWPE. Discussion/Conclusion. Standard UHMWPE, vitamin E-added UHMWPE and crosslinked UHMWPE were chosen because of their diffusion in the clinical use. Previously we showed that vitamin E addition to the UHMWPE reduces the adhesive ability of various staphylococcal strains, compared with standard UHMWPE, and we correlated this results with its antioxidant properties. The results of this study indicate a quite similar significant reduction of bacterial and fungal adhesion on either vitamin E-added UHMWPE and crosslinked UHMWPE, if compared to standard UHMWPE at 48h. Further analysis on the chemical- physical characteristics of the UHMWPE surfaces and on their morphology are needed to explain the different adhesions

Crosslinking has been already used for about 80 years to enhance the longevity of polyethylene cables. The polymer alteration has been achieved with peroxide, silane or irradiation. The medical devices industry discovered the benefit of this technology for its tribological applications like hip or knee bearings in the 2000s as crosslinking improves considerably the abrasion resistance of the material. The more current methods used are Gamma and Beta irradiation. On the basis of economical (rising prices of Cobalt), environmental (the radioactive source can not be turned off), technological (low dose rate) drawbacks for Gamma respectively low penetration for Beta irradiation we decided to investigate an alternative technology: the X-Ray irradiation, which provides a homogeneous crosslinking in a relatively short time. We analyzed the wear, mechanical, thermal, oxidative and network properties of two vitamin E doped UHMWPE: first crosslinked with E-Beam, second with X-Ray. There wasn't any significant difference between the X-Ray and the E-Beam crosslinked material

A pin-on-disc tribometer test with a rotating disc and a sector-wise loaded pin was used to determine friction coefficients for different material pairings. The four pin materials porcine cartilage, subchondral bone of the porcine cartilage, UHMWPE, vitamin E enhanced, crosslinked UHMWPE (VEPE) in combination with the three-disc materials zirconia toughened alumina ceramic (ZTA), CoCr, carbon-fibre-reinforced carbon (CrC) were tested. Stepwise loading was employed with the forces 10 N, 5 N, 2 N and 1 N. Test duration was 1 h. Diluted calf serum according ISO 14242-1 was used to determine the friction coefficients. The surface topography of all pins was examined using optical profilometry before and after the rotation tribometer tests. - No wear related modifications of the surface roughness parameters could be found. The coefficients of friction (COF) were lowest for the cartilage pins against all three-disc materials, with steady-state values between 0.01 and 0.02 for the highest applied load (10 N). Friction of subchondral bone yielded COF in the range 0.2 … 0.6, depending on the counterpart material. The two polyethylene materials behaved similar in this friction test with COF of about 0.1. The Ra roughness values of the different pins reflect the COF results: Ra of subchondral bone was one order of magnitude higher than Ra of the cartilage. This is in-line with the COF-values of bone being one order of magnitude higher than those of cartilage. These results will be discussed in view of the use of the disc materials as orthopaedic hemi-prostheses

Background. Simply stated, carbon reinforced carbon (C/C) may be considered as fibre reinforced pyrocarbon. Pyrocarbon is used e.g. in finger joints and artificial heart valves. Aim of the present study was to evaluate if C/C could broaden the field of orthopaedic applications compared to pyrocarbon. Technically, C/C is used e.g. for brakes of F-1 race cars. Methods. The mechanical strength of the C/C material was characterised by a biaxial flexural bending test according ISO 6474-1. Three C/C shoulder heads articulating against vitamin E stabilised, highly cross-linked UHMWPE (E-XLPE) underwent a shoulder simulator study up to 106 cycles. The Coefficient of Friction (CoF) of C/C disks (Ra: 0.045 μm) against cartilage was analysed by a reciprocal cartilage wear tester. The test was conducted in cell culture medium for 4 h and 12 h using bovine cartilage. All test data is compared to the corresponding test results with Al2O3 ceramic. Conclusions. The strength of C/C is 30 % lower than that of Al2O3 ceramic. Its wear rate measured in the shoulder simulator against E-XLPE is in tendency higher than that of ceramic heads. The CoF against cartilage is double compared to the same test with Al2O3. - C/C seems to have limited a potential as material for orthopaedic application. However, more investigations and optimisation of the C/C type and quality are necessary. Level of evidence. Laboratory test on material samples. Study financed by Mathys Ltd Bettlach

Background. When reversing the hard-soft articulation in inverse shoulder replacement, i.e. hard inlay and soft glenosphere, the tribological behaviour of such a pairing has to be tested thoroughly. Therefore, two hard materials for the inlay, CoCr alloy and alumina toughened zirconia ceramic (ATZ) articulating on two soft materials, conventional UHMWPE and vitamin E stabilised, highly cross-linked PE (E-XLPE) were tested. Methods. The simulator tests were performed analogue to standardised gravimetric wear tests for hip prosthesis (ISO 14242-1) with load and motion curves adapted to the shoulder. The test parameters differing from the standard were the maximum force (1.0 kN) and the range of motion. A servo-hydraulic six station joint simulator (EndoLab, Rosenheim) was used to run the tests up to 5 times 106 cycles with diluted calf serum at 37° C as lubricant. Results. The wear rates measured in the simulator when the CoCr alloy inlay articulated on UHMWPE and E-XLPE were respectively 32.50 +/− 3.48 mg/Mcycle and 10.65 +/− 2.36 mg/Mcycle. In comparison, when the ATZ inlay articulated on UHMWPE and E-XLPE the wear rates were 20.34 +/− 1.14 mg/Mcycle and 5.99 +/− 0.79 mg/Mcycle respectively. Conclusions. The simulator wear rate of the standard articulation CoCr – UHMWPE is similar to that found in the corresponding pairing for hip endoprosthesis. Replacing UHMWPE by E-XLPE, the wear rate is reduced to about 1/3 for both hard counterparts, CoCr and ZTA, respectively. Replacing the CoCr inlay by a part made from ZTA lowers wear by about 37 % in articulation against UHMWPE and about 44 % against E-XLPE. The lowest wear rate, with a reduction of about 80 % compared to the standard CoCr – UHMWPE, exhibits the pairing of both advanced materials, ZTA – E-XLPE. However, long-term clinical follow-up will confirm if this in-vitro wear reduction leads to longer in-vivo survival. Level of evidence. Laboratory test on sample implants. Study financed by Mathys Orthopaedie GmbH

Summary Statement. Antioxidant containing UHMWPE particles induced similar levels of in vitro macrophage proliferation and in vivo inflammation in the mouse air pouch model as UHMWPE particles alone. Benefit of antioxidant in reducing wear particle induced inflammation requires further investigation. Introduction. Wear particles derived from UHMWPE implants can provoke inflammatory reaction and cause osteolysis in the bone, leading to aseptic implant loosening. Antioxidants have been incorporated into UHMWPE implants to improve their long term oxidative stability. However it is unclear if the anti-inflammatory property of the antioxidant could reduce UHMWPE particle induced inflammation. This study evaluated the effect of cyanidin and vitamin E on UHMWPE induced macrophage activation and mouse air pouch inflammation. Methods. Four types of UHMWPE were used: (1) compression molded (CM) conventional GUR1020 (PE); (2) CM GUR1020 blended with 300 ppm cyanidin (C-PE); (3) CM GUR1020 blended with 1000 ppm α-tocopherol (BE-PE); and (4) CM GUR1020, gamma irradiated at 100kGy, diffused with α-tocopherol, and sterilised at 30kGy (DE-PE). Particles were generated by cryomilling. Particle count, size, and aspect ratio were determined using SEM and Image Pro. Each particle group was cultured with RAW264.7 macrophage cells at four concentrations (0.625, 1.25, 2.5, and 5 μg/mL) in a standard medium for 4 days. Cell numbers were quantified using MTT assay. Cytokine expression (IL-1β, TNFα, and IL-6) was measured using RT-PCR and ELISA. Particles were also suspended in PBS at 2 concentrations (0.2 or 1 mg) and injected into subcutaneous air pouches in BALB/c mice. Control animals were injected with PBS alone. Six days post-injection air pouches were harvested, half of which were fixed for histology to measure membrane thickness and inflammatory cell quantity. Remaining air pouches were frozen and analyzed by ELISA for cytokine production. Data were analyzed using one-way ANOVA with post hoc testing. P<0.05 was considered significant. Results. All 4 materials showed similar particle characteristics after cryomilling. Particle size ranged from 1 to 19 μm with 33% of particle population smaller than 2 μm. All particle groups supported macrophage proliferation, showing an inverse correlation between proliferation rate and particle dose. Gene expression of IL-1β and TNFα also showed an inverse correlation with particle dose. Expression of IL-1β, TNFα, and IL-6 appeared lower in cells cultured with C-PE than the other 3 materials. The accumulative protein productions of IL-1β and TNFα were significantly lower while IL-6 production was moderately lower in C-PE, BE-PE and DE-PE when compared to PE. Injection of polyethylene particles increased the air pouch membrane thickness significantly compared to the PBS control in all particle types and doses. Higher particle dose induced thicker membrane in all 4 materials. A similar trend was also observed in the percentage of inflammatory cell infiltration in the pouch membrane. C-PE and DE-PE particles at low dose and C-PE particles at high dose induced lower levels of IL-1β and TNFα than PE. IL-6 production was similar between PE and other 3 groups. Discussion/Conclusion. Antioxidant incorporated in UHMWPE did not alter the level of macrophage proliferation and air pouch inflammation induced by UHMWPE particles, although it reduced cytokine gene expression. Future investigation in a synovial joint environment is desired to evaluate the chronic inflammation response to antioxidant containing UHMWPE wear particles and to verify the effect of antioxidant in UHMWPE properties