Aims. The aim of this study was to evaluate the performance of first-generation annealed highly cross-linked polyethylene (HXLPE) in cementless total hip arthroplasty (THA). Methods. We retrospectively evaluated 29 patients (35 hips) who underwent THA between December 2000 and February 2002. The survival rate was estimated using the Kaplan-Meier method. Hip joint function was evaluated using the Japanese Orthopaedic Association (JOA) score. Two-dimensional polyethylene wear was estimated using Martell’s Hip Analysis Suite. We calculated the wear rates between years 1 and 5, 5 and 10, 10 and 15, and 15 and final follow-up. Results. The mean follow-up period was 19.1 years (SD 0.6; 17.3 to 20.1). The 19-year overall survival rate with the end point of all-cause revision was 97.0% (95% confidence interval (CI) 91 to 100). The mean JOA score improved from 43.2 (SD 10.6; 30 to 76) before surgery to 90.2 (SD 6.4; 76 to 98) at the final follow-up (p < 0.001). There was no osteolysis or loosening of the acetabular or femoral components. The overall steady-state wear rate was 0.013 mm/year (SD 0.012). There was no hip with a steady-state wear rate of > 0.1 mm/year. There was no significant difference in wear rates for each period. We found no significant correlation between the wear rate and age, body weight, BMI, or cup inclination. Conclusion. First-generation annealed HXLPE shows excellent wear resistance and no acceleration of wear for approximately 20 years, with low all-cause revision rates. Cite this article: Bone Joint J 2022;104-B(2):200–205

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

Introduction:. Due to absence of fusion in guided-growth devices for EOS (growing rods, Shilla, LSZ) movement of the rods against their attachment is possible resulting in wear debris formation. It is important to understand the wear resistance of materials used in these devices under appropriate conditions. Aim:. The aim of our work was to investigate wear resistance of titanium alloy Ti-6Al-4V and superelastic Nitinol. Nitinol has been used recently for correcting scoliosis and may provide a better and more gradual correction than other materials. Methodology:. Wear tests were conducted using pin-on-disc configuration in diluted calf serum, as required by ISO 18192 for spinal devices. Pins were made of titanium alloy Ti-6Al-4V and Nitinol (simulation of rods material). All discs were made of Ti6-Al-4V alloy. Results and Discussion:. Superelastic Nitinol has better wear resistance since its volume wear loss is 100 times less than that of Ti-6Al-4V. However volumetric loss from Nitinol/Ti-6Al-4V friction pair (sum of both components) was found to be just about 3 times less in comparison with Ti-6Al-4V/Ti-6Al-4V pair due to wear of the titanium component. Deposition of ceramic coatings of titanium nitride (TiN) and diamond like carbon (DLC) significantly improves the wear resistance of Nitinol/Ti-6Al-4V friction pair due to effective protection of Ti-6Al-4V alloy component from the wear damage. Wear of Nitinol used for spinal rods is not expected to be as great as the wear of titanium, additionally it is possible to reduce the wear of Nitinol/titanium combination further by using coatings on the titanium alloy. Conflict Of Interest Statement: No conflict of interest

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

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

Highly cross linked polyethylenes have been shown to be substantially wear resistant. Typically, crosslinking is achieved by radiation in a low oxygen environment. While the early wear-simulation data is encouraging, concerns remain about the potential for aging and oxidative damage on exposure to oxygen during storage or in the body. This study measured wear rates in highly crosslinked liners that had been exposed to room air for up to 4 years.

Polyethylene liners were divided into four groups: two groups of highly crosslinked liners, XL (freshly opened) and XL-Aged (aged); and two groups of nominally crosslinked liners, N (freshly opened) and N-Aged (aged). The highly crosslinked liners were crosslinked with 9.5 Mrad of warm electron-beam irradiation, treated to a post-cross linking heat treatment to quench free radicals (WIAM), followed by ethylene oxide sterilization. The nominally cross linked liners were sterilized with 2.5 Mrad. The aged liners (XL-Aged and N-Aged) were stored in saline (at 37°C) exposed to room air for 4 years. Three liners from each group were tested in a hip-wear simulator (90% bovine serum) for 5 million cycles. Gravimetric wear measurements were made at 500,000 cycle intervals.

The N and N-Aged groups wore at rates of 14.76 ±3.1 and 15.58 ±1.21 mg/million cycles, respectively. The wear in both XL and XL-Aged groups was not measurable, resulting in weight gains of 2.73±0.5 and 2.17 ±1.1 mg/million cycles, respectively.

WIAM cross linked polyethylene has been reported to generate the least free radicals and has the least potential for oxidative damage. There have been concerns regarding the validity of artificial aging by the high-temperature oxidation. Aging in saline at body temperature while exposed to room air is more representative of in vivo aging. This data supports the results of artificial aging and the long-term durability of WIAM polyethylene.

To prevent aseptic loosening resulting from osteolysis induced by polyethylene (PE) wear particles in THA, it is necessary to develop a high wear-resistance bearing material. We have investigated the bearing surface mimicking the articular cartilage; grafting a biocompatible polymer, poly(2-methacryloyloxyethyl phosphorylcholine) (PMPC), onto the PE surface. High wear-resistance of PMPC-grafted surface has been revealed in the hip simulator wear test of 20 million cycles. Additionaly, in THA, oxidation degradation induced by residual free radicals resulting from gamma-ray irradiation for cross-linking or sterilization is also regarded as serious issue. Recently, gas plasma (GP) sterilization has been used as a less residual radical sterilization method. In this study, we ask a question: the GP sterilization would affect to PMPC surface and/or PE substrate? Hence, we investigated surface chemical, wear, mechanical, physical and oxidation properties of GP sterilized PMPC-grafted highly cross-linked PE (CLPE).

GP-sterilized CLPE and PMPC-grafted CLPE (CLPE (GP) and PMPC-CLPE (GP), respectively; GUR 1020 resin, 75 kGy irradiation), and 25 kGy-gamma-sterilized PMPC-grafted CLPE (PMPC-CLPE (g); GUR 1020 resin, 50 kGy irradiation) were evaluated. Surface property of PMPC layer was evaluated by X-ray photoelectron spectroscopy (XPS), fourier-transform infrared (FT-IR) spectroscopy, fluorescence microscope and cross-sectional transmission electron microscope (TEM) observations. Wettability and lubrication of the PMPC-CLPE surface were evaluated by static water contact angle measurement and ball-on-plate friction test, respectively. Wear properties of the acetabular cups were examined by using hip simulator in the combination with Co-Cr-Mo femoral heads. To evaluate the GP sterilization effect to the CLPE substrate, tensile test, izod impact test, small punch test, gel content, residual radical concentration and oxidation degradation were conducted. Oxidation degradation was evaluated as oxidation index by using a FT-IR spectroscopy.

By the XPS and FT-IR measurements, phosphorus peak and P-O peak attributed to grafted PMPC were observed, respectively. Uniform PMPC layer (100–200 nm thick) was observed on both surfaces of PMPC-CLPE (g) and PMPC-CLPE (GP) [Fig. 1]. Water contact angle of CLPE (GP) was almost 100 degree, while those for PMPC-CLPE (g) and PMPC-CLPE (GP) decreased dramatically to almost 10 degree. Dynamic coefficient of friction of PMPC-CLPE (g) and PMPC-CLPE (GP) was lower than that for CLPE (GP). In the hip simulator wear test, PMPC-CLPE (g) and PMPC-CLPE (GP) cups showed significantly lower amount of wear than that of CLPE (GP) [Fig. 2]. The number of the wear particles was extremely less in PMPC-CLPE (g) and PMPC-CLPE (GP), though the size was not different of all cases. Water thin film might be formed at the grafted PMPC layer, which acted as significantly efficient lubricant. There was no difference in the mechanical and physical properties among three groups. Oxidation index for PMPC-CLPE (GP) after acceleration of aging was lower than that of PMPC-CLPE (g). The GP sterilization might affect only to the PMPC-grafted surface, whereas gamma irradiation affects also to the PE substrate.

From these results, the PMPC-CLPE (GP) is expected to be one of the great bearing materials having not only high-wear resistance but also high-oxidation resistance, which could give further longevity of implantation.

Majority of ultra-high molecular weight polyethylene (UHMWPE) medical devices used in total joint arthroplasty are crosslinked using gamma radiation to improve wear resistance. Alternative methods of crosslinking are urgently needed to replace gamma radiation due to rapid decline in its supply. Peroxide crosslinking is a candidate method with widespread industrial applications. Oxidative stability and biocompatibility, which are critical requirements for medical device applications, can be achieved using vitamin-E as an additive and by removing peroxide by-products through high temperature melting, respectively. We investigated compression molded UHMWPE/vitamin-E/di-cumyl peroxide blends followed by high-temperature melting in inert gas as a material candidate for tibial knee inserts. Wear resistance increased and mechanical properties remained largely unchanged. Oxidation induction time was higher than most of the other clinically available formulations. The material passed the local-end point biocompatibility tests per ISO 10993. Compounds found in exhaustive extraction were of no concern with margin-of-safety values well above the accepted level, indicating a desirable toxicological risk profile. Peroxide crosslinked, vitamin-E stabilized, and high temperature melted UHMWPE has recently been cleared for clinical use in tibial knee inserts. With all the salient characteristics needed in a material that can provide superior long-term performance in total joint patients, peroxide crosslinking can replace gamma radiation crosslinking of UHMWPE for use in all total joint replacement implant including acetabular liners

Aims. Limited implant survival due to aseptic cup loosening is most commonly responsible for revision total hip arthroplasty (THA). Advances in implant designs and materials have been crucial in addressing those challenges. Vitamin E-infused highly cross-linked polyethylene (VEPE) promises strong wear resistance, high oxidative stability, and superior mechanical strength. Although VEPE monoblock cups have shown good mid-term performance and excellent wear patterns, long-term results remain unclear. This study evaluated migration and wear patterns and clinical and radiological outcomes at a minimum of ten years’ follow-up. Methods. This prospective observational study investigated 101 cases of primary THA over a mean duration of 129 months (120 to 149). At last follow-up, 57 cases with complete clinical and radiological outcomes were evaluated. In all cases, the acetabular component comprised an uncemented titanium particle-coated VEPE monoblock cup. Patients were assessed clinically and radiologically using the Harris Hip Score, visual analogue scale (pain and satisfaction), and an anteroposterior radiograph. Cup migration and polyethylene wear were measured using Einzel-Bild-Röntgen-Analyze software. All complications and associated treatments were documented until final follow-up. Results. Clinical assessment showed persistent major improvement in all scores. On radiological assessment, only one case showed a lucent line (without symptoms). At last follow-up, wear and migration were below the critical thresholds. No cup-related revisions were needed, indicating an outstanding survival rate of 100%. Conclusion. Isoelastic VEPE cups offer high success rates and may prevent osteolysis, aseptic loosening, and the need for revision surgeries in the long term. However, longer follow-up is needed to validate our findings and confirm the advantages offered by this cup. Cite this article: Bone Jt Open 2024;5(10):825–831

Aims. Highly cross-linked polyethylene (HXLPE) greatly reduces wear in total hip arthroplasty, compared to conventional polyethylene (CPE). Cross-linking is commonly achieved by irradiation. This study aimed to compare the degree of cross-linking and in vitro wear rates across a cohort of retrieved and unused polyethylene cups/liners from various brands. Methods. Polyethylene acetabular cups/liners were collected at one centre from 1 April 2021 to 30 April 2022. The trans-vinylene index (TVI) and oxidation index (OI) were determined by Fourier-transform infrared spectrometry. Wear was measured using a pin-on-disk test. Results. A total of 47 specimens from ten brands were included. The TVI was independent of time in vivo. A linear correlation (R. 2. = 0.995) was observed between the old and current TVI standards, except for vitamin E-containing polyethylene. The absorbed irradiation dose calculated from the TVI corresponded to product specifications for all but two products. For one electron beam-irradiated HXLPE, a mean dose of 241% (SD 18%) of specifications was determined. For another, gamma-irradiated HXLPE, a mean 41% (SD 13%) of specifications was determined. Lower wear was observed for higher TVI. Conclusion. The TVI is a reliable measure of the absorbed irradiation dose and does not alter over time in vivo. The products of various brands differ by manufacturing details and consequently cross-linking characteristics. Absorption and penetration of electron radiation and gamma radiation differ, potentially leading to higher degrees of cross-linking for electron radiation. There is a non-linear, inverse correlation between TVI and in vitro wear. The wear resistance of the HXLPE with low TVI was reduced and more comparable to CPE. Cite this article: Bone Joint Res 2024;13(11):682–693

While high-performance ceramics like alumina and zirconia exhibit excellent wear resistance, they provide poor osseointegration capacity. As osseointegration is crucial for non-cemented joint prostheses, new techniques have been successfully developed for biofunctionalizing high-performance ceramic surfaces. Stable cell adhesion can be achieved by covalently bound specific peptides. In this study we investigate the effect of sterilization processes on organo-chemically functionalized surfaces. To enhance the performance of alumina-toughened zirconia ceramics (ATZ), a 3-aminopropyldiisopropylethoxysilane (APDS) monolayer was applied and coupled with cyclo-RGD peptides (cRGD) by using bifunctional crosslinker bis(sulfosuccinimidyl)suberat (BS³). The samples were sterilized using e-beam or gamma-sterilization at 25 kGy, either before or after biofunctionalization with cRGD. Functionalization stability was investigated by contact angle measurements. The functionality of cRGD after sterilization was demonstrated using proliferation tests and cytotoxicity assays. Immunofluorescence staining (pFAK, Actin, DAPI) was conducted to evaluate the adhesion potential between the samples and human mesenchymal stem cells (hMSCs). Functionalized samples before and after sterilization showed no significant difference regarding their contact angles. A proliferation test demonstrated that the cells on functionalized samples proliferate significantly more than on untreated samples before and after sterilization. hMSCs showed a significant higher proliferation on gamma sterilized samples compared to all other groups after 14 days. It was confirmed that the samples did not exhibit cytotoxic behavior before or after sterilization. Fluorescence microscopy demonstrated that both, cells on sterilized and on non-sterilized samples, expressed high levels of pFAK-Y397. The investigated functionalization enables improved adhesion and proliferation of hMSCs and is stable against the investigated sterilization processes. This is of importance as the option of having a sterile product enables the start of the translation of this biofunctional coating towards preclinical and subsequently first-in-man applications. Acknowledgments: We acknowledge the financial support of the Federal Ministry of Education and Research, BMBF (13GW0452A-C)

Introduction. According to American Joint Replacement Registry, particle mediated osteolysis represents 13 % of the knee revision surgeries performed in the United States. The comprehension of mechanical and wear properties of materials envisioned for TJR is a key step in product development. Furthermore, the maintenance of UHMWPE mechanical properties after material modification is an important aspect of material success. Initial studies conducted by our research group demonstrated that the incorporation of ibuprofen in UHMWPE had a minor impact on UHMWPE physicochemical and mechanical properties. Drug release was also evaluated and resulted in an interesting profile as a material to be used as an anti-inflammatory system. Therefore, the present study investigated the effect of drug release on the mechanical and biological properties of ibuprofen-loaded UHMWPE. Experimental. UHMWPE resin GUR 1020 from Ticona was for sample preparation. Samples with drug concentrations of 3% and 5% wt were consolidated as well as samples without anti-inflammatory addition through compression molding at 150 °C and 5 MPa for 15 minutes. Mechanical properties were evaluated via the tensile strength experiment (ASTM D638) and dynamic mechanic tests. Wear resistance was measured using the pin on disc (POD) apparatus. Finally, cytotoxicity analysis was conducted based on ISO 10993–5. Results. Dynamic-mechanic analysis demonstrated no difference in flexion modulus and stress for all materials (Table 1). No difference was also verified during cyclical loading experiments (Table 1), which indicates that the drug concentration added to material composition did not affect these properties. POD experiments were proposed to evaluate wear resistance of ibuprofen-loaded UHMWPE samples considering the combination of materials similar to those employed in TJR. Results from POD tests are presented in Table 1. Volumetric wear was close to zero for all samples after 200 thousand cycles. Comprehension of the effect of drug release on mechanical properties is essential to estimate how the material will behave after implantation. Therefore, mechanical properties were assessed after 30 days of ibuprofen release and the results were compared with those obtained in samples as prepared (Table 2). Initial results demonstrated a decrease in elastic modulus in samples prepared with ibuprofen. However, no difference was verified between UHMWPE, UHMWPE 3% IBU and UHMWPE 5% IBU after ibuprofen release. Finally, cell viability of UHMWPE 3% IBU and UHMWPE 5% was found to be superior to 100% (Figure 1). Therefore, both materials can be considered nontoxic. Conclusions. Ibuprofen-loaded UHMWPE did not demonstrate a significant influence on the mechanical and biological behavior of UHMWPE. Dynamic-mechanical tests demonstrated constancy for all samples under analysis. Wear testing resulted in gravimetric wear close to zero, for all tested materials. Mechanical properties conducted after 30 days of ibuprofen release also had a positive outcome. Although presenting a difference in modulus prior and after release tests, modulus and tensile yield stress remained inside acceptable range indicated to UHMWPE used in orthopedic implants. Furthermore, after drug elution UHMWPE 3% IBU and UHMWPE 5% IBU recovered original UHMWPE properties. Cytotoxicity assessment was performed and both ibuprofen-based formulations were considered nontoxic according to ISO 10993–5. For any figures or tables, please contact the authors directly

Poly (vinyl alcohol) (PVA) hydrogel with high water content is one of the potential materials for artificial cartilage. In the previous study, the wear behavior of PVA hydrogel prepared by freeze-thawing (FT) method (PVA-FT gel) showed the excellent friction and wear property in simulated biological environment. However, the improvement of mechanical strength and wear resistance would be also needed for clinical application of PVA hydrogel as artificial cartilage. The different kind of physically-crosslinked PVA hydrogels prepared by cast-drying (CD) method (PVA-CD gel) and hybrid method of FT and CD (PVA-CD on FT hybrid gel) were also developed, and these two hydrogels have different mechanical properties and showed low friction compared with PVA-FT gel in saline. In this study, PVA hydrogel prepared by CD and hybrid methods were newly developed and friction and wear behavior of PVA-CD gel and PVA-CD on FT hybrid gel were evaluated in simulated biological environment. A sliding pair of an ellipsoidal reciprocating upper specimen of hydrogel and a flat stationary lower specimen of hydrogel was tested in reciprocating friction test. The thicknesses of PVA-CD gel and PVA-CD on FT hybrid gel were 2.0mm and 1.7mm, respectively. The applied load was 2.94 N. The sliding velocity was 20 mm/s and the total sliding distance was 1.5 km. In this study, solutions that contain hyaluronic acid, phospholipid and proteins were prepared as simulated synovial fluid and used as a lubricant for friction test. Molecular weight of sodium hyaluronate was 9.2×10. 5. L-alpha dipalmitoylphosphatidylcholine (DPPC) was selected as phospholipid constituent and was dispersed in saline as liposome. This liposomal solution was used as a base lubricant. Albumin and gamma-globulin, which are main protein constituents in natural synovial fluid, were used as additives as protein constituents. As shown in Fig.1, PVA-CD gel showed low friction such as below 0.02 at initial state of friction test. However, friction coefficient of PVA-CD gel rapidly increased and reached to about 0.5. In contrast, PVA-CD on FT hybrid gel kept low friction within the friction test. After friction test, many deep scratches were observed on the worn surface of PVA-CD gel (Figs. 2(a)-(c)). In contrast, the original surface structure of PVA-CD on FT hybrid gel almost remained while some scratches were observed (Figs. 2(d)-(f)). These results indicated that PVA-CD gel could show low friction but low wear resistance. The hybridization of FT and CD improved the wear resistance of PVA-CD gel. Therefore, the hybridization of FT and CD method is one of the prospective preparation methods of artificial cartilage with low friction and low wear. It is important to elucidate the mechanism of excellent lubricating property of PVA-CD on FT hybrid gel and develop the highly-functioned artificial hydrogel cartilage with low friction and high wear resistance

The main objective of joint arthroplasty is to improve activities of daily living of the patient. However, normal daily activities may lead to separation of articular surfaces of an artificial joint, possibly as a result of a combined impact and sliding motion. Therefore, the properties of articular surfaces define the durability of implant materials. Modification of bearing surfaces with poly(2-methacryloyloxyethyl phosphorylcholine) (PMPC) increases the hydration of the surfaces and decreases the wear of the substrates. Hence, a PMPC layer can potentially cushion the impact and improve the resistance of cross-linked polyethylene (CLPE). This study aimed to explore the fatigue and wear resistance of PMPC-grafted hydrated CLPE under impact-to-wear conditions using a pin-on-disk tester. The surfaces of a CLPE disk (3- or 6-mm thick) were modified with PMPC by photoinduced polymerization and were sterilized using gamma rays. The wear resistance of PMPC-grafted CLPE disks against a Co-Cr-Mo alloy pin was evaluated and compared to that of untreated disks. The disks were fixed to the tester with a metal plate (Ti-6Al-4V alloy) that had a central hole. The test was performed for 2 × 10. 6. cycles of repetitive impact and unidirectional sliding with the maximum load of 150 N, sliding distance of 10 mm, and frequency of 1 Hz [Fig. 1]. Gravimetric wear was determined by weighing the disks, and soak controls were used to compensate for fluid absorption. Volumetric changes in the surfaces of the disks were evaluated using a three-dimensional non-contact optical profiler. The average gravimetric wear (mg) after 2 × 10. 6. cycles was 0.000/0.120 for CLPE (3/6 mm) and −0.073/–0.137 for PMPC-CLPE (3/6 mm). The weight gain of the PMPC-CLPE disks was due to their greater fluid absorption compared to that of the soak controls under the impact-to-wear conditions, as judged from the fact that during the load-soak in the lubricant this gain was observed for all the disks irrespectively of PMPC grafting. PMPC-grafting decreased the gravimetric wear of CLPE (p < 0.01) in the 6-mm group, whereas the thickness of the CLPE disks had no substantial effect on the wear resistance [Fig. 2]. In all cases, three-dimensional measurements detected a remarkable volumetric penetration in the impact-sliding surfaces and an extrusion of CLPE from the backside surfaces into the hole in the metal plate. Both the volumetric penetration and backside extrusion were smaller in the 6-mm group. The PMPC grafting had no discernible effect on these volumetric changes [Fig. 3]. Even after 2 × 10. 6. cycles of impact loads, mechanical fracture or delamination of the impact-sliding or backside surfaces were hardly observed in all the groups. The results of this study revealed that: (1) PMPC-grafting of CLPE surfaces decreased the gravimetric wear irrespectively of the disk thickness; and (2) thinner CLPE increased the risk of volumetric changes, including penetration in the impact-sliding surface and extrusion of the backside surface. In conclusion, PMPC grafting can potentially improve the wear resistance of the bearing surface of biomaterials even under impact-to-wear conditions, increasing the longevity of artificial joints

Introduction. Radiation cross-linked UHMWPE is preferred in total hip replacements due to its wear resistance [1]. In total knees, where stresses are higher, there is concern of fatigue damage [2]. Antioxidant stabilization of radiation cross-linked UHMWPE by blending vitamin E into the polymer powder was recently introduced [3]. Vitamin E greatly hinders radiation cross-linking in UHMWPE [4]. In contrast peroxide cross-linking of UHMWPE is less sensitive to vitamin E concentration [5]. In addition, exposing UHMWPE to around 300°C, increases its toughness by inducing controlled chain scission and enhanced intergranular diffusion of chains, simultaneously [6]. We present a chemically cross-linked UHMWPE with high vitamin E content and improved toughness by high temperature melting. Methods and Materials. Medical grade GUR1050 UHMWPE was blended with vitamin E and with 2,5-Di(tert-butylperoxy)-2,5-dimethyl-3-hexyne or P130 (0.5% Vitamin-E and 0.9% P130). The mixed powder was consolidated into pucks. The pucks were melted for 5 hours in nitrogen at 300, 310 and 320°C. One set of pucks melted at 310°C was accelerated aged at 70°C at 5 atm. oxygen for 2 weeks. Tensile mechanical properties were determined using ASTM D638. Izod impact toughness was determined using ASTM D256 and F648. Wear rate was determined using a bidirectional pin-on-disc (POD) tester with cylindrical pins of UHMWPE against polished CoCr discs in undiluted, preserved bovine serum. Results. The vinyl index increased as a function of temperature (Fig 1a). Cross-link density steadily decreased and impact strength increased with increasing vinyl index (Fig 1b). The ultimate tensile strength (UTS) was not affected by HTM (Table 2). Impact strength was significantly improved for all treatment temperatures (P<0.05) and wear was significantly increased only for the sample melted at 320°C (Table 2). Discussion. High temperature melting (HTM) was shown to increase toughness of UHMWPEs presumably due to controlled chain scissioning and increased intergranular diffusion of chains [6]. For radiation cross-linked UHMWPE, it was shown that an increase in elongation-at-break and impact strength could be obtained without sacrificing wear resistance up to an elongation of about 500% [7]. This vitamin E-blended, peroxide cross-linked, high temperature melted UHMWPE has very high oxidation resistance due to its high antioxidant content, high wear resistance due to cross-linking and much improved toughness, representing an optimum joint replacement surface. For figures/tables, please contact authors directly.

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

The modification of bearing surfaces with poly(2-methacryloyloxyethyl phosphorylcholine) (PMPC) is known to increase the hydration of the surfaces and decrease the wear of the substrates. PMPC grafting to acetabular liner of total hip arthroplasty showed a drastic reduction of cross-linked polyethylene (CLPE) wear in a long-term hip simulator test and achieved a good short-term clinical result. To apply this technique to other joint prostheses, the wear resistance under various conditions needs to be evaluated because every joint has a different wear mode. ASTM F732 gives a method that disk shaped polymer specimen is loaded with hemispherical pin using pin-on-disk tester, which is suitable for hydrated polymer because the lubricant is supplied every loading cycle on the surface. The purpose of this study is to evaluate the performance of PMPC-grafted hydrated CLPE under multidirectional wear condition in anticipation of applying PMPC to various prostheses. The CLPE disks of 3 or 6-mm in thickness were machined from a bar stock. The PMPC was grafted onto the CLPE surfaces using a photoinduced polymerization of MPC in aqueous medium. All disks were irradiated with a total amount of 75-kGy gamma-ray. The wear resistance of the CLPE and PMPC-grafted CLPE disks against Co-Cr-Mo alloy pin was evaluated using Ortho-POD pin-on-disk tester. The disks were fixed to the tester with a Ti-6Al-4V alloy plate that has screw hole in the center. The test conditions were a static load of 213 N, sliding shape of 5 mm × 10 mm rectangular, frequency of 1 Hz and maximum cycles of 1.0 × 10. 6. [Fig. 1]. Gravimetric wear was determined by weighing the disks and soak controls were used to compensate for the fluid absorption. After the wear test, volumetric changes of sliding and backside surfaces of disks were evaluated using a noncontact optical three-dimensional profiler. The PMPC-grafted surface showed decrease in the gravimetric wear drastically [Fig. 2]. The thickness of CLPE had no substantial effect on the wear resistance. Three-dimensional profile measurements of sliding surfaces detected a substantial volumetric penetration; the corner of sliding track were deeper than the straight-line portion. Backside extrusion was observed in all disks. The thickness of CLPE affected both volumetric penetration and backside extrusion for both untreated and PMPC-grafted CLPE. The PMPC grafting had no discernible effect on volumetric changes [Fig. 3]. Results of this study revealed: (1) the PMPC-grafted surface decreases wear of CLPE, however, the thickness of disk has no effect, in contrast, (2) thinner thickness of CLPE increases the volumetric changes including penetration in sliding surface and extrusion in back surface but the PMPC-grafted surface has no effect. Gravimetric wear did not correlate with the volumetric penetration in sliding surface because the volumetric penetration might be caused by not only the wear but also the creep deformation. In conclusion, hydrated bearing surface and thickness of bearing substrate are essential for the wear and fatigue resistance properties for an increasing longevity of artificial joint. In addition, PMPC grafting is a promising technique for increasing the longevity of various joint prostheses

Introduction. Ultra-high molecular weight polyethylene (UHMWPE) is the sole polymeric material currently used for weight- bearing surfaces in total joint replacement. However, the wear of UHMWPE in knee and hip prostheses after total joint replacement is one of the major restriction factors on the longevity of these implants. In order to minimize the wear of UHMWPE and to improve the longevity of artificial joints, it is necessary to clarify the factors influencing the wear of UHMWPE. A number of studies have investigated the factors influencing the wear of UHMWPE acetabular cup liner in hip prosthesis. Most of these studies, however, have focused on the main articulating surfaces between the femoral head and the polyethylene liner. Materials and Methods. In a previous study (Cho et al., 2016), the generations of cold flow into the screw holes in the metal acetabular cup were observed on the backside of the retrieved UHMWPE acetabular cup liners as shown in Figure 1. We focused on the screw holes in the metal acetabular cup (Figure 2) as a factor influencing the wear behavior of polyethylene liner in hip prosthesis. In this study, computer simulations of the generation of cold flow into the screw holes were performed using the finite element method (FEM) in order to investigate the influence of the screw holes in the metal acetabular cup on the mechanical state and wear behavior of polyethylene liner in hip prosthesis. Results. An example of the results of the FEM simulations performed in this study is shown in Figure 3. In the region which the cold flow into the screw holes occurred, it was found that locally high contact stresses which exceed the yield stress of UHMWPE and considerable plastic strains were generated throughout the overall thickness between the backside and top surface of the polyethylene liners. On the contrary, in the case of the polyethylene liner combined with the metal acetabular cup without screw hole, although the regions of high contact stress and high plastic strain had a tendency to be limited around contact surface compared with those of the combination with screw holes, the values of contact stress and plastic strain were lower than the combination with screw holes. Discussion and Conclusions. The results of this study suggest that the cold flow generated by the existence of the screw holes in the metal acetabular cup of hip prosthesis reduces the wear resistance of the UHMWPE acetabular cup liner. It would appear that the cold flow into the screw holes contributes to structural weakening of the UHMWPE and reduction of the polyethylene thickness, thus increase of internal stresses and plastic strains in and around the regions of cold flow. Therefore, it is required that improvement of the screw holes in the metal acetabular cup and/or improvement of fixation method of the metal acetabular cup to a pelvis in order to enhance the wear resistance of the polyethylene liner. For any figures or tables, please contact authors directly

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

During the past five years, much research has focused on the effects of sterilisation on UHMWPE wear and mechanical properties. Gamma irradiation sterilisation of UHMWPE causes polymer chain scission and oxidation, which adversely affects both wear and mechanical properties. However, gamma irradiation can also produce crosslinking of the polymer chains, which improves wear resistance. Enhanced polyethylenes or highly crosslinked polyethylenes have been developed to further improve the wear resistance of the material. Highly crosslinked polyethylenes demonstrate markedly improved wear behaviour in hip simulator studies, but they also have a decrease in mechanical properties (yield strength, ultimate tensile strength, and fatigue strength). In a highly conforming joint such as the hip where contact stresses are relatively low due to the large surface area of contact, surface wear mechanisms (abrasion and adhesion) predominate while in a less conforming joint such as a fixed bearing knee replacement, where contact stresses are high, fatigue wear mechanisms occur more typically (delamination and pitting). Modifications to improve the wear resistance of UHMWPE such as the highly crosslinked materials may therefore be more appropriate for hip replacements than for fixed bearing knee replacements. Gravimetric wear measurements of UHMWPE from hip simulators have been used to predict in vivo behaviour of new materials. However, UHMWPE implants absorb fluid so that measurements of weight loss from wear simulators must be corrected with use of fluid soaked control specimens. There are still some inaccuracies in this technique leading to negative reported wear rates for some highly crosslinked polyethylenes. The biologic response to particulate debris may be more dependent on the size and number of particles rather than the volume of debris generated. The average particle size appears to decrease with greater amounts of crosslinking suggesting that for some highly crosslinked polyethylenes the number of particles may be greater than for non-crosslinked polyethylene, even though the volume of wear debris is decreased. Previous efforts to improve the wear behaviour of polyethylene such as the addition of carbon fibres (carbon reinforced polyethylene), hot isostatic pressing (Hylamer), and heat pressing have not demonstrated improvements in vivo. While current joint simulator studies may predict in vivo wear behaviour, clinical studies will ultimately be necessary to determine if highly crosslinked polyethylenes enhance the longevity of total joint arthroplasty