In vivo oxidation of retrieved cross-linked ultra-high-molecular-weight polyethylene acetabular components with residual free radicals

Wear of ultra-high-molecular-weight polyethylene (UHMWPE) contributes to debris that can lead to periprosthetic osteolysis in total hip arthroplasty. Irradiation not only decreases wear of UHMWPE but also generates residual free radicals that can oxidize the UHMWPE in the long term. Melting or annealing is used to quench the free radicals. Melting is more effective than annealing. We hypothesized that the postirradiation annealed UHMWPE components would oxidize in vivo and that postirradiation melted ones would not. We analyzed surgical explants of UHMWPE acetabular liners. The irradiated and annealed explants showed embrittlement, oxidation, and an increase in crystallinity. The irradiated and melted UHMWPE explants showed no oxidation, no increase in crystallinity, and no embrittlement. To prevent long-term chemical changes in highly cross-linked UHMWPE components, the residual free radicals must be stabilized after irradiation, preferably by melting and not annealing.     

Vitamin E diffused, highly crosslinked UHMWPE: a review

Highly crosslinked UHMWPE has become the bearing surface of choice in total hip arthroplasty. First generation crosslinked UHMWPEs, clinically introduced in the 1990s, show significant improvements compared to gamma sterilised, conventional UHMWPE in decreasing wear and osteolysis. These crosslinked UHMWPEs were thermally treated (annealed or melted) after irradiation to improve their oxidation resistance. While annealing resulted in the retention of some oxidation potential, post-irradiation melted UHMWPEs had reduced fatigue strength due to the crystallinity loss during melting. Thus, the stabilisation of radiation crosslinked UHMWPEs by the diffusion of the antioxidant vitamin E was developed to obtain oxidation resistance with improved fatigue strength by avoiding post-irradiation melting. A two-step process was developed to incorporate vitamin E into irradiated UHMWPE by diffusion to obtain a uniform concentration profile. Against accelerated and real-time aging in vitro, this material showed superior oxidation resistance to UHMWPEs with residual free radicals. The fatigue strength was improved compared to irradiated and melted UHMWPEs crosslinked using the same irradiation dose. Several adverse testing schemes simulating impingement showed satisfactory behaviour. Peri-prosthetic tissue reaction to vitamin E was evaluated in rabbits and any effects of vitamin E on device fixation were evaluated in a canine model, both of which showed no detrimental effects of the inclusion of vitamin E in crosslinked UHMWPE. Irradiated, vitamin E-diffused, and gamma sterilised UHMWPEs have been in clinical use in hips since 2007 and in knees since 2008. The clinical outcome of this material will be apparent from the results of prospective, randomised clinical studies.     

Effect of sterilization method and other modifications on the wear resistance of acetabular cups made of ultra-high molecular weight polyethylene. A hip-simulator study

BACKGROUND: Wear of ultra-high molecular weight polyethylene acetabular cups in hip prostheses produces billions of submicrometer wear particles annually that can cause osteolysis and loosening of the components. Thus, substantial improvement of the wear resistance of ultra-high molecular weight polyethylene could extend the clinical life span of total hip prostheses. It has become apparent that the conditions under which ultra-high molecular weight polyethylene cups have been sterilized can markedly affect their long-term wear properties, and new sterilization methods and other modifications have been developed to minimize the negative effects. METHODS: In the present study, a hip-joint simulator was used to assess whether it is preferable to sterilize ultra-high molecular weight polyethylene cups without gamma irradiation, to avoid radiation-induced oxidative degradation, or to sterilize with gamma irradiation while the cups are packaged in a suitable low-oxygen atmosphere to minimize oxidation while retaining the increased wear resistance conferred by the radiation-induced cross-linking. Ion-implanted cups and cups made of a highly crystalline polyethylene (Hylamer) also were investigated. Cups made of each material were subjected to wear-testing prior to and after artificial thermal aging to accelerate oxidative degradation. RESULTS: The results of the present study demonstrated that the cross-linking induced by gamma irradiation improves the wear resistance of ultra-high molecular weight polyethylene, while oxidation reduces it. Without thermal aging, the two types of cups that were sterilized with gamma irradiation while in low-oxygen packaging exhibited about a 50 percent lower rate of wear than did either the nonsterilized cups or the nonirradiated cups sterilized with gas plasma. There was a comparable advantage in the rate of wear after fourteen days of thermal aging. However, after thirty days of aging, the cups sterilized with gamma irradiation in low-oxygen packaging wore several times faster than did the nonirradiated cups. Ion-implanting improved the wear resistance without thermal aging, but after extensive thermal aging the oxidation and wear were greater than those of the controls. Hylamer cups (that is, those that were sterilized with gas plasma) exhibited wear properties very close to those of the nonsterilized ultra-high molecular weight polyethylene cups (the controls) with or without aging. CONCLUSIONS: Sterilizing an ultra-high molecular weight polyethylene acetabular cup without radiation (for example, with ethylene oxide or gas plasma) avoids immediate and long-term oxidative degradation of the implant but does not improve the inherent wear resistance of the polyethylene. Sterilizing with use of gamma irradiation with the implant packaged in a low-oxygen atmosphere avoids immediate oxidation and cross-links the polyethylene, thereby increasing its wear resistance, but long-term oxidation of the residual free radicals may markedly reduce the wear resistance. Ideally, cross-linking with gamma irradiation to reduce wear should be done in a manner that avoids both immediate and long-term oxidation.     

Knee simulator wear of vitamin E stabilized irradiated ultrahigh molecular weight polyethylene

Wear and damage of ultrahigh molecular weight polyethylene (UHMWPE) tibial inserts used in total knee arthroplasty are accelerated by oxidation. Radiation crosslinking reduces wear but produces residual free radicals adversely affecting stability. One alternative to stabilize radiation-crosslinked UHMWPE is to infuse the material with vitamin E (vit E). We investigated the properties of 100-kGy e-beam-irradiated UHMWPE that was subsequently doped with vitamin E in comparison with conventional UHMWPE. Both polymers were sterilized with gamma irradiation in vacuum packaging. Vitamin E-doped UHMWPE showed lower wear before and after aging (2.4 ± 0.5 and 2.5 ± 0.8 mg/million cycle, respectively, vs 26.9 ± 3.5 and 40.8 ± 3.0 mg/million cycle for conventional UHMWPE). Conventional UHMWPE showed oxidation after accelerated aging, and its mechanical properties were adversely affected, whereas vit E-doped UHMWPE showed no oxidation or changes in its mechanical properties. Vitamin E stabilization of radiation-crosslinked UHMWPE resulted in low wear and high oxidation resistance; it is an alternative load-bearing material for total knee applications.     

Effect of crosslinking, remelting, and aging on UHMWPE damage in a linear experimental wear model.

The objective of this study was to establish the effect of postirradiation melting as a function of irradiation dose on the wear behavior and material characteristics of ultrahigh molecular weight polyethylene. Our hypothesis was that a low dose of irradiation followed by melting would have the same improved wear performance as is found with higher doses of irradiation, but without the disadvantages associated with reduced fracture toughness. The hypothesis was tested by measuring the wear performance (wear track area, incidence of pitting and delamination) in a linear doubly curved-on-flat cyclic test, material behavior (elastic modulus, fracture toughness), and aging response (density changes through the thickness) of the following materials: elevated crosslinked groups--radiated at 25, 65, and 120 kGy, melted, sterilized and aged; a melted group--melted, sterilized, and aged; and a control group--sterilized and aged. Our findings suggest that postirradiation melting, not the irradiation dose, dominates the material property changes and wear response. Melting ensured reduced modulus and therefore decreased contact stresses, superior wear performance, and good resistance to aging, even after low levels of irradiation (25 kGy). The low modulus of the 25 kGy elevated crosslinked group, coupled with increased fracture toughness compared to samples irradiated at higher doses and a resistance to aging not found in the melted group, support our hypothesis. A low dose of irradiation followed by heat treatment has the same beneficial effects in terms of improved wear performance, but without the disadvantages of reduced fracture toughness found with higher doses of irradiation.     

Effect of molecular weight, calcium stearate, and sterilization methods on the wear of ultra high molecular weight polyethylene acetabular cups in a hip joint simulator.

Orthopaedic surgeons must currently choose from several types of ultra high molecular weight polyethylene acetabular cups that differ in their material properties and in the methods used for their sterilization. Information on the wear resistance of these different cups may help in the selection process. This study included two separate tests for wear run on a hip simulator to investigate the effect of molecular weight, calcium stearate, and sterilization methods on the wear resistance of ultra high molecular weight polyethylene acetabular cups. Test 1 revealed nearly identical wear rates for acetabular cups with molecular weights in two distinct ranges, as well as for cups with molecular weights in the same range but with or without calcium stearate added. In Test 2, cups that were sterilized in air with gamma irradiation exhibited lower rates of wear than those sterilized with ethylene oxide, presumably due to the crosslinking induced by the irradiation. In addition, cups that were irradiated while packed in a partial vacuum to minimize oxygen absorbed in the surface layer initially showed lower rates of wear than those irradiated in air, with the wear rates becoming similar as wear penetrated the more oxidized surface layer and the more crosslinked subsurface region. Because these tests were run a few months after the irradiation, the potential effects of long-term oxidation of any residual free radicals in the irradiated materials could not be taken into account. After artificial aging to accelerate oxidative degradation of the materials, the wear rates could be markedly different. Analyses performed after wear indicated that the irradiated (i.e., crosslinked) cups exhibited a smaller proportion of, as well as shorter, fibrils in the wear debris and an increased crystallinity and melting temperature and that gamma irradiation in the low-oxygen environment reduced the level of oxidation and increased the level of crosslinking in the surface region of the cups.     

Highly cross-linked ultrahigh molecular weight polyethylene with improved fatigue resistance for total joint arthroplasty: recipient of the 2006 Hap Paul Award

Eliminating postirradiation melting and stabilizing the residual free radicals of radiation cross-linked ultrahigh molecular weight polyethylene (UHMWPE) with vitamin E resulted in improved fatigue crack propagation resistance without compromising wear resistance. We designed a cantilever postbending test to determine the bending fatigue resistance of alpha-tocopherol-doped, irradiated UHMWPE (alpha-TPE) in comparison to conventional UHMWPE. The bending fatigue behavior of alpha-TPE was comparable to conventional UHMWPE. Upon accelerated aging, the fatigue resistance of alpha-TPE was substantially better than that of conventional UHMWPE. alpha-TPE has shown improved wear and oxidation resistance, migration stability of vitamin E, and improved mechanical properties. The use of this material may be beneficial in total knee arthroplasty where its improved fatigue properties may be an advantage under high stresses.     

Characterization of a highly cross-linked ultrahigh molecular-weight polyethylene in clinical use in total hip arthroplasty

This article reports on a commercially available extensively cross-linked ultrahigh molecular-weight polyethylene (HXPE) produced by subjecting molded GUR 1050 ultrahigh molecular-weight polyethylene (UHMWPE) to 100 ± 10 kGy of electron beam radiation followed by melt annealing and sterilization by gas plasma. When compared to contemporary conventional molded GUR 1050 UHMWPE sterilized by 37 kGy of gamma radiation, the HXPE material has enhanced wear properties, has no detectable free radicals, and is resistant to oxidation and oxidative-related material property changes. The relative wear improvement of the HXPE is maintained in the presence of bone cement or alumina particles. The HXPE produced greater than 90% fewer wear particles in all size ranges and statistically significantly (P < .0001) smaller average-size particles than did the conventional UHMWPE.     

A highly crosslinked UHMWPE for CR and PS total knee arthroplasties

X3 is a highly crosslinked ultrahigh molecular weight polyethylene (UHMWPE) produced by a sequential irradiation and annealing process. The sequential process results in a material with a free radical content that is 1% that of conventional UHMWPE gamma sterilized in nitrogen resulting in an oxidation resistance similar to that of virgin UHMWPE. Yield strength and ultimate tensile strength exceed American Society for Testing and Materials minimum rates for UHMWPE. Simulator testing of contemporary cruciate retaining (CR) and posterior-stabilized knee inserts (Triathlon) manufactured by the sequential process demonstrated 68% and 64% less wear, respectively, compared to conventionally processed inserts. The wear and mechanical integrity of sequentially processed posterior-stabilized inserts was unaffected by accelerated aging, whereas conventional UHMWPE exhibited increased wear, cracking, and delamination.     

How have new sterilization techniques and new forms of polyethylene influenced wear in total joint replacement?

Polyethylene has undergone many changes over the past several decades, including changes in consolidation processes, resin types, sterilization methods, packaging, and the extent of cross-linking. We believe that new sterilization techniques and forms of polyethylene have generally improved wear performance. Polyethylene sterilized without the use of radiation has been shown to have relatively high rates of wear in vivo. Ram-extruded polyethylene sterilized via gamma irradiation in air has been the most commonly used bearing material in the past several decades. Recently, components molded and gamma-sterilized without oxygen as well as highly cross-linked material have found increased clinical use. Exposure of polyethylene to radiation, either to sterilize it or to intentionally cross-link it, has been shown to improve the wear performance of the material. Newer second-generation methods of cross-linking polyethylene include the use of vitamin E, which quenches free radicals and demonstrates promise in providing low wear and desirable mechanical properties.     

Do First-generation Highly Crosslinked Polyethylenes Oxidize In Vivo?

Background

Highly crosslinked and thermally treated polyethylenes were clinically introduced to reduce wear and osteolysis. Although the crosslinking process improves the wear performance, it also introduces free radicals into the polymer that can subsequently oxidize. Thermal treatments have been implemented to reduce oxidation; however, the efficacy of these methods with regard to reducing in vivo oxidative degradation remains to be seen. Polyethylene oxidation is a concern because it can compromise the ultimate strength and ductility of the material.

Questions/purposes

We analyzed the oxidation, oxidation potential, and mechanical behavior of thermally treated highly crosslinked polyethylene retrieved acetabular liners.

Methods

Three hundred seven acetabular liners were collected from consecutive revision surgeries at six institutions over a 10-year period. Twenty-four were sterilized using nonionizing methods, 43 were sterilized in an inert environment, 80 were highly crosslinked and annealed, and 160 were highly crosslinked and remelted. Oxidation and oxidation potential were assessed by Fourier transmission infrared spectroscopy. Mechanical behavior was assessed by the small punch test.

Results

Oxidation and hydroperoxide (oxidation potential) indices were elevated in the annealed and gamma inert sterilized groups compared with those of the remelted liners and uncrosslinked gas sterilized controls, particularly at the rim. We also detected an increase in oxidation over time at the bearing surface of the remelted group. Ultimate strength of the polyethylene at the bearing surface was negatively correlated with implantation time for the annealed liners.

Conclusions

Within the first decade of implantation, the clinical outlook for first-generation highly crosslinked polyethylene remains promising. However, ongoing research continues to be warranted for first-generation highly crosslinked polyethylene bearings to monitor the implications of elevated oxidation at the rim of annealed liners as well as to better understand the subtle changes in oxidation at the bearing surface of remelted liners that occur in vivo.

     

Exponential model for the tensile true stress-strain behavior of as-irradiated and oxidatively degraded ultra high molecular weight polyethylene

Following sterilization by gamma radiation, ultra high molecular weight polyethylene components for total joint replacement undergo oxidative degradation upon exposure to air and the in vivo environment. Oxidative degradation is accompanied by an increase in density. The primary objective of this study was to develop a mathematical model to predict the monotonic tensile mechanical behavior of these sterilized components as a function of changes in density arising from oxidative degradation. Tensile specimens of ultra high molecular weight polyethylene were sterilized with gamma radiation and then oxidatively degraded in an air furnace. The average density of each specimen was measured using a density gradient column. Differential scanning calorimetry and Fourier transform infrared spectroscopy were conducted on selected specimens to characterize the physical and chemical changes due to accelerated aging as opposed to ambient shelf aging. Mechanical testing was conducted in monotonic uniaxial tension. An exponential model was fitted to the true stress-strain data (up to a true strain of 0.12). The observed fitted stress had a correlation coefficient of 0.996. The model permits a quantitative prediction of the association between the true stress-strain curve and density for the ultra high molecular weight polyethylene components. The proposed exponential model effectively describes changes in the large-strain monotonic tensile behavior of as-irradiated and oxidatively degraded ultra high molecular weight polyethylene components.     

Comparison of cross-linked polyethylene materials for orthopaedic applications

Cross-linked polyethylenes are being marketed by orthopaedic manufacturers to address the problem of osteolysis caused by polyethylene particulate wear debris. Wear testing of these cross-linked polyethylenes in hip simulators has shown dramatic reduction in wear rate compared with standard ultrahigh molecular weight polyethylene, either gamma irradiated in air or nitrogen - or ethylene oxide-sterilized. However, this reduction in wear rate is not without cost. The cross-linking processes can result in materials with lower mechanical properties than standard ultrahigh molecular weight polyethylene. To evaluate the effect of the various cross-linking processes on physical and mechanical properties of ultrahigh molecular weight polyethylene, commercially available cross-linked polyethylenes from six orthopaedic manufacturers were tested. This study was the culmination of collaboration with these manufacturers, who provided cross-linked polyethylene for this study, wear characteristics of the material they provided, and review of the physical and mechanical properties measure for their polyethylene. Cross-linked materials were evaluated as received and after an accelerated aging protocol. Free radical identity and concentration, oxidation, crystallinity, melt temperature, ultimate tensile strength, elongation at break, tensile stress at yield, and toughness are reported for each material. By comparing these physical and mechanical properties, surgeons can evaluate the trade-off that results from developing materials with substantially lower wear rates.     

Observation on retrieved Hylamer glenoids in shoulder arthroplasty: problems associated with sterilization by gamma irradiation in air

Hylamer is an ultra-high molecular weight polyethylene that was used in the glenoid prosthesis of the Global Shoulder. It was developed from a joint venture with DePuy Orthopaedics, Inc, and E.I. DuPont Company. In presterilization evaluations it was noted to have improved mechanical strength with superior creep and wear resistance. However, after sterilization was performed with gamma irradiation in an air environment from 1990 to 1993, the Hylamer glenoids were affected by oxidation, which altered the mechanical properties, and they became brittle and eroded. From 1993 to 1995 Hylamer glenoids were sterilized by gamma irradiation in a nitrogen environment. From 1995 to 1998 sterilization was by gas plasma processes, which do not create the oxidation problem. Since 1998 the glenoid prosthesis of the Global Shoulder has been made exclusively of Enduron and is gas sterilized. The primary purpose of this article is to provide orthopaedic surgeons the best information available about Hylamer glenoids. We make suggestions concerning the diagnosis and treatment of the patients who had a Hylamer glenoid inserted between 1990 and 1993.     

Polyethylene as an implant material

Since the early 1960s, ultrahigh-molecular weight polyethylene (UHMWPE) has been one of the most frequently and successfully used materials in total joint replacement. However, in the course of clinical usage, various weaknesses of the material became apparent including wear and aging properties. As a result of research on this polymer, several improvements in the quality of the raw material, the processing, and the sterilization have been introduced.These changes paired with an improved knowledge of the viscoelastic behavior of UHMWPE have led to an improved design of the components to meet the requirements of the given material characteristics and in turn to better clinical results. In the 1990s, investigations focused on the influence of radiation on the molecular structures of polyethylene.Gamma radiation treatment in air leads to an important decrease in the molecular weight with reduced tribological behavior and accelerated aging. In contrast, a nitrogen atmosphere during irradiation and storage can improve the linkage of the polyethylene and promote the positive effects of radiation treatment.This effect can be further intensified by increased radiation levels.Such highly cross-linked polyethylenes demonstrate extremely low wear rates in vitro;however, other material properties are also changed.First reports on fissures in highly cross-linked polyethylene explants demonstrate that only long-term clinical trials can allow a final verdict on the clinical potential of highly cross-linked polyethylenes.     

Increase in early polyethylene wear after sterilization with ethylene oxide: radiostereometric analyses of 201 total hips

We evaluated polyethylene wear by measuring femoral head penetration in 201 THA (median age 62 (31-81) years, 117 women) extracted from 5 randomized studies aimed to assess various fixation principles. There were 30 cemented all-polyethylene Lubinus cups sterilized by gamma irradiation in a reduced oxygen environment, 65 porous-coated Trilogy cups with liners gamma-sterilized in inert gas. Moreover, 37 cemented cups were sterilized with ethylene oxide (Reflection all-poly) and 69 porous-coated cups had liners sterilized in ethylene oxide (Reflection). 28 mm femoral heads were used in all cups. The patients were followed with repeated radiostereometric measurements (RSA) up to 2 years. The activity level of the patients was evaluated by a questionnaire. After 2 years, cups with polyethylene sterilized in EtO had almost twice the proximal and 3D penetration rates, as compared with gamma-sterilized polyethylene. The penetration did not differ between the gamma-irradiated designs. Using stepwise linear regression analysis, we found that the type of sterilization, age and weight were the most important predictors and that they determined the direction of the proximal penetration rate. Activity score, male gender and proximal migration of the cup had little effect. The accelerated wear observed with the EtO-sterilized polyethylene causes concerns about long-term problems and especially in younger patients.     

Increase in early polyethylene wear after sterilization with ethylene oxideRadiostereometric analyses of 201 total hips

We evaluated polyethylene wear by measuring femoral head penetration in 201 THA (median age 62 (31-81) years, 117 women) extracted from 5 randomized studies aimed to assess various fixation principles. There were 30 cemented all-polyethylene Lubinus cups sterilized by gamma irradiation in a reduced oxygen environment, 65 porous-coated Trilogy cups with liners gamma-sterilized in inert gas. Moreover, 37 cemented cups were sterilized with ethylene oxide (Reflection all-poly) and 69 porous-coated cups had liners sterilized in ethylene oxide (Reflection). 28 mm femoral heads were used in all cups. The patients were followed with repeated radiostereometric measurements (RSA) up to 2 years. The activity level of the patients was evaluated by a questionnaire. After 2 years, cups with polyethylene sterilized in EtO had almost twice the proximal and 3D penetration rates, as compared with gamma-sterilized polyethylene. The penetration did not differ between the gamma-irradiated designs. Using stepwise linear regression analysis, we found that the type of sterilization, age and weight were the most important predictors and that they determined the direction of the proximal penetration rate. Activity score, male gender and proximal migration of the cup had little effect. The accelerated wear observed with the EtO-sterilized polyethylene causes concerns about long-term problems and especially in younger patients.     

Increase in early polyethylene wear after sterilization with ethylene oxide

We evaluated polyethylene wear by measuring femoral head penetration in 201 THA (median age 62 (31-81) years, 117 women) extracted from 5 randomized studies aimed to assess various fixation principles. There were 30 cemented all-polyethylene Lubinus cups sterilized by gamma irradiation in a reduced oxygen environment, 65 porous-coated Trilogy cups with liners gamma-sterilized in inert gas. Moreover, 37 cemented cups were sterilized with ethylene oxide (Reflection all-poly) and 69 porous-coated cups had liners sterilized in ethylene oxide (Reflection). 28 mm femoral heads were used in all cups. The patients were followed with repeated radiostereometric measurements (RSA) up to 2 years. The activity level of the patients was evaluated by a questionnaire. After 2 years, cups with polyethylene sterilized in EtO had almost twice the proximal and 3D penetration rates, as compared with gamma-sterilized polyethylene. The penetration did not differ between the gamma-irradiated designs. Using stepwise linear regression analysis, we found that the type of sterilization, age and weight were the most important predictors and that they determined the direction of the proximal penetration rate. Activity score, male gender and proximal migration of the cup had little effect. The accelerated wear observed with the EtO-sterilized polyethylene causes concerns about long-term problems and especially in younger patients.