High Oxidation Stability of Tea Polyphenol-stabilized Highly Crosslinked UHMWPE Under an in Vitro Aggressive Oxidative Condition.

BACKGROUND: Synovial fluid components, especially lipids, can trigger oxidation of ultrahigh-molecular-weight polyethylene (UHMWPE) artificial joint components in vivo. The use of antioxidants such as vitamin E effectively diminishes the oxidative cascade by capturing free radicals and reducing the oxidation potential of UHMWPE implants. Using a thermo-oxidative aging method, we recently found that tea polyphenols can enhance the oxidation resistance of irradiated UHMWPE in comparison with commercial vitamin E. However, it is yet unknown whether tea polyphenols can reduce lipid-induced oxidation. QUESTIONS/PURPOSES: We explored whether tea polyphenol-stabilized UHMWPE would exhibit (1) lower squalene absorption; (2) stronger oxidation resistance; and (3) lower content of free radicals than vitamin E-stabilized UHMWPE under a physiologically-motivated in vitro accelerated-aging model. METHODS: Tea polyphenol (lipid-soluble epigallocatechin gallate [lsEGCG]) and vitamin E were blended with UHMWPE powders followed by compression molding and electron beam irradiation at 100 and 150 kGy. Small cubes (n = 3, 60 mg, 4 × 4 × 4 mm) cut from the blocks were doped in squalene at 60°, 80°, 100°, and 120° C for 2 hours. Gravimetric change of the cubes after squalene immersion was measured to assess absorption. Thin films (n = 3, ∼60 µm) were also microtomed from the blocks and were doped at 120° C for 24 hours. Oxidation induction time (n = 3, 5 mg of material from the cubes) and incipient oxidation temperature (n = 3, thin films) were obtained to determine the oxidation stability. Signal intensity of the free radicals, obtained by electron spin resonance spectroscopy, was used to qualitatively rank the antioxidant ability of vitamin E and lsEGCG. RESULTS: Squalene absorption was comparable between lsEGCG/UHMWPE and vitamin E/UHMWPE at a given temperature and radiation dose. The oxidation induction time of 100 kGy-irradiated UHMWPE was increased with lsEGCG compared with vitamin E except at 120° C. For example, the oxidation induction time value of 100 kGy-irradiated lsEGCG/UHMWPE immersed at 60 C was 25.3 minutes (24.2-27.8 minutes), which was 8.3 minutes longer than that of 100 kGy-irradiated vitamin E/UHMWPE which was 17.0 minutes (15.0-17.1 minutes) (p = 0.040). After squalene immersion at 120° C, the incipient oxidation temperature of 100 and 150 kGy irradiated lsEGCG/UHMWPE was 234° C (227-240° C) and 227° C (225-229° C), which was higher than vitamin E-stabilized counterparts with value of 217° C (214-229° C; p = 0.095) and 216° C (207-218° C; p = 0.040), respectively. The electron spin resonance signal of 150 kGy irradiated lsEGCG/UHMWPE was qualitatively weaker than that of 150 kGy irradiated vitamin E/UHMWPE. CONCLUSIONS: lsEGCG-stabilized UHMWPE demonstrated higher oxidation resistance than vitamin E-stabilized UHMWPE after squalene immersion, likely because lsEGCG donates more protons to eliminate macroradicals than vitamin E. CLINICAL RELEVANCE: Our in vitro findings provide support that lsEGCG may be effective in protecting against oxidation that may be associated with synovial fluid-associated oxidation of highly crosslinked UHMWPE joint replacement components.

Increased oxidative protection by high active vitamin E content and partial radiation crosslinking of UHMWPE.

Vitamin E stabilization successfully improved long-term oxidation resistance of wear-resistant ultra-high-molecular-weight polyethylene (UHMWPE) used for joint implants. Stabilization can be achieved by blending an antioxidant into the UHMWPE resin powder before consolidation and irradiation. Balancing the wear resistance and vitamin E content in the blend is the current challenge with this approach, because vitamin E hinders crosslinking of UHMWPE during irradiation, which decreases wear resistance. The vitamin E concentration in the blend is generally limited to less than 0.3 wt%. Wear- and oxidation-resistant UHMWPE has been obtained previously by consolidating blends of pre-irradiated UHMWPE powders (XPE) into an unmodified polyethylene matrix (PE), where the improvement in wear rate depended on the radiation dose and fraction of XPE. We hypothesized that increasing the vitamin E content in the unirradiated matrix would not compromise wear and would further improve the oxidative stability of XPE/PE blends. Pin-on-disk wear testing showed that the XPE/PE blends containing 0.1-1.0 wt% vitamin E in the matrix had comparable wear rates. We used an aggressive accelerated aging test in the presence of the pro-oxidant squalene and oxidation induction time (OIT) test and found that higher amounts of vitamin E resulted in stronger oxidation resistance for XPE/PE blends. The mechanical strength and toughness of the blends were not affected by changing the vitamin E content in the matrix. Stabilizing UHMWPE with higher vitamin E content may extend the service life of UHMWPE implants. © 2017 Orthopaedic Research Society. Published by Wiley Periodicals, Inc. J Orthop Res 36:1860-1867, 2018.

Vitamin E-stabilized highly crosslinked polyethylenes: The role and effectiveness in total hip arthroplasty.

Morphology and design of ultra-high molecular weight polyethylene (UHMWPE or simply PE) acetabular components used in total hip arthroplasty (THA) have been evolving for more than half a century. Since the late-1990s, there were two major technological innovations in PE emerged from necessity to overcome the wear-induced periprosthetic osteolysis, i.e., the development of highly crosslinked PEs (HXLPEs). There are many literature reporting that radiation crosslinked and remelted/annealed (first-generation) HXLPEs markedly reduced the incidence of osteolysis and aseptic loosening. Regardless of such clinical success in the first-generation technologies, there were some recent shifts in Japan toward the use of new second-generation HXLPEs subjected to sequential irradiation/annealing or antioxidant vitamin E (α-tocopherol) incorporation. Although the selection rate of first-generation liners still account for more than half of all the PE THAs (∼58% in 2015), the use of vitamin E-stabilized liners has been steadily growing each year since their clinical introduction in 2010. In these contexts, it is of great importance to evaluate and understand the real clinical benefits of using the new second-generation liners as compared to the first generation. This article first summarizes structural evolution and characteristic features of first-generation HXLPEs, and then provides a detailed description of second-generation antioxidant HXLPEs in regard to the role of vitamin E incorporation on their chemical and mechanical performances in THA.

J-integral fracture toughness, Tearing modulus and tensile properties of Vitamin E stabilized radiation crosslinked UHMWPE.

Radiation crosslinking of ultra-high molecular weight polyethylene (UHMWPE) increases its wear resistance in total joint replacement prostheses. Unfortunately, it is accompanied by a dose-dependent decrease in several mechanical properties. In this study, the tensile properties and fracture behavior of radiation crosslinked, Vitamin E stabilized UHMWPE was studied as a function of radiation dose. The Rice and Sorensen model, applicable to elastic-plastic materials, was utilized to obtain the initial crack driving force, J1c, steady state J-integral fracture toughness, Jss and the Tearing modulus. Tensile tests showed the dependence of tensile properties on radiation dose. Jss of non-crosslinked UHMWPE was higher than for crosslinked UHMWPE׳s but there was no dose dependent change in Jss whereas there was almost no change in J1c over the entire dose range. Finally, a monotonic decrease in Tearing modulus was observed with radiation dose.

Oxidation and other property changes of retrieved sequentially annealed UHMWPE acetabular and tibial bearings.

This investigation analyzed retrieved sequentially crosslinked and annealed (SXL) ultra-high molecular weight polyethylene bearings to determine whether the material is chemically stable in vivo. A series of retrieved tibial and acetabular components were analyzed for changes in ketone oxidation, crosslink density, and free radical concentration. Oxidation was observed to increase with in vivo duration, and the rate of oxidation in tibial inserts was significantly greater than in acetabular liners. SXL acetabular bearings oxidized at a rate comparable to gamma-sterilized liners, while SXL tibial inserts oxidized at a significantly faster rate than their gamma-sterilized counterparts. A significant decrease in crosslink density with increased mean ketone oxidation index was observed, suggesting that in vivo oxidation may be causing material degradation. Furthermore, a subsurface whitened damage region was also found in a subset of the bearings, indicating the possibility of a clinically relevant decrease in mechanical properties of these components.

The effect of an additional phosphite stabilizer on the properties of radiation cross-linked vitamin E blends of UHMWPE.

Antioxidant stabilization of radiation cross-linked ultrahigh molecular weight polyethylene (UHMWPE) has been introduced to improve the oxidative stability of total joint implant bearing surfaces. Blending of an antioxidant with UHMWPE resin powder followed by consolidation and radiation cross-linking has been cleared by the FDA for use in both total hips and total knees for designs incorporating two antioxidants, namely vitamin E and Covernox™ (a medical grade version of Irganox™ 1010). The antioxidants in the polymer are expected to protect the polymer during consolidation, during radiation cross-linking, on the shelf before implantation, and in vivo after implantation. To maximize the protection of the polymer afforded by the antioxidant in vivo, a novel approach may be the use of multiple antioxidants, especially to protect the primary antioxidant for a longer period of time. We hypothesized that the addition of a phosphite stabilizer (Irgafos 168™) commonly used in conjunction with hindered phenolic antioxidants in polymer processing could improve the oxidative stability of radiation cross-linked blends of vitamin E. To test our hypothesis, we prepared UHMWPE blends with 0.05 wt% Irgafos and 0.05 wt% vitamin E and compared its cross-link density, wear resistance, tensile properties, and impact strength to control blends containing only vitamin E. Our hypothesis was not supported; the cross-link density of UHMWPE was significantly decreased by the additive without additional benefit to oxidative stability. To our knowledge, this was the first attempt at using multiple stabilizers in medical grade UHMWPE.

Computer-aided orbital wall defects treatment by individual design ultrahigh molecular weight polyethylene implants.

UNLABELLED: Despite of well-known advantages of high molecular weight polyethylene (Medpor, Synpore) in orbital reconstructions, the thickness of those implants significantly exceeds 0.5 mm and precise modification of thickness is limited. The aim of this study was to present the application of a self-developed method of treatment orbital wall fracture by custom implant made of ultrahigh molecular weight polyethylene (UHMW-PE). MATERIAL AND METHOD: First, the test of influence of sterilization process upon implant deformation was performed (autoclaving, ethylene oxide, gas plasma, irradiation). Next, ten cases for delayed surgical treatment of orbital fracture were included into this study (7 males, 3 females). Based on CT scan and mirrored technique, a CAD model of virtual implant for repairing orbital wall was made. Then, an implant was manufactured with a computer numerical controlled milling machine from UHMW-PE block, sterilized and used during a surgical procedure. Clinically used implants had thickness from 0.2 to 4.0 mm. RESULTS: The best method of sterilization is ethylene oxide process, and the worst is autoclaving. In this series of delayed surgical cases, functional results of orbital surgery are worse than in simpler, early treated cases, but long-term subsidence of diplopia is noticeable [10% poor results]. The results of the treatment depend on the initial level of diplopia where severe initial diplopia to be corrected requires thicker implants (p < 0.01). It also leads to longer surgical procedures (p < 0.01), but prolongation of the surgery had no negative influence upon results of any investigated follow-up examinations. Obviously, the orbital destruction intensity is related to injury-evoked initial diplopia but it also influences whole results of treatment up to 12 months post-op. Interesting result is presented by the relation of maximal implant thickness to 12-month diplopia evaluation. Thicker implants used result in lower residual diplopia (p < 0.05). This is important because of the correlation between the higher orbital destruction intensity with a thicker UHMW-PE implant (p < 0.05) applied in this series. CONCLUSION: Patient-specific ultrahigh molecular weight polyethylene implants enable precise reconstructions of orbital wall. One should not be afraid of a significant eye globe reposition caused by these thickness modulated implants, as such repositioning is essential for an efficient correction of enophthalmos.

Surface cross-linked UHMWPE can enable the use of larger femoral heads in total joints.

Limiting cross-linking to the articular surfaces of ultrahigh molecular weight polyethylene (UHMWPE) to increase wear resistance while preventing detrimental effects of cross-linking on mechanical strength has been a desirable goal. A surface cross-linked UHMWPE can be achieved by blending UHMWPE with a free radical scavenger, such as vitamin E, consolidating the blend into an implant shape, extracting the vitamin E from the surface, and radiation cross-linking the surface extracted blend. This process results in high cross-link density in the vitamin E-depleted surface region because vitamin E hinders cross-linking during irradiation. In this study, we described the properties of successful extraction media and the manipulation of the wear and mechanical properties of extracted, irradiated blends. We showed that these formulations could have similar wear and significantly improved mechanical properties compared to currently available highly cross-linked UHMWPEs. We believe that these materials can enable thinner implant forms and more anatomical designs in joint arthroplasty and may provide a feasible alternative to metal-on-metal implants.

Gamma-irradiation sterilization in an inert environment: a partial solution.

BACKGROUND: In the mid to late 1990 s, to sterilize UHMWPE bearings, manufacturers changed from gamma-irradiation-in-air (gamma-air) sterilization, which initiated oxidation leading to bearing fatigue, to gamma-irradiation sterilization in an inert environment (gamma-inert). The change to gamma-inert sterilization reportedly prevented shelf oxidation before implantation but not in vivo oxidation. QUESTIONS/PURPOSES: We asked: (1) Has the change to gamma-inert sterilization prevented shelf oxidation that led to early in vivo fatigue damage in gamma-air-sterilized tibial inserts? And (2) has the change to gamma-inert sterilization prevented the occurrence of fatigue secondary to in vivo oxidation? METHODS: We rated 183 retrieved gamma-air- and 175 retrieved gamma-inert-sterilized tibial inserts for clinical fatigue damage and analyzed 132 gamma-air- and 174 gamma-inert-sterilized tibial inserts for oxidation by Fourier transform infrared spectroscopy. RESULTS: Oxidation led to decreased mechanical properties in shelf-aged gamma-air-sterilized tibial inserts. Barrier packaging prevented shelf oxidation in gamma-inert-sterilized tibial inserts. Gamma-air- and gamma-inert-sterilized inserts oxidized in vivo. Fatigue damage (delamination) occurred more frequently in inserts retrieved after longer time in vivo. Longer in vivo time correlated with higher oxidation and more accumulated cycles of use. CONCLUSIONS: Published oxidation projections suggest gamma-inert-sterilized tibial inserts would reach the critical oxidation for the onset of fatigue after 11 to 14 years in vivo. These retrievals appear to follow the projected oxidation trends. Frequency of fatigue damage increased with increasing oxidation. CLINICAL RELEVANCE: Fatigue of tibial inserts becomes more likely, especially in active patients, after more than a decade of good clinical performance.

Submicron sized ultra-high molecular weight polyethylene wear particle analysis from revised SB Charité III total disc replacements.

Submicron sized particles are frequently observed in retrieved total hip and knee periprosthetic tissues and appear to be critical in the activation of the phagocytic inflammatory response. In this paper the concentration, size and shape of ultra-high molecular weight polyethylene (UHMWPE) wear particles between 0.05 and 2.00µm were determined after isolation from periprosthetic tissues from retrieved lumbar SB Charité III total disc replacements (TDR) using scanning electron microscopy (SEM). For comparison, UHMWPE wear particles were isolated from γ-radiation-air sterilized total hip arthroplasty (THA) revision tissues. The mean concentration of UHMWPE particles in TDR tissues was 1.6×10(9)g(-1)tissue (range 1.3-2.0), which was significantly lower than the concentration of 2.3×10(9)g(-1) THA revision tissue (range 1.8-3.2) (P=0.03). The mean particle size (equivalent circular diameter: TDR, 0.46µm; THA 0.53µm, P=0.60) and mean shape were comparable between TDR and THA (aspect ratio: TDR, 1.89; THA, 1.99, P=0.35; roundness: TDR, 0.58; THA, 0.56, P=0.35). However, the TDR particles tended to be smaller and more round. Although no correlations were found between visible damage to the UHMWPE core and the concentration or shape of the UHMWPE particles, a positive correlation was found between increasing particle size and increasing rim penetration of the TDR core (P=0.04). The presence of UHMWPE particles of similar size and shape in TDR tissue, albeit lower in concentration, might explain why, unlike THA, pain rather than osteolysis is the major reason for revision surgery.

The effect of radiation dose on the tensile and impact toughness of highly cross-linked and remelted ultrahigh-molecular weight polyethylenes.

Several highly cross-linked and remelted ultrahigh-molecular weight polyethylenes (UHMWPE) were introduced in 1998 as bearing materials for orthopaedic implants to achieve superior wear performance. However, gamma radiation and the subsequent postirradiation thermal treatment are associated with decreased mechanical properties such as ductility, toughness, and fatigue strength compared to noncross-linked materials. The purpose of this study was (a) to characterize the toughness (tensile and impact) of highly cross-linked and remelted UHMWPE of varying doses (0-255 kGy) and (b) determine whether a correlation exists between both toughness measures. As radiation dose increased, tensile toughness and impact toughness were shown to decrease in a nonlinear fashion; largely a result of the decrease in ductility, which was also observed. Impact toughness and tensile toughness were also found to be strongly correlated to one another (R(2) = 0.97).

[The effect of ultraviolet irradiation on the biocompatibility of Medpor].

OBJECTIVE: To investigate the effect of ultraviolet ( UV) irradiation on the biocompatibility of Medpor. METHODS: The Medpor implant, 2 mm in thickness, was divided into several pieces with the size of 1 cm x 1 cm. 12 Japanese big ear rabbits were divided into experimental (n=6) and control group (n=6). The 1 cm x 1 cm auricular cartilage defects were made in each rabbit ear. Then the defects were repaired with UV-treated Medpor implants in experimental group, and Medpor implants in control group. The levels of the total hemolytic complement (CH50) were measured 3 d hefore operation, and 1, 3, 7, 14, 21, 30, 60, 90 d after operation. The wound healing was observed. 90 d after operation, the animals were killed to get the specimens for gross observation and histologic examination. The change of CH50 level after operation was significantly different between the two groups ( P < 0.05) . The CH50 level was comparatively stable in experimental group. Compared with control group, the local inflammatory reaction was not obvious in experimental group. A great amount of tissue, including big vessels was growing into the mini-pores of Medpor, resulting a close combination between the implant and surrounding tissue. CONCLUSION: It suggests that ultraviolet irradiation can improve the biocompatibility of Medpor and promote the wound recovery.

Drug release responses of zinc ion crosslinked poly(methyl vinyl ether-co-maleic acid) matrix towards microwave.

The drug release characteristics of beads made of poly(methyl vinyl ether-co-maleic acid) using Zn2+ as the crosslinking agent were investigated with respect to the influence of microwave irradiation. The beads were prepared by an extrusion method with sodium diclofenac as a model water-soluble drug. They were subjected to microwave irradiation at 80W for 5 and 20 min, and at 300W for 1 min 20s and 5 min 20s. The profiles of drug dissolution, drug content, drug-polymer interaction and polymer-polymer interaction were determined by dissolution testing, drug content assay, differential scanning calorimetry and Fourier transform infrared spectroscopy. Treatment of beads by microwave at varying intensities of irradiation can aid to retard the drug release with a greater reduction extent through treating the beads for a longer duration of irradiation. The treatment of beads by microwave induced the formation of multiple polymeric domains of great strength and extent of polymer-polymer and drug-polymer interaction. The release of drug from beads was retarded via the interplay of O-H, N-H, C-H, (CH2)n and C-O functional groups of these domains, and was mainly governed by the state of polymer relaxation of the matrix unlike that of the untreated beads of which the release of drug was effected via drug diffusion and polymer relaxation. In comparison to Ca2+ crosslinked matrix which exhibited inconsistent drug release retardation behavior under the influence of microwave, the extent and rate of drug released from the Zn2+ crosslinked beads were greatly reduced by microwave and the release of drug from these beads was consistently retarded in response to both high and low intensity microwaves.

Structural and chemical changes in ultra-high-molecular-weight polyethylene due to gamma radiation-induced crosslinking and annealing in air.

Ultra-High-Molecular-Weight-Polyethylene (UHMWPE) is the material of choice for one of the articulating surfaces in many total joint replacements, notably hip and knee prostheses. The various methods used by the orthopaedic biomaterials industry to sterilize and anneal UHMWPE components, and the resulting oxidation and crosslinking, affect the mechanical wear resistance properties in ways still unknown at the microscopic and molecular levels. Transmission electron microscopy and chemical pyrolysis were used to quantify crosslinking induced by gamma irradiation and annealing in air. Changes in lamellar stacking and the amount of crosslinking suggest two types of crosslinking: relatively unstable crosslinks in the amorphous region initially resulting from gamma irradiation which are later replaced by more thermally stable crosslinks resulting from rearrangements at the annealing temperature. Lamellar mobility, the ability of crystalline lamellae to flow in the material, is enhanced during the transition from one type of bond to the other, and this appears to optimize near eight hours of annealing time. Results from decomposition and percent crystallinity measurements provide further support for this theory.

Effects of microwave on drug release property of poly(methyl vinyl ether-co-maleic acid) matrix.

The drug release behavior of beads made of poly(methyl vinyl ether-co-maleic acid) was investigated with respect to the influence of microwave irradiation. The beads were prepared by an extrusion method with sodium diclofenac as a model water-soluble drug. The beads were subjected to microwave irradiation at 80 W for 5 and 20 min, and at 300 W for 1 min 20 s and 5 min 20 s. The profiles of drug dissolution, drug content, drug-polymer interaction, and polymer-polymer interaction were determined by using dissolution testing, drug content assay, differential scanning calorimetry, and Fourier transform infra-red spectroscopy. Keeping the level of supplied irradiation energy identical, treatment of beads by microwave at varying intensities of irradiation did not bring about similar drug release profiles. The extent and rate of drug released from beads were markedly enhanced through treating the samples by microwave at 80 W as a result of loss of polymer-polymer interaction via the (CH(2))(n) moiety, but decreased upon treating the beads by microwave at 300 W following polymer-polymer interaction via the O-H, COOH, and COO(-) moieties as well as drug-polymer interaction via the N-H, O-H, COO(-), and C-O moieties. The beads treated by microwave at 300 W exhibited a higher level of drug release retardation capacity than those that were treated by microwave at 80 W in spite of polymer-polymer interaction via the (CH(2))(n) moiety was similarly reduced in the matrix. The mechanism of drug release of both microwave-treated and untreated beads tended to follow zero order kinetics. The drug release was markedly governed by the state of polymer relaxation of the matrix and was in turn affected by the state of polymer-polymer and/or drug-polymer interaction in beads.

Deformation, yielding, fracture and fatigue behavior of conventional and highly cross-linked ultra high molecular weight polyethylene.

Medical grade ultra high molecular weight polyethylene (UHMWPE) has been used as the bearing surface of total joint replacements for over four decades. These polymeric devices are susceptible to accumulated cyclic damage in vivo. Wear debris formation that ultimately leads to a need for revision surgery is linked to the plasticity, fatigue and fracture mechanisms of UHMWPE. This paper examines the deformation, yielding, fracture and fatigue behavior of conventional and highly cross-linked medical grade UHMWPE. Such properties play an important role in determining the long-term success of orthopedic devices. The mechanical properties discussed include the deformation behavior of UHMWPE, the yielding associated with quasi-static tension and compression, fracture toughness, cyclic loading, and fatigue resistance.

J-integral fracture toughness and tearing modulus measurement of radiation cross-linked UHMWPE.

Radiation and chemical cross-linking of medical grade ultrahigh molecular weight polyethylene (UHMWPE) has recently been utilized in an effort to improve wear performance of total joint replacement components. However, reductions in mechanical properties with cross-linking are cause for concern regarding the use of cross-linked UHMWPE for high-stress applications such as in total knee replacement prostheses. In this study, the fracture behavior of radiation cross-linked UHMWPE was compared to that of uncross-linked UHMWPE. The Rice and Sorensen model that utilizes mechanical parameters obtained from uniaxial tensile and compact tension tests was used to calculate the steady state J-integral fracture toughness, Jss, for radiation cross-linked UHMWPE. Jss decreased monotonically with increase in radiation dose. UHMWPE exhibited tough, ductile tearing behavior with stable crack growth when it was cross-linked using a gamma radiation dose of 0-50 kGy. However, in cross-linked UHMWPE irradiated to a dose of 100 and 200 kGy, unstable fracture occurred spontaneously upon attaining the initial crack driving force, J1c. This indicates that a high degree of cross-linking is less desirable for high-stress applications in orthopaedic implants. However, a substantial increase in J1c, even at a low degree of cross-linking, suggests that a low degree of cross-linking may be beneficial for resistance to delamination and catastrophic failure, both of which require an initiation step for the fracture to propagate in the material. This mechanical test should, however, be considered along with fatigue tests and joint simulator testing before determination of an appropriate amount of cross-linking for total joint replacement prostheses that experience high stresses.

Effect of an accelerated aging protocol on viscoelastic properties of UHMWPE.

The values of two viscoelastic properties (storage modulus and loss angle) of four sets of ultra-high-molecular-weight polyethylene specimens were obtained. Two sets comprised specimens that had been sterilized (using gamma radiation in air or ethylene oxide gas) while the other two sets comprised specimens that were sterilized and then exposed to an accelerated aging protocol that, in the literature, has been proposed as simulating 5 years of real-time shelf aging. An analysis of the present results from the four specimen sets and those obtained, in a previous study by the present author, on specimens machined from real-time shelf aged tibial inserts suggests that the claim made for the accelerated aging protocol may be conservative.

[Evaluation of Chirulen biopolymer properties based on molecular and super-molecular structure changes caused by plastic strain and radiation sterilization]. / Ocena wlasciwosci biopolimeru Chirulen na podstawie zmian budowy molekularnej i nadczasteczkowej, wywolanych odksztalceniem plastycznym i sterylizacja radiacyjna.

The paper presents an analysis of the effect of plastic strain and sterilization treatment by an electron beam as well as the joint effect of both of the two external factors on the change of molecular and supermolecular characteristics of the Chirulen biopolymer which is used for the production of Weller endoprosthesis cups. It has been shown how, due to these influences, the weighted mean molar mass, differentiation of macromolecule sizes, crystalline phase fraction and the degree of order of polymer internal structure are changing. In terms of such changes the effects on the cup material are presented connected with hardness, the modulus of elasticity and polymer susceptibility to undurable deformations. Simultaneously, conclusions were formed concerning possible biopolymer behaviors during endoprosthesis service if the described effects and accompanying modification of the internal structure occur.

Accelerated aging studies of UHMWPE. I. Effect of resin, processing, and radiation environment on resistance to mechanical degradation.

The resin and processing route have been identified as potential variables influencing the mechanical behavior, and hence the clinical performance, of ultra-high molecular weight polyethylene (UHMWPE) orthopedic components. Researchers have reported that components fabricated from 1900 resin may oxidize to a lesser extent than components fabricated from GUR resin during shelf aging after gamma sterilization in air. Conflicting reports on the oxidation resistance for 1900 raise the question of whether resin or manufacturing method, or an interaction between resin and manufacturing method, influences the mechanical behavior of UHMWPE. We conducted a series of accelerated aging studies (no aging, aging in oxygen or in nitrogen) to systematically examine the influence of resin (GUR or 1900), manufacturing method (bulk compression molding or extrusion), and sterilization method (none, in air, or in nitrogen) on the mechanical behavior of UHMWPE. The small punch testing technique was used to evaluate the mechanical behavior of the materials, and Fourier transform infrared spectroscopy was used to characterize the oxidation in selected samples. Our study showed that the sterilization environment, aging condition, and specimen location (surface or subsurface) significantly affected the mechanical behavior of UHMWPE. Each of the three polyethylenes evaluated seem to degrade according to a similar pathway after artificial aging in oxygen and gamma irradiation in air. The initial ability of the materials to exhibit post-yield strain hardening was significantly compromised by degradation. In general, there were only minor differences in the aging behavior of molded and extruded GUR 1050, whereas the molded 1900 material seemed to degrade slightly faster than either of the 1050 materials.