AU2012203503A1 - Ultra high molecular weight polyethylene articles and methods of forming ultra high molecular weight polyethylene articles - Google Patents

Abstract

The present invention generally provides a vitamin E stabilized, consolidated, irradiation crosslinked ultra high molecular weight polyethylene blend, the crosslinked blend 10 comprising a uniform dispersion of vitamin E within a surface region. C:%*kord\SPEC-944379.docx

Description

AUSTRALIA Patents Act COMPLETE SPECIFICATION (ORIGINAL) Class Int. Class Application Number: Lodged: Complete Specification Lodged: Accepted: Published: Priority Related Art: Name of Applicant: Zimmer GmbH Actual Inventor(s): Werner Schneider-Storrer, Niels A. Abt Address for Service and Correspondence: PHILLIPS ORMONDE FITZPATRICK Patent and Trade Mark Attorneys 367 Collins Street Melbourne 3000 AUSTRALIA Invention Title: ULTRA HIGH MOLECULAR WEIGHT POLYETHYLENE ARTICLES AND METHODS OF FORMING ULTRA HIGH MOLECULAR WEIGHT POLYETHYLENE ARTICLES Our Ref: 944379 POF Code: 221787/473663 The following statement is a full description of this invention, including the best method of performing it known to applicant(s): - 1 SOOsq ULTRA HIGH MOLECULAR WEIGHT POLYETHYLENE ARTICLES AND METHODS OF FORMING ULTRA HIGH MOLECULAR WEIGHT POLYETHYLENE ARTICLES The present application is a divisional application from Australian Patent Application No. 2005335669. The entire disclosures of which are incorporated herein by reference. BACKGROUND Many endoprosthetic joint replacements currently implanted in patients include a highly polished metal or ceramic component articulating on an ultra high molecular weight polyethylene (UHMWPE)material or blend. Wear and abrasion resistance, coefficient of friction, impact strength, toughness, density, biocompatibility and biostability are some of the properties that make UHIMWPE a suitable material for such implants. Although UIMWPE has been used in implants for many years, there is continuing interest in the wear and durability characteristics of implants incorporating UHMWPE. One method employed to improve the durability and other physical characteristics of UHMvWPE implants has been to expose such implants to radiation, for example gamma radiation or electron beam radiation, to induce crosslinking in the UHMWPE. Similar radiation sources have also been used to sterilize UHMWPE implants prior to distribution. Despite the benefits of irradiating UHMWPE implants, the irradiation process may lead to increased rates of oxidation in the UHMWPE implant. In particular, irradiation has been shown to generate free radicals, which react in the presence of oxygen to form peroxyl radicals. These free radicals and peroxyl radicals may react with the polyethylene backbone and with each other to form oxidative degradation products and additional radical species. This cycle of oxidation product and radical species formation may occur over several years (both prior to and after implantation) as oxidation levels in the implant increase. One method that has been utilized to reduce oxidation in irradiated UHMWPE materials is the addition of a stabilizing component to the UHMWPE 2 material to inhibit the oxidation cycle. However, the addition of a stabilizer or stabilizing components, such as vitamin E, to UHMWPE prior to irradiation has been shown to have an adverse effect on crosslinking during irradiation. See Parth et al., "Studies on the effect of electron beam radiation on the molecular structure of ultra-high molecular weight polyethylene under the influence of a-tocopherol with respect to its application in medical implants, "Journal of Materials Science: Materials In Medicine", 13 (2002), pgs. 917-921. For this reason, the addition of stabilizers to UHMWPE materials after forming and irradiating via diffusion has been proposed. See e.g., PCT Published Application No.W02004/101009. However, the addition of stabilizers after irradiation has several limitations. For example, vitamin E diffusion may provide a less uniform distribution of stabilizer in UHMWPE than pre-irradiation mixing. Diffusion of the vitamin E may also require separate irradiation steps to induce crosslinking prior to adding vitamin E and then to sterilize the implant after adding vitamin E. Therefore, it would be beneficial to provide a method of forming a crosslinked UHMWPE material for use in implanted articles that overcomes one or more of these limitations. SUMMARY In one embodiment, the present invention provides a vitamin E stabilized, consolidated, irradiation crosslinked ultra high molecular weight polyethylene blend, the crosslinked blend comprising a uniform dispersion of vitamin E within a surface region. In another embodiment the present invention provides a method of forming a crosslinked ultra high molecular weight polyethylene blend comprising: combining vitamin E dissolved in an alcohol with ultra-high molecular weight polyethylene powder to form an ultra-high molecular weight polyethylene blend; consolidating the ultra-high molecular weight polyethylene blend; and irradiating the consolidated ultra-high molecular weight polyethylene blend to crosslink said consolidated ultra-high molecular weight polyethylene blend to form a crosslinked blend; wherein at least some of the vitamin E is uniformly dispersed within a surface region of the 3 crosslinked blend. In yet another embodiment the present invention provides an implantable article comprising: a crosslinked ultra high molecular weight polyethylene blend wherein the blend is produced by a method comprising combining vitamin E dissolved in an alcohol with ultra-high molecular weight polyethylene powder to form an ultra-high molecular weight polyethylene blend; consolidating the ultra-high molecular weight polyethylene blend; and irradiating the consolidated ultra-high molecular weight polyethylene blend to crosslink said consolidated ultra-high molecular weight polyethylene blend to form a crosslinked blend; wherein at least some of the vitamin E is uniformly dispersed within a surface region of the crosslinked blend BRIEF DESCRIPTION OF FIGURES Figs. 1A-IC are flow-charts illustrating methods of preparing UHMWPE implants according to embodiments of the present invention. Figs. 2A-2B are flow-charts illustrating methods of preparing UHMWPE implants according to additional embodiments of the present invention. Fig. 3 is a line graph illustrating the swell ratio of several UHMWPE samples, described in the Example, at various radiation dose rates. Figs. 4A-4C are bar graphs illustrating the TVI (4A), swell ratio (4B) and soluble fraction (4C), of several UHMWPE samples. Fig. 5 is a line graph illustrating the vitamin E concentration of several UHMWPE samples at a range of depths. Fig. 6 is a prior art line graph showing the vitamin E index of samples prepared pursuant to U.S. Published Application No. 2004/0156879. Fig. 7 is a line graph showing the oxidation levels of several UHMWPE samples at a range of depths. Fig. 8 is a bar graph showing the tensile strength of several UHMWPE samples. Fig. 9 is a bar graph showing the elongation percent at break of several UHMWPE samples. Fig. 10 is a bar graph showing the Charpy impact strength of several UHMWPE samples. 4 DETAILED DESCRIPTION UHMWPE is a semicrystalline, linear homopolymer of ethylene, which may be produced by stereospecific polymerization with a Ziegler-Natta catalyst at low pressure (6-8 bar) and low temperature (66-80*C.). The synthesis of nascent UHMWPE results in a fine granular powder. The molecular weight and its distribution can be controlled by process parameters such as temperature, time and pressure. UHMWPE generally has a molecular weight of at least about 2,000,000 g/mol. Suitable UHMWPE materials for use as raw materials in the present invention may be in the form of a powder or mixture of powders. The UHMWPE material may be prepared almost entirely from UHMWPE powder, or may be formed by combining UHMWPE powder with other suitable polymer materials. In one embodiment, the UHMWPE material may include at least about 50 w/w/o UHMWPE. Examples of suitable UHMWPE materials include GUR 1020 and GUR 1050 available from Ticona Engineering Polymers. Suitable polymer materials for use in combination with the UHMWPE materials may include disentangled polyethylene, high pressure crystallized polyethylene and various other "super tough" polyethylene derivatives. In addition, biocompatible non-polyethylene polymers may also be suitable for use in certain embodiments. Suitable additives to the UHMWPE material include radiopaque materials, antimicrobial materials such as silver ions, antibiotics, and microparticles and/or nanoparticles serving various functions. Preservatives, colorants and other conventional additives may also be used. Suitable stabilizers for addition to the UHMWPE material generally include materials that can be added in an effective amount to the UHMWPE material in order to, at least in part, inhibit the oxidation cycle caused by irradiation of UHMWPE. Vitamin E is particularly suitable for use in embodiments of the present invention. As used herein "vitamin E" refers generally to derivatives of tocopherol including a-tocopherol. Other suitable stabilizers may include phenolic antioxidants such as butylated hydroxytoluene, and ascorbic acid. The vitamin E stabilizer and UHMWPE material may be combined via a number of known processes to form a UHMWPE blend. Such processes include 5 physical mixing, mixing with the aid of a solvent, mixing with the aid of a solvent (e.g. Coe) under supercritical temperature and pressure conditions, and ultrasonic mixing. Suitable mixing processes of these types are also described, for example, in U.S. Patent Nos. 6,448,315 and 6,277,390, the disclosures of which are hereby incorporated by reference. In one embodiment, vitamin E is dissolved in ethanol and is drop-wise added to a powdered UHMWPE material while mixing. The ethanol may then be removed via a vacuum dryer or similar apparatus. Figures IA-IC and 2A-2B are flowcharts illustrating methods for preparing implants from UHMWPE blends according to embodiments of the present invention. The general steps for processing the implant include a consolidating/compressing the UHMWPE blend, cross-linking the UHMWPE blend, manufacturing an implant from the compressed UHMWPE blend, packaging the implant, and sterilizing the packaged implant. As reflected in Figs. IA-C and 2A-2B, these steps may be carried out in varying order, in multiple steps, or simultaneously in accordance with embodiments of the present invention. The UHMWPE blend may first be consolidated and/or compressed into suitable form for use as (or as part of) a prosthetic device or other implant. Suitable compression and/or consolidation techniques include, for example, compression molding, direct compression molding, hot isostatic pressing, ram extrusion, high pressure crystallization, injection molding, sintering or other conventional methods of compressing and/or consolidating UHMWPE. If desired, the compressed/consolidated UHMWPE blend may be further processed or manufactured by milling, machining, drilling, cutting, assembling with other components, and/or other manufacturing or pre-manufacturing steps conventionally employed to manufacture implants from UHMWPE. Prior to and/or after processing the implant as reported above, the UHMWPE blend may be crosslinked by exposure to radiation at a high radiation dose and/or dose rate to form a crosslinked UHMWPE blend. In one embodiment, the UHMWPE blend may be exposed to electron beam radiation at a dose of at least about 25 kiloGrey, more particularly at least about 80 kiloGrey, and even more particularly at least about 95 kiloGrey. In another embodiment, the UHMWPE blend may be exposed to radiation at a dose rate of at least 1 MegaGrey per hour, more particularly at least about 15 MegaGrey per hour, and even more particularly about 18 MegaGrey per 6 hour. In certain embodiments, the desired radiation dose may be achieved in a single exposure step at a high dose rate. In other embodiments, a series of high dose rate irradiation steps may be employed to expose the UHMWPE blend to a desired dose of radiation In certain embodiments, the radiation source is electron beam radiation. Electron beam radiation exposure may be performed using conventionally available electron beam accelerators. One commercial source for such an accelerator is IBA Technologies Group, Belgium. Suitable accelerators may produce an electron beam energy between about 2 and about 50 MeV, more particularly about 10 MeV, and are generally capable of accomplishing one or more of the radiation doses and/or dosage rates reported herein. Electron beam exposure may be carried out in a generally inert atmosphere, including for example, an argon, nitrogen, vacuum, or oxygen scavenger atmosphere. Exposure may also be carried out in air under ambient conditions according to one embodiment. Gamma and x-ray radiation may also be suitable for use in alternate embodiments of the invention. The present invention need is not necessarily limited to a specific type of source of radiation. Optionally, prior to and/or after electron beam irradiation, the UHMWPE blend may be subjected to one or more temperature treatments. In one embodiment, the UHMWPE blend may be heated above room temperature, more particularly above about 100 *C, even more particularly between about 120 *C and 130 *C, prior to irradiation. U.S. Patent No. 6,641,617 to Merril et al., which is hereby incorporated by reference, reports methods of employing such temperature treatment steps in greater detail. In another embodiment, the UHMWPE blend may remain at room temperature or may even be cooled below room temperature, for example, below the glass transition temperature of the UHMWPE blend. After irradiation, the crosslinked UHMWPE blend may be annealed at a temperature of up to about 200 *C for up to about 72 hours, more particularly at about 150 *C for about 5 hours. Alternatively or additionally, the crosslinked UHMWPE blend may be subjected to the mechanical annealing processes reported in U.S. Patent No. 6,853,772 to Muratoglu, which is hereby incorporated by reference. In one embodiment, however, no pre- or post-irradiation temperature and/or annealing treatments are performed. As part of the implant manufacturing process, additional components may be 7 combined with the UHMWPE blend at any time during the process reported herein. In one embodiment, tribological components such as metal and/or ceramic articulating components and/or preassembled bipolar components may be joined with the UHMWPE blend. In other embodiments, metal backing (e.g. plates or shields) may be added. In further embodiments, surface components such a trabecular metal, fiber metal, beats, Sulmesh@ coating, meshes, cancellous titanium, and/or metal or polymer coatings may be added to or joined with the UHMWPE blend. Still further, radiomarkers or radiopacifiers such as tantalum, steel and/or titanium balls, wires, bolts or pegs may be added. Further yet, locking features such as rings, bolts, pegs, snaps and/or cements/adhesives may be added. These additional components may be used to form sandwich implant designs, radiomarked implants, metal-backed implants to prevent direct bone contact, functional growth surfaces, and/or implants with locking features. A variety of implants, and in particular endoprosthetic joint replacements, may be prepared by employing the methods reported herein. Examples of such implants include artificial hips and knees, cups or liners for artificial hips and knees, spinal replacement disks, artificial shoulder, elbow, feet, ankle and finger joints, mandibles, and bearings of artificial hearts. After manufacturing of the implant has been completed, it may be packaged and sterilized prior to distribution. Packaging is generally carried out using either gas permeable packaging or bather packaging utilizing a reduced oxygen atmosphere. Because the presence of vitamin E in the UHMWPE blend inhibits the oxidation cycle, conventional gas permeable packing may be suitable for embodiments of the present invention. Bather packaging with an inert gas backfill (e.g. argon, nitrogen, oxygen scavenger) is also suitable. As reflected in Figs. IA-IC and 2A-2B, sterilization may be accomplished either by radiation exposure during crosslinking of the UHMWPE blend, or as part of a separate processing step. A number of conventional sterilization techniques exist including gas plasma sterilization, ethylene oxide sterilization, gamma radiation sterilization and e-beam radiation. In the embodiments illustrated in Figs. IA, IC and 2B, crosslinking is carried out prior to packaging. In the embodiments illustrated in Figs. lB and 2A, sterilization and crosslinking are carried out by e-beam irradiation in a single step after packaging the implant. 8 Sterilization generally occurs after packaging. In certain embodiments, sterilization is carried out at the same time as crosslinking, and therefore utilizes e-beam radiation. In embodiments in which crosslinking occurs before sterilization, additional suitable sterilization methods include gamma irradiation (either inert or in air), gas plasma exposure or ethylene oxide exposure. As further exemplified in the Examples set forth below, the crosslinked U1-1 1 VIWPE blends produced according to embodiments of the present invention may have several beneficial characteristics. Notably, such blends exhibit lower levels of oxidation when compared to unstabilized UHMWPE materials, while still exhibiting suitable levels of crosslinking. The use of a high radiation dose rate or a series of high radiation dose rates, at least in part, contributes to improved crosslinking densities for the UHMWPE blend, which is contrary to prior art reports that suggest that suitable crosslinking densities are difficult to achieve when irradiating stabilized UHMWPE blends. Also, such UHMWPE blends may have a generally uniform distribution of vitamin E at least a surface region of the blend. As used herein, the phrase "surface region" refers to a region of a crosslinked UHMWPE blend extending from a surface of the blend to some depth or range of depths below the surface. For example, the implants formed from the crosslinked UHMWPE blend of certain embodiments may exhibit a substantially uniform distribution of vitamin E to a surface depth of at least 3 mm, more particularly, at least 5 mm. Other embodiments may exhibit a substantially uniform distribution of vitamin E to a surface depth of at least 10 mm, more particularly at least 15 mm, even more particularly at least 20 mm. In further embodiments, the UHMWPE blend may have a substantially uniform distribution of vitamin E throughout the blend. EXAMPLES Table I sets forth the processing parameters for Samples A-I. 9 TABLE 1 SAMLE Rw E- Befre Inadon Irradon Irrnaton Rarndan Annanng Material Ce Ia- aon Dose Dose Rate Environment Source Process _____ GUR wI'w* -C ko ________ A 1020 0.0 N/A 25-40 03 to N 2 Gamma N/A B 1020 0.0 N/A N/A N/A N/A N/A N/A C 1020 0.1 N/A N/A N/A N/A N/A N/A D 1020 0.1 N/A 25-40 05 to 10 N2 Gamma N/A E 1020 0.0 120 95 18Air eeam 15C F 1020 0.1 120 95 18Air eBeam .150"C G 1020 0.1 N/A 95 Air eBeam N/A H 1020 0.1 N/A 95 03 to Air Gamma N/A I 1050 0.0 120 95 Ai eBeam ' As set forth in Table 1, GUR 1020 and GUR 1050 brand UHMWPE powders are available from Ticona GmbH, FrankfurtMain, DE. The vitamin E used for Samples C, D and F-H was a-tocopherol obtained from DSM Nutritional Products AG, Basel, Switzerland. For Samples C, D and F-H, the a-tocopherol was dissolved in ethanol in a concentration of 50 g/1 and mixed into the UHMWPE drop-wise using a Nauta-Vrieco brand screw-cone mixer. The ethanol was then removed from the UHMWPE blend in a vacuum dryer at 50*C for 6 hours, resulting in a UHMWPE blend having a concentration of a-tocopherol of about 0.1 w/w/o. The resulting UHMWPE blend was then sintered for 7 hours at 220*C and 35 bar to produce UHMWPE plates having a thickness of 60 mm and a diameter of 600 mm. Homogeneity of the a-tocopherol in the UHMWPE blend was measured by standard HPLC methods and determined to vary up to +/-2% from the desired content. Samples A, D and H were irradiated using a Studer IR- 168 Gamma Irradiator utilizing a Co 6 * radiation source. Samples E-G and I were irradiated using a 10 MeV Rhodotron electron accelerator available from IBA SA, Louvain-La-Neuve using a 120 kW power setting. 10 RESULTS Fig. 3 shows a line graph illustrating the swell ratio of unstabilized polyethylene versus a polyethylene blend stabilized with Vitamin E. The swell ratio is a useful indicator of the crosslinking density of a particular material. In particular, lower relative swell ratios are indicative of higher levels of crosslinking, and vice versa. The swell ratio was determined according to ASTM F2214-02. Specifically, 4-6 mm cubes of each of Samples H, F, G and E were placed in a container filled with o-Xylene at 25*C and placed in a dynamical mechanical analyzer (DMA, DMA 7e available from Perkin Elmer) for 10 minutes. A first sample height (Ho) was then taken for each sample. The samples were then heated at a rate of 5K/min to a maintained temperature of 130*C. A second sample height (Hf) was then taken after 120 minutes at 130*C. The swell ratio was then calculated according to the following equation: qs = (Hr/Ho) 3 The data points for the lower flat line include a swell ratio standard for unstabilized UHMWPE (obtained from the interlaboratory comparison in ASTM F2214-02 at a dose rate of 89 kGy) and unstabilized Sample E. These data points indicate that dose rates do not have a substantial effect on crosslink density. The data points for the upper descending line include Samples H, F and G. Notably, the increased irradiation dosage rates used for Samples F and G resulted in a decreased swell ratio when compared to sample H, and consequently, an increased crosslink density. Figs. 4A-4C are three bar graphs illustrating several characteristics of Samples B, C, and E-H. Fig. 4A is a bar graph illustrating the trans-Vinylene Index (TVI) levels of the Samples. The TVI was determined by the method described in Muratoglu et aL, "Identification and quantification of irradiation in UHMWPE through trans-vinylene yield." TVI levels are an indicator of the radiation absorption efficiency of UHMWPE. Fig. 4A indicates that the Samples E and F, which were preheated before irradiation and annealed after irradiation, possessed higher radiation absorption efficiency than other samples. Fig. 4B is a bar graph illustrating the swell ratio of the same samples 11 reported in Fig. 4A. Notably, Sample H, which was gamma-irradiated, shows a higher swell ratio (and therefore lower crosslink density) than the e-beam irradiated Samples E, F and G. Fig. 4C is a bar graph of the soluble fraction of the samples reported in Fig. 4A. The soluble fraction indicates the percentage of fully crosslinked material in the sample. The soluble fraction for each sample was determined in accordance with ASTM 2765-01. Specifically, powdered UHMWPE was taken from a location 10 mm under the surface of the sample by a rasping technique. This sample was then weighed in a wire mesh and backfluxed for 12 hours in xylene. After backfluxing, the remaining gel portion was placed in a vacuum furnace and dried at a temperature of 140*C and a pressure of less than 200 mbar, and was then conditioned in an exsiccator before being weighted again. The resulting gel portion and soluble portion was computed by weighing the sample before and after the procedure. Sample H, which was gamma irradiated, shows a higher soluble fraction than e-beam irradiated Samples E, F and G. Fig. 5 is a line graph indicating the vitamin E content at a range of depths from the surface of Samples C, F, G and H. Fig. 5 indicates that a uniform vitamin E concentration is maintained in each Sample in a surface region at least up to the measured depth of 20 mm. This uniform distribution of vitamin E is particularly notable when compared to Prior Art Fig. 6 reported in U.S. Published Application No 2004/0156879, in which the vitamin E index of diffused vitamin E samples steadily decreased as depth increased. Fig. 7 is a line graph illustrating the oxidation levels of Samples E, F, G and H. Notably, oxidation levels at certain depths from the surface of the sample material were higher for Sample E (did not include vitamin E) and Sample H (gamma irradiated) as compared to Samples G and F (e-beam irradiated). Figs. 8-10 are a series of bar graphs illustrating various mechanical properties of Samples A, D, E, F, G, H and L Fig. 8 illustrates the mechanical strength of each sample, and generally indicates that the pre-heating and annealing processing methods utilized with samples E, F and I resulted in somewhat decreased mechanical strength as compared to the cold irradiation method used for Sample G and H. Fig. 9 illustrates the elongation percent at the breaking point of each sample. Fig. 10 illustrates the impact strength of each sample based on the Charpy impact 12 scale (kT/m 2 ), and generally indicates that the presence of vitamin E increases the impact strength of crosslinked UHMWPE. 13

Claims (15)

1. A vitamin E stabilized, consolidated, irradiation crosslinked ultra high molecular weight polyethylene blend, the crosslinked blend comprising a uniform dispersion of vitamin E within a surface region.

2. The crosslinked blend of claim 1 wherein the surface region extends from an exposed surface of the crosslinked blend to a depth of at least about 5 millimeters from the surface of the crosslinked blend.

3. The crosslinked blend of any one of claims 1-2 wherein the surface region extends from an exposed surface of the crosslinked blend to a depth of at least about 15 millimeters from the surface of the crosslinked blend.

4. The crosslinked blend of any one of claims 1-3 wherein the uniformly dispersed vitamin E is at least 0.02 w/w/o of the crosslinked blend.

5. The crosslinked blend of any one of claims 1-4 wherein the vitamin E is dispersed substantially uniformly throughout the crosslinked blend.

6. The crosslinked blend of any one of claims 1-5, wherein the crosslinked blend has a swell ratio of less than about 4.

7. The crosslinked blend of any one of claims 1-6, wherein the crosslinked blend has a swell ratio of less than about 3.5.

8. A method of forming a crosslinked ultra high molecular weight polyethylene blend comprising: combining vitamin E dissolved in an alcohol with ultra-high molecular weight polyethylene powder to form an ultra-high molecular weight polyethylene blend; consolidating the ultra-high molecular weight polyethylene blend; and 14 irradiating the consolidated ultra-high molecular weight polyethylene blend to crosslink said consolidated ultra-high molecular weight polyethylene blend to form a crosslinked blend; wherein at least some of the vitamin E is uniformly dispersed within a surface region of the crosslinked blend.

9. The method of claim 8, wherein the crosslinked blend has a swell ratio of less than about 4.

10. The method of any one of claims 8-9, wherein the irradiation comprises electron-beam radiation at an absorbed dose of at least 60 kiloGrey and a dose rate of at least 1 MegaGrey per hour.

11. The method of any one of claims 8-10 wherein the surface region extends from an exposed surface of the crosslinked blend to a depth of at least about 5 millimeters from the surface of the crosslinked blend.

12. The method of any one of claims 8-11 wherein the surface region extends from an exposed surface of the crosslinked blend to a depth of at least about 15 millimeters from the surface of the crosslinked blend.

13. The method of any one of claims 8-12 wherein the vitamin E is dispersed substantially uniformly throughout the crosslinked blend.

14. The method of any one of claims 8-13 comprising preheating the ultra-high molecular weight polyethylene blend to above room temperature prior to irradiation.

15. The method of any one of claims 8-14 wherein the ultra-high molecular weight polyethylene blend is annealed after irradiation at a temperature less than or equal to about 200 *C. 15