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Ultra-high-molecular-weight polyethylene (UHMWPE, UHMW) is a subset of the thermoplastic polyethylene. Also known as high-modulus polyethylene (HMPE), it has extremely long chains, with a molecular mass usually between 3.5 and 7.5 million amu.[1] The longer chain serves to transfer load more effectively to the polymer backbone by strengthening intermolecular interactions. This results in a very tough material, with the highest impact strength of any thermoplastic presently made.[2]
UHMWPE is odorless, tasteless, and nontoxic.[3] It embodies all the characteristics of high-density polyethylene (HDPE) with the added traits of being resistant to concentrated acids and alkalis, as well as numerous organic solvents.[4] It is highly resistant to corrosive chemicals except oxidizing acids; has extremely low moisture absorption and a very low coefficient of friction; is self-lubricating (see boundary lubrication); and is highly resistant to abrasion, in some forms being 15 times more resistant to abrasion than carbon steel. Its coefficient of friction is significantly lower than that of nylon and acetal and is comparable to that of polytetrafluoroethylene (PTFE, Teflon), but UHMWPE has better abrasion resistance than PTFE.[5][6]
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Polymerization of UHMWPE was commercialized in the s by Ruhrchemie AG,[1][7] which has changed names over the years. Today UHMWPE powder materials, which may be directly molded into a product's final shape, are produced by Ticona, Braskem, Teijin (Endumax), Celanese, and Mitsui. Processed UHMWPE is available commercially either as fibers or in consolidated form, such as sheets or rods. Because of its resistance to wear and impact, UHMWPE continues to find increasing industrial applications, including the automotive and bottling sectors. Since the s, UHMWPE has also been the material of choice for total joint arthroplasty in orthopedic and spine implants.[1]
UHMWPE fibers branded as Dyneema, commercialized in the late s by the Dutch chemical company DSM, and as Spectra, commercialized by Honeywell (then AlliedSignal), are widely used in ballistic protection, defense applications, and increasingly in medical devices, sailing, hiking equipment, climbing, and many other industries.
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Structure of UHMWPE, with n greater than 100,000UHMWPE is a type of polyolefin. It is made up of extremely long chains of polyethylene, which all align in the same direction. It derives its strength largely from the length of each individual molecule (chain). Van der Waals forces between the molecules are relatively weak for each atom of overlap between the molecules, but because the molecules are very long, large overlaps can exist, adding up to the ability to carry larger shear forces from molecule to molecule. Each chain is attracted to the others with so many van der Waals forces that the whole of the inter-molecular strength is high. In this way, large tensile loads are not limited as much by the comparative weakness of each localized van der Waals force.
When formed into fibers, the polymer chains can attain a parallel orientation greater than 95% and a level of crystallinity from 39% to 75%. In contrast, Kevlar derives its strength from strong bonding between relatively short molecules.
The weak bonding between olefin molecules allows local thermal excitations to disrupt the crystalline order of a given chain piece-by-piece, giving it much poorer heat resistance than other high-strength fibers. Its melting point is around 130 to 136 °C (266 to 277 °F),[8] and, according to DSM, it is not advisable to use UHMWPE fibres at temperatures exceeding 80 to 100 °C (176 to 212 °F) for long periods of time. It becomes brittle at temperatures below &#;150 °C (&#;240 °F).[9]
The simple structure of the molecule also gives rise to surface and chemical properties that are rare in high-performance polymers. For example, the polar groups in most polymers easily bond to water. Because olefins have no such groups, UHMWPE does not absorb water readily, nor wet easily, which makes bonding it to other polymers difficult. For the same reasons, skin does not interact with it strongly, making the UHMWPE fiber surface feel slippery. In a similar manner, aromatic polymers are often susceptible to aromatic solvents due to aromatic stacking interactions, an effect aliphatic polymers like UHMWPE are immune to. Since UHMWPE does not contain chemical groups (such as esters, amides, or hydroxylic groups) that are susceptible to attack from aggressive agents, it is very resistant to water, moisture, most chemicals, UV radiation, and micro-organisms.
Under tensile load, UHMWPE will deform continually as long as the stress is present&#;an effect called creep.
When UHMWPE is annealed, the material is heated to between 135 °C (275 °F) and 138 °C (280 °F) in an oven or a liquid bath of silicone oil or glycerine. The material is then cooled down at a rate of 5 °C/h (2.5 °F/ks) to 65 °C (149 °F) or less. Finally, the material is wrapped in an insulating blanket for 24 hours to bring to room temperature.[10]
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Ultra-high-molecular-weight polyethylene (UHMWPE) is synthesized from its monomer ethylene, which is bonded together to form the base polyethylene product. These molecules are several orders of magnitude longer than those of familiar high-density polyethylene (HDPE) due to a synthesis process based on metallocene catalysts, resulting in UHMWPE molecules typically having 100,000 to 250,000 monomer units per molecule each compared to HDPE's 700 to 1,800 monomers.
UHMWPE is processed variously by compression moulding, ram extrusion, gel spinning, and sintering. Several European companies began compression molding UHMWPE in the early s. Gel-spinning arrived much later and was intended for different applications.
In gel spinning a precisely heated gel (of a low concentration of UHMWPE in an oil) is extruded through a spinneret. The extrudate is drawn through the air, the oil extracted with a solvent which does not affect the UHMWPE, and then dried removing the solvent. The end-result is a fiber with a high degree of molecular orientation, and therefore exceptional tensile strength. Gel spinning depends on isolating individual chain molecules in the solvent so that intermolecular entanglements are minimal. Entanglements make chain orientation more difficult, and lower the strength of the final product.[11]
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LIROS Dyneema hollowDyneema and Spectra are brands of lightweight high-strength oriented-strand gels spun through a spinneret. They have yield strengths as high as 2.4 GPa (350,000 psi) and density as low as 0.97 g/cm (0.087 oz/in) (for Dyneema SK75).[12] High-strength steels have comparable yield strengths, and low-carbon steels have yield strengths much lower (around 0.5 GPa (73,000 psi)). Since steel has a specific gravity of roughly 7.8, these materials have a strength-to-weight ratios eight times that of high-strength steels. Strength-to-weight ratios for UHMWPE are about 40% higher than for aramid. The high qualities of UHMWPE filament were discovered by Albert Pennings in , but commercially viable products were made available by DSM in and Southern Ropes soon after.[13]
Derivatives of UHMWPE yarn are used in composite plates in armor, in particular, personal armor and on occasion as vehicle armor. Civil applications containing UHMWPE fibers are cut-resistant gloves, tear-resistant hosiery, bow strings, climbing equipment, automotive winching, fishing line, spear lines for spearguns, high-performance sails, suspension lines on sport parachutes and paragliders, rigging in yachting, kites, and kite lines for kites sports.
For personal armor, the fibers are, in general, aligned and bonded into sheets, which are then layered at various angles to give the resulting composite material strength in all directions.[14][15] Recently developed additions to the US Military's Interceptor body armor, designed to offer arm and leg protection, are said to utilize a form of UHMWPE fabric.[16] A multitude of UHMWPE woven fabrics are available in the market and are used as shoe liners, pantyhose,[17] fencing clothing, stab-resistant vests, and composite liners for vehicles.[18]
The use of UHMWPE rope for automotive winching offers several advantages over the more common steel wire rope. The key reason for changing to UHMWPE rope is improved safety. The lower mass of UHMWPE rope, coupled with significantly lower elongation at breaking, carries far less energy than steel or nylon, which leads to almost no snap-back. UHMWPE rope does not develop kinks that can cause weak spots, and any frayed areas that may develop along the surface of the rope cannot pierce the skin like broken steel wire strands can. UHMWPE rope is less dense than water, making water recoveries easier as the recovery cable is easier to locate than wire rope. The bright colours available also aid with visibility should the rope become submerged or dirty. Another advantage in automotive applications is the reduced weight of UHMWPE rope over steel cables. A typical 11 mm (0.43 in) UHMWPE rope of 30 m (98 ft) can weigh around 2 kg (4.4 lb), the equivalent steel wire rope would weigh around 13 kg (29 lb). One notable drawback of UHMWPE rope is its susceptibility to UV damage, so many users will fit winch covers in order to protect the cable when not in use. It is also vulnerable to heat damage from contact with hot components.
Spun UHMWPE fibers excel as fishing line, as they have less stretch, are more abrasion-resistant, and are thinner than the equivalent monofilament line.
In climbing, cord and webbing made of combinations of UHMWPE and nylon yarn have gained popularity for their low weight and bulk. They exhibit very low elasticity compared to their nylon counterparts, which translates to low toughness. The fiber's very high lubricity causes poor knot-holding ability, and it is mostly used in pre-sewn 'slings' (loops of webbing)&#;relying on knots to join sections of UHMWPE is generally not recommended, and if necessary it is recommended to use the triple fisherman's knot rather than the traditional double fisherman's knot.[19][20]
Ships' hawsers and cables made from the fiber (0.97 specific gravity) float on sea water. "Spectra wires" as they are called in the towing boat community are commonly used for face wires [21] as a lighter alternative to steel wires.
It is used in skis and snowboards, often in combination with carbon fiber, reinforcing the fiberglass composite material, adding stiffness and improving its flex characteristics.[clarification needed] The UHMWPE is often used as the base layer, which contacts the snow, and includes abrasives to absorb and retain wax.[clarification needed]
It is also used in lifting applications, for manufacturing low weight, and heavy duty lifting slings. Due to its extreme abrasion resistance it is also used as an excellent corner protection for synthetic lifting slings.
High-performance lines (such as backstays) for sailing and parasailing are made of UHMWPE, due to their low stretch, high strength, and low weight.[22] Similarly, UHMWPE is often used for winch-launching gliders from the ground, as, in comparison with steel cable, its superior abrasion resistance results in less wear when running along the ground and into the winch, increasing the time between failures. The lower weight on the mile-long cables used also results in higher winch launches.
UHMWPE was used for the 30 km (19 mi) long, 0.6 mm (0.024 in) thick space tether in the ESA/Russian Young Engineers' Satellite 2 of September, .[23]
Dyneema Composite Fabric (DCF) is a laminated material consisting of a grid of Dyneema threads sandwiched between two thin transparent polyester membranes. This material is very strong for its weight, and was originally developed for use in racing yacht sails under the name 'Cuben Fiber'. More recently it has found new applications, most notably in the manufacture of lightweight and ultralight camping and backpacking equipment such as tents, backpacks, and bear-proof food bags.
In archery, UHMWPE is widely used as a material for bowstrings because of its low creep and stretch compared to, for example, Dacron (PET).[citation needed] Besides pure UHMWPE fibers, most manufacturers use blends to further reduce the creep and stretch of the material. In these blends, the UHMWPE fibers are blended with, for example, Vectran.
In skydiving, UHMWPE is one of the most common materials used for suspension lines, largely supplanting the earlier-used Dacron, being lighter and less bulky.[citation needed] UHMWPE has excellent strength and wear-resistance, but is not dimensionally stable (i.e. shrinks) when exposed to heat, which leads to gradual and uneven shrinkage of different lines as they are subject to differing amounts of friction during canopy deployment, necessitating periodic line replacement. It is also almost completely inelastic, which can exacerbate the opening shock. For that reason, Dacron lines continue to be used in student and some tandem systems, where the added bulk is less of a concern than the potential for an injurious opening. In turn, in high-performance parachutes used for swooping, UHMWPE is replaced with Vectran and HMA (high-modulus aramid), which are even thinner and dimensionally stable, but exhibit greater wear and require much more frequent maintenance to prevent catastrophic failure. UHMWPE are also used for reserve parachute closing loops when used with automatic activation devices, where their extremely low coefficient of friction is critical for proper operation in the event of cutter activation.
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UHMWPE has a clinical history as a biomaterial for use in hip, knee, and (since the s), for spine implants.[1] An online repository of information and review articles related to medical grade UHMWPE, known as the UHMWPE Lexicon, was started online in .[24]
Joint replacement components have historically been made from "GUR" resins. These powder materials are produced by Ticona, typically converted into semi-forms by companies such as Quadrant and Orthoplastics,[1] and then machined into implant components and sterilized by device manufacturers.[25]
UHMWPE was first used clinically in by Sir John Charnley and emerged as the dominant bearing material for total hip and knee replacements in the s.[24] Throughout its history, there were unsuccessful attempts to modify UHMWPE to improve its clinical performance until the development of highly cross-linked UHMWPE in the late s.[1]
One unsuccessful attempt to modify UHMWPE was by blending the powder with carbon fibers. This reinforced UHMWPE was released clinically as "Poly Two" by Zimmer in the s.[1] The carbon fibers had poor compatibility with the UHMWPE matrix and its clinical performance was inferior to virgin UHMWPE.[1]
A second attempt to modify UHMWPE was by high-pressure recrystallization. This recrystallized UHMWPE was released clinically as "Hylamer" by DePuy in the late s.[1] When gamma irradiated in air, this material exhibited susceptibility to oxidation, resulting in inferior clinical performance relative to virgin UHMWPE. Today, the poor clinical history of Hylamer is largely attributed to its sterilization method, and there has been a resurgence of interest in studying this material (at least among certain research circles).[24] Hylamer fell out of favor in the United States in the late s with the development of highly cross-linked UHMWPE materials, however negative clinical reports from Europe about Hylamer continue to surface in the literature.
Highly cross-linked UHMWPE materials were clinically introduced in and have rapidly become the standard of care for total hip replacements, at least in the United States.[1] These new materials are cross-linked with gamma or electron beam radiation (50&#;105 kGy) and then thermally processed to improve their oxidation resistance.[1] Five-year clinical data, from several centers, are now available demonstrating their superiority relative to conventional UHMWPE for total hip replacement (see arthroplasty).[24] Clinical studies are still underway to investigate the performance of highly cross-linked UHMWPE for knee replacement.[24]
In , manufacturers started incorporating anti-oxidants into UHMWPE for hip and knee arthroplasty bearing surfaces.[1] Vitamin E (a-tocopherol) is the most common anti-oxidant used in radiation-cross-linked UHMWPE for medical applications. The anti-oxidant helps quench free radicals that are introduced during the irradiation process, imparting improved oxidation resistance to the UHMWPE without the need for thermal treatment.[26] Several companies have been selling antioxidant-stabilized joint replacement technologies since , using both synthetic vitamin E as well as hindered phenol-based antioxidants.[27]
Another important medical advancement for UHMWPE in the past decade has been the increase in use of fibers for sutures. Medical-grade fibers for surgical applications are produced by DSM under the "Dyneema Purity" trade name.[28]
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UHMWPE is used in the manufacture of PVC (vinyl) windows and doors, as it can endure the heat required to soften the PVC-based materials and is used as a form/chamber filler for the various PVC shape profiles in order for those materials to be 'bent' or shaped around a template.
UHMWPE is also used in the manufacture of hydraulic seals and bearings. It is best suited for medium mechanical duties in water, oil hydraulics, pneumatics, and unlubricated applications. It has a good abrasion resistance but is better suited to soft mating surfaces.
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Fluoropolymer / HMWPE insulation cathodic protection cable is typically made with dual insulation. It features a primary layer of a fluoropolymer such as ECTFE which is chemically resistant to chlorine, sulfuric acid, and hydrochloric acid. Following the primary layer is an HMWPE insulation layer, which provides pliable strength and allows considerable abuse during installation. The HMWPE jacketing provides mechanical protection as well.[29]
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UHMWPE is used in marine structures for the mooring of ships and floating structures in general. The UHMWPE forms the contact surface between the floating structure and the fixed one. Timber was and is used for this application also. UHMWPE is chosen as facing of fender systems for berthing structures because of the following characteristics:[30]
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Ultra-High Molecular Weight Polyethylene (UHMWPE) is used in biomedical applications due to its high wear-resistance, ductility, and biocompatibility. A great deal of research in recent decades has focused on further improving its mechanical and tribological performances in order to provide durable implants in patients. Several methods, including irradiation, surface modifications, and reinforcements have been employed to improve the tribological and mechanical performance of UHMWPE. The effect of these modifications on tribological and mechanical performance was discussed in this review.
Few review articles [ 2 , 18 , 34 ] have been published to correlate the mechanics and morphology of UHMWPE with its wear and mechanical properties. In one review [ 35 ], the influence of CNT and graphene as reinforcements for UHMWPE is evaluated. In a few review articles [ 3 , 36 ], other advances in UHMWPE for improving wear and mechanical performance are discussed. However, in such articles, many studies on other polymeric materials are considered for supporting the evidence and there is a lack of clarity regarding the optimal values of the effective methods. The objective of this study is to summarize the existing practices for the enhanced tribological and mechanical performance of UHMWPE. The influence of irradiation, reinforcements and surface modifications is briefly discussed and a tabular data is presented for estimating the optimal values or materials. As a conclusion, by using the UHMWPE, mechanical and tribological findings were further improved in order to provide durable implants in patients.
UHMWPE has high wear-resistance, toughness, durability, and biocompatibility. Therefore, it is commonly used as a bearing material with ceramic or metallic counter surfaces in joint arthroplasty [ 8 , 9 ] UHMWPE&#;s significance for achieving outstanding performance in total joint arthroplasties is unquestionable [ 10 , 11 ]. For long-term clinical applications, its tribological performance and lifetime are key aspects [ 12 , 13 ]. However, UHMWPE implants have limited life due to their wear complications. When the UHMWPE is used in the periprosthetic environment it induces osteolysis followed by loosening of the implant. This implant loosening is joined with fatigue causes the aseptic loosening which ultimately causes the implant&#;s failure. [ 14 , 15 , 16 , 17 ]. Many methods such as improving cross-linking [ 18 , 19 , 20 , 21 ], or crystallinity percentage [ 22 , 23 , 24 , 25 ] through irradiation [ 26 ], surface modification through plasma treatment [ 27 , 28 ], or introducing effective textures [ 29 , 30 ], and reinforcements with particles or fibers [ 31 , 32 , 33 ] have been used for enhancing properties of UHMWPE.
Ultra-High Molecular Weight Polyethylene (UHMWPE) is an engineering polymer that varies from high-density polyethylene (HDPE) in terms of average molecular weight and average chain length [ 1 ]. According to the International Standards Organization (ISO), UHMWPE has a molecular weight of at least 1 million g/mole and degree of polymerization of 36,000, while according to the American Society for Testing and Materials (ASTM) it has a molecular weight of greater than 3.1 million g/mole and degree of polymerization of 110,000 [ 2 ]. The properties of UHMWPE are highly dependent on their microstructure rather than molecular mass [ 3 ]. UHMWPE is a semi-crystalline polymer that contains fully crystalline and fully amorphous phases as an interfacial all-trans phase [ 4 , 5 ]. In the crystalline phase, the particular lamellar shape of crystallite is due to the chain folding with the chain axis, which enlarges the chain fold area. In the amorphous phase, the chains are interconnected through occasional crosslinks and random entanglements instead of proper chain folding. The relation between amorphous and crystalline phases are provided by tie molecules. The crystallinity of UHMWPE depends on its volumetric percentage of crystallites [ 6 ]. The properties of UHMWPE are determined by the connections between amorphous and crystalline phases, i.e., tie molecules, crystallinity, the degree of crosslinks and entanglements; and the positions of the crystallites. The average properties of UHMWPE and HDPE are presented in .
Crosslinking of UHMWPE significantly improves wear performance [37,38,39,40], which can be achieved through the use of a silane [41,42], or chemical methods using peroxides [38,43] and irradiation [44,45,46]. The free radicals produced by these methods create the inter-chain covalent bonds, leading to the formation of crosslinking. Moreover, these long-lived free radicals react with oxygen, resulting in a cascade of different reactions [47]. The overall free oxidation mechanism is a chain reaction that involves polymer chain scission and produces different end products such as carboxylic acids and ketones [48]. This oxidation reduces the mechanical performance of UHMWPE [49,50]. The reduction in properties is associated with molecular weight and cross-link density.
Among all methods of crosslinking, irradiation is the most common and effective method for sterilizing and/or crosslinking UHMWPE [45,51,52,53]. However, the irradiation produces free radicals in UHMWPE and the trapped radicals decay slowly in it [52]. The decay of free radicals is important, as it provides information about the overall reaction mechanism in the presence of oxygen. Along with crosslinking, the formation of transvinylene units and chain scission are the common processes in UHMWPE in the result of irradiation. The transvinylene content and crosslink density increased at a higher radiation dose [54]. The irradiated component with higher transvinylene contents showed a higher oxidation rate. The level of oxidation can be assessed through the content of transvinylene units [54,55]. After irradiation, the chain-folded crystallization and recrystallization occur in UHMWPE in the presence of crosslinks. These changes in chain folding kinetics, result in decreased crystallinity [56,57,58]. Since the reduced crystallinity allows oxygen to diffuse deeper into the UHMWPE through the amorphous region. Additionally, the allylic hydrogens at trans-vinylene bonds are easier to extract than the hydrogens at tertiary alkyl carbons. These factors combined with induced strain energies facilitate the oxidation mechanism, probably by reducing the energy barrier for chain scissions reaction at more reactive sites. Fung showed [59] a relation between initial transvinylene content and maximum oxidation. The critical oxidation levels were determined for gamma and e- beam treatments at different radiation doses. It was found that the oxidation levels were highly dependent on radiation dose for both sources. The increase in ketone oxidation index with irradiation dose in terms of loss in mechanical properties is observed. Premnath [60] irradiated UHMWPE specimens in the air with electrons and then these were aged at room temperature for different times to investigate the alterations in molecular rearrangements and micro-molecular structure. The crystallinity of UHMWPE for several radiation doses, and for different time intervals are shown in . The increase in crystallinity with increasing irradiation dose was observed, probably due to the rearrangement of chains at the amorphous domain following the chain scission of molecules in this interface. The plot of absorbed dose in terms of oxidation index and irradiation time is presented in a,b. The oxidation index with dose was almost in a linear manner at all times whereas increment in oxidation index was higher at starting time interval as compared to higher times. The oxidation varies approximately linearly with dose because of the linear variations in free radicals concentration with dose. The decrease in oxidation rate was probably due to the diffusion of free radicals from the crystalline region to the amorphous domain and/or diffusion of oxygen from the amorphous interface to the radical along with crystal stalks; and/or reaction kinetics of different oxidation reactions. Karuppiah [22] investigated the effect of crystallinity on the wear performance of UHMWPE and found that the scratch depth and friction force tended to decrease with increasing the crystallinity. Their study suggested that the wear resistance can be increased with increasing the degree of crystallinity.
Open in a separate windowOpen in a separate windowMultiple factors influenced the crystallinity and oxidative degradation by irradiation [61,62]. The dose and dose rate of irradiation strongly influence the crystallinity and oxidation of UHMWPE [55,63,64,65,66,67,68,69]. A suitable post-irradiation process eliminates free radicals to prevent degradation of UHMWPE over the long period and to promote the stability against oxidation. [18,55,59]. Subjecting UHMWPE to a subsequent below-melt annealing or remelting step reduces radicals and the degree of oxidation. The UHMWPE chains can be fold and the crystalline lamellae can be formed by heating the UHMWPE at high pressure and cooling it above the melting temperature. The resulting crystallinity of UHMWPE is increased after the formation of a crystalline structure [70,71,72].
Other different parameters, such as temperature [73,74], packaging atmosphere and packaging [75,76,77], processing conditions [78], also influence the distribution and the amount of the oxidation products. In general, the irradiation at high temperatures, low dose rates and in the presence of oxygen enhance the oxidation process, which strongly degrades the UHMWPE. Bracco [45] analyzed gamma sterilized prosthetic components to study the effect of implant packaging materials and temperature. Three groups of packaging materials including multilayer polymeric barrier packaging, gas permeable packaging, and a combination of polymeric and metallic foils packaging were used. The concentration of oxygen and alkyl macro-radicals was assessed by FTIR analysis. The ROOH are more important than carbonyl in oxidation because ROOH are the first oxidation products. The hydroperoxides/ketones concentration was low for first two packaging groups, while was very high for third packaging group. The difference in concentration is due to the different oxygen permeability of packaging materials. The rate of decomposition was proportional to local temperature during sterilization. It is concluded that the negligence in selection of irradiation parameters can cause the unpredictable oxidation and degradation of UHMWPE.
With aging, the reaction of trapped free radicals with oxygen enhances due to the deep diffusion of oxygen and causes more oxidation. The active free radicals in UHMWPE undergo the intramolecular and intermolecular decompositions resulting in the time-dependent chain scission. This process gradually reduces the crosslinking in the aged UHMWPE. With this, the tie chain scission process allows growth to occur and, further crystal perfection thus the aged UHMWPE has higher crystallinity. The oxidation index increases due to the thickening of the oxidized surface layer with an increase in aging time. In addition, the irradiation of aged samples showed low crosslinking as well as higher oxidation [79,80,81,82,83,84]. This shows crosslinking and oxidation both are highly dependent on aging. The variations in the level of cross-linking, crystallinity, and oxidation during aging cause the change in mechanical properties. The brittleness in the aged UHMWPE liners enables the production of cracks under sliding shear and tensile stress states and eventually, it can enhance the wear of UHMWPE. Lee [85] compared the wear performance of un-irradiated and gamma-irradiated UHMWPE specimens and studied the effect of aging. The wear was measured in terms of weight loss. The wear of gamma-irradiated specimens was lower than un-irradiated specimens and it was increased with aging time. However, the oxidation index of un-irradiated specimens was lower than irradiated specimens. To investigate the influence of oxidation on wear the specimens were artificially aged for 2 to 8 days and tested at knee simulator under sliding conditions. Bell [86] investigated the influence artificially induced subsurface on the wear of UHMWPE. shows the change in wear track volume for untreated and aged (oxidized) specimens. The large volumetric change at the initial stage for all specimens is attributed to the creep of the UHMWPE [87].
Open in a separate windowChang [88] investigated the tribological performance of aged UHMWPE specimens and confirmed the obvious influence of aging conditions on wear and mechanical performance. The coefficient of friction of aged UHMWPE specimens for different aging periods is shown in . The coefficient of friction (COF) was increased up to 65.96% for 720 h aging time and 80 °C aging temperature. It was found that the tribological and mechanical degradation was attributed to the damage in the molecular structure of UHMWPE.
Open in a separate windowDelamination is the catastrophic type of wear in UHMWPE bearing components [3,86]. The diffusion of free radicals out to polymer matrix or into the polymer as a result of irradiation can lead to the development of a subsurface oxidized band. This subsurface oxidation region can lead to delamination and in many cases, failure occurs from subsurface crack initiation and propagation [4]. Bell [86] investigation on retrieved total knee implants has shown that oxidation of UHMWPE can be influenced by stresses induced during everyday activities or by post-irradiation associated with the subsurface band. This study showed that the delamination occurred only in the presence of the subsurface oxidized band and propagated through this band. In wear test, an increase in oxidation produced increased surface wear without delamination. Similarly, in fatigue and tensile tests, there was a reduction in the fatigue resistance and in ultimate tensile strength of oxidized UHMWPE specimens. Oxidation increased the fatigue crack growth rate. It was also observed that the resistance to oxidation was different in different grades of UHMWPE. The wear mechanism of UHMWPE can be better understood by treating it anisotropic material [2,89]. The strength of UHMWPE depends on the direction in which load is applied. So a wear mechanism can be better assessed by multidimensional wear tests [90]. Wang [91] performed hip-joint simulator experiments on both linear and crosslinked UHMWPE to investigate the effect of molecular chain orientation on the wear surfaces and within wear debris. The UHMWPE specimens sterilized by ethylene oxide gas in the air and by gamma irradiation in nitrogen were used for tests. Crosslinking was not achieved by ethylene oxide gas sterilization. Results obtained from the hip simulator test indicated that the wear resistance of UHMWPE can be significantly improved by radiation-induced cross-linking. The strength of bearing surfaces in multidirectional sliding experiments was lower than the bearing surfaces in uniaxial tensile tests. The phenomenon of strain-softening in UHMWPE bearing surfaces is also due to the structural anisotropy. This study recommends maintaining the homogenous and isotropic molecular structure of UHMWPE bearing surfaces for achieving high résistance to strain to harden. A large number of wear models have been developed to explain the morphology of wear debris [84,92,93]. Wang [94] proposed a theoretical model for UHMWPE based on the concept of frictional work under multi-directional lubricated sliding conditions. Based on the theory, the wear volume loss per unit load and sliding distance was related to the cross-link density, COF, and the maximum shear angle. The COF and wear volume rate of UHMWPE were decreased with increasing the cup/head clearance. The linear increase in wear volume loss was observed with an increased COF. The wear rate was shown to increase linearly with increasing the COF. The wear rate can be decreased by irradiation as indicated by results in hip simulator. The effect of radiation dose on crosslinking and wear factor is shown in . The linear increase in wear rate was observed with increasing the molecular weight into crosslinks.
Open in a separate windowThe mechanical degradation of UHMWPE is very important for high stressed bearing components which may cause large deformations or fatigue damage such as or delamination or pitting. The multiaxial deformation of UHMWPE is more important than the deformation under uniaxial loading conditions for clinical relevance. After irradiation UHMWPE deforms a spatially non-uniform towards a more brittle (less ductile) behavior. Edidin [95] investigated the mechanisms of mechanical degradation of UHMWPE, including both the linear and non-linear responses, as a function of aging. An increase in elastic modulus and a decrease in work to failure, ultimate displacement and ultimate load as a result of accelerated and natural aging were demonstrated in this study.
The influence of irradiation on the level of crystallinity, tribological performance and mechanical performance reported in the literature is presented in . The parameters and their values in percentage are presented as compared to pure UHMWPE.
All results reported in show that the optimal value for radiation dose is in the range of 25&#;50 kGy in terms of less oxidation and high tribological properties. The variation in optimal value suggests that the selection of radiation dose depends upon the several conditions discussed in previous sections. So careful selection of the amount of radiation dose is mandatory. The significant difference in gel content percentage and crosslink density percentage can be observed for the mentioned results. The increase in the crystallinity percentage is in the range of 5 to 26%. The values of the oxidation index and transvinylene index are increased from 10&#;125% and 2&#;12% respectively as compared to pure UHMWPE. Several mechanical properties such as toughness, elongation at break, impact strength, ultimate displacement, ultimate load, and ultimate displacement are decreased, while hardness and tensile strength are increased or maintained.
It is well established that irradiation results in the mechanical degradation of UHMWPE [59,66,76,98,99]. Therefore, it needs to focus on methods to enhance crosslinking by maintaining mechanical properties. Muratoglu [100] irradiated UHMWPE in the air at high temperature by a high dose-rate electron beam with adiabatic heating and then melted. The wear resistance was improved by this method with maintaining the mechanical performance of UHMWPE for hip implants because of the absence of free radicals and as a result of high oxidation resistance. The three years follow-up showed an equal decrease in wear rate for argon sterilized and air sterilized UHMWPE due to the initial creep after implantation and thereafter wear rate decreased steadily slow. The argon sterilized UHMWPE liners showed more stable due to the less wear rate as compared to air-sterilized liners after nine years follow-up. Despite their different patterns and amounts of wear, no difference in osteolytic tissue reaction is demonstrated [101].
Sterilizing UHMWPE in the oxygen-depleted atmospheres, like vacuum packaging or inert gas, can reduce the degree of oxidative degradation [47,62]. Faris [102] observed less wear in inert-sterilized molded liners than air-sterilized extruded liners after a 6 years follow-up in 150 patients. He concluded that the molded UHMWPE is more resistant to wear than the extruded UHMWPE [103]. Goosen [101] observed a difference in wear rate between the AIR and ARGON liners based on multivariate analysis during a follow-up of 3&#;12 years. There was no significant difference in wear rate for three years after implantation. Thereafter, the ARGON liner showed a decreased wear rate tan AIR liner.
Bracco [45] postulated that unsaturated additives can be added into UHMWPE to enhance the cross-linking to increase the reactions involving terminal double bonds. UHMWPE specimens soaked in ethylene, methyl-acetylene, and 1,7-octadiene respectively, were irradiated using different doses of an electron beam. Gel fraction results showed that all irradiated samples are crosslinked, and 1,7-octadiene exhibits the most efficient additive for enhancing crosslinking. The mechanical results revealed a significant decrease in ultimate stress and elongation at break with high doses of an electron beam in multiple passages.
Vitamin E has been considered as an important antioxidant to reduce the oxidation and wear degradation of UHMWPE components [104,105]. Vitamin E reacts with trapped free radicals into the UHMWPE, impending them to react with oxygen. Thus, it prevents oxidative degradation of UHMWPE and increases its resistance to wear and fatigue [72,106,107]. Costa [99] investigated the efficiency of vitamin E for stabilizing UHMWPE. UHMWPE powder was blended with pharmaceutical grade vitamin E and consolidated into large slabs. The formation of a stable-tocopheryl radical due to the interaction between macro-alkyl radicals and vitamin E results in a decrease of macro-alkyl radicals. The reactions between macro-alkyl radicals with oxygen can be inhibited due to the decrease in alkyl radicals (which react with vitamin E) and to the vitamin E reaction with peroxy macroradical. The data is shown in . Moreover, the crosslinking effectiveness is reduced due to the possibility of the reaction between macro-alkyl radicals with vinyl double bonds, or vitamin E.
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