Ultra-High-Molecular-Weight-Polyethylene (UHMWPE) as a Promising Polymer Material for Biomedical Applications: A Concise Review

26 Oct.,2022


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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 .

2. Irradiation

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.

2.1. Crosslinking and Crystallinity

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.

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Multiple 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.

2.2. Aging

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].

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Chang [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.

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2.3. Wear and Mechanical Degradation Mechanism

Delamination 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.

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The 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.

Table 2

Ref.Radiation SourceRadiation Dose/Optimum ValueCrystallinity/CrosslinkingTribological ResultsMechanical Results[96]Gamma50–255 kGy/50 kGy Impact Toughness-67%
Tensile Toughness-64%
Elongation-74%[91]Gamma Gel content->650%Wear rate-35% [60]Electron25–200 kGy/50 kGyCrystallinity-110% Oxidation Index-110%[45]Electron25–100 kGy/25 kGybranching in 1,7-octadiene-570% Ultimate Tensile Stress-111%
Elongation at break-89.25%[85]Gamma25 kGyCross-linking (%)-228%
crystallinity-105%Wear loss-150%Oxidation index-225%[87]Gamma Gas plasma25 kGy Tension fatigue-Crack inception
Gamma air-88%
Gamm inert-86%
Gas Plasma-99%[5]60Co35 kGyCrystallinity-119% [95]Gamma25–40 kGyCrystallinity (%)->116% Elastic modulus-273%
Peak Load-90%
Ultimate load-41%[55]Gamma irradiated in N2 and air25 kGy, 50 kGy, 100 kGy/100 kGy at 2.5 k Gy/h dose rateGel content (%)-164%
Extract fraction (%)-27%
Swell ratio-24%Relative wear rate-140% at 50 kGyOxidation index-200%
Trans-vinylene index-112%
At 25 k Gy/h the values are lower[59]Electron-beam50, 75 &100 kGy/50 kGyCrosslink density (dm3/mole)-116% Tensile strength (MPa)-103%
Transvinylene index-102%[97]Gamma35 & 70 kGy/70 kGy Tensile modulus-86.6%
Tensile strength-95.4%
Elongation at break-58.1%[39]gamma33-500 kGy/14.5 MradCrystallinity %-126.5%
Crosslink density-<747%Wear rate->6%Impact of strength-50%
Tensile strength-87%
Elongation at break (%)-61%Open in a separate window

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.

2.4. Methods for Minimizing Degradation

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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