Modeling the oxidative degradation of ultra‐high‐molecular‐weight polyethylene

Understanding the sequence of reactions that occur in ultra‐high‐molecular‐weight polyethylene (UHMWPE) following ⁶⁰Co γ irradiation has been the focus of numerous experimental studies. In the study reported here, we have incorporated recent experimental findings into a mathematical model for UHMWPE oxidation. Simulation results for shelf aging and accelerated aging are presented. It is shown that very reasonable simulations of shelf‐aging and accelerated‐aging data can be obtained. It is also shown that simulations of shelf aging in reduced oxygen environments predict that the subsurface peaks of ketones will be shifted to the exterior surface. In vivo aging can be simulated if we assume that the oxygen level in the synovial fluid is about one‐eighth that of atmospheric levels. Some reduced irradiation doses are predicted to significantly reduce the ketone formation for shelf‐aging periods of up to 10 years. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 814–826, 2003     

Oxidation resistance and abrasive wear resistance of vitamin E stabilized radiation crosslinked ultra‐high molecular weight polyethylene

The effect of gamma radiation on the oxidation and wear resistance of ultra‐high molecular weight polyethylene (UHMWPE) has been extensively studied since these properties are critical for the longevity of UHMWPE components of total joint replacement prostheses. While gamma radiation increases wear resistance of UHMWPE, the free radical generated in the lamellar regions by radiation must be stabilized before oxidative degradation occurs as the polymer ages. Initially, post‐radiation melting conducted to quench free radicals but this treatment also decreases its mechanical properties. Recently, it has been replaced by incorporation of Vitamin E into UHMWPE to combat oxidative degradation. In this study, we assessed wear resistance of Vitamin E stabilized UHMWPE under abrasive wear conditions and oxidation resistance by shelf‐aging irradiated components for 2 years. Equilibrium swelling experiments showed that Vitamin E decreased crosslink density, which affected wear resistance, but oxidation resistance was better preserved with increasing concentration of Vitamin E. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44125.     

Photo‐oxidation of polymers: Validation of oxygen uptake and relationship with extent of hydroperoxidation

In this piece of work we focused our attention on the peroxidation step and alongside considered hydroperoxides as probes for the overall oxidative process. This technique of oxygen uptake actually monitors the amount of oxygen consumed during polymer degradation. Our present work aimed to investigate this technique to evaluate the oxygen uptake during in situ photoirradiation, under controlled atmosphere. Our experimental results clearly elucidate that the oxygen consumption data accounts for a very early stage of aging during the photo‐oxidation of polymers and provides us with an accurate and sensitive diagnosis about the formation of hydroperoxides. A straight‐line relationship was exhibited under our experimental conditions while observing a relation between oxygen pressure drop and hydroperoxide content in the polymer. This correlation was dependent upon the nature of polymer and of course on the aging conditions (temperature, irradiation, oxidative atmosphere). The impact of environmental atmosphere on aging was particularly kept in mind. To conclude, we emphasized that oxygen uptake is a promisingly powerful tool to identify the impact of the overall environmental parameters on the polymer photoaging. An important implication was on the understanding of atmospheric factors (including pollutants such as O₃, NO_x, etc.), which is usually given minor importance, on the degradation of polymer upon outdoor weathering. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci, 2006     

FREE RADICAL ELIMINATION IN IRRADIATED UHMWPE THROUGH CRYSTAL MOBILITY IN PHASE TRANSITION TO THE HEXAGONAL PHASE

Ultra-high molecular weight polyethylene (UHMWPE) is radiation cross-linked to decrease wear in total joint applications. Irradiation decreases the strength of UHMWPE and introduces residual free radicals, which can cause oxidation in the long-term. We advanced a method eliminating the free radicals without a reduction in strength. UHMWPE exhibits a hexagonal phase at high pressure and temperature, where chain mobility in the crystalline phase is increased, leading to the formation of extended chain crystals. We hypothesized that the increased chain mobility during transformation from the orthorhombic to hexagonal phase could be used to eliminate the residual free radicals in irradiated UHMWPE. We eliminated the free radicals in 25-, 65- and 100-kGy irradiated UHMWPEs and these materials did not show oxidation after accelerated aging. The ultimate tensile strength and work-to-failure of 25 and 65-kGy irradiated UHMWPEs were improved significantly while that of 100-kGy irradiated UHMWPE was lower compared to irradiated UHMWPE melted at ambient pressure.     

Effect of gamma ray irradiation on processability and properties of ultra high molecular weight polyethylene

Ultra high molecular weight polyethylene (UHMWPE) has been widely used in many fields due to its outstanding properties. However, it is virtually impossible to be processed by the conventional method due to its high molecular weight and very tight chain entanglement. To solve this problem, a new method was proposed in this article. Gamma ray irradiation was adopted to cause the oxidation degradation of UHMWPE. The degraded products which generated in situ and dispersed in UHMWPE evenly were utilized as self‐lubricant and heat transfer intermediary. These low molecular weight fractions thus could improve the processability of UHMWPE. The effects of irradiation dose on the structure and properties of UHMWPE were studied by fourier transform infrared (FTIR) spectroscopy, gel content measurement, wide angle x‐ray diffraction (WAXD), Haake torque rheometer, mechanical properties measurements and sliding wear tests. The experimental results showed that gamma ray irradiation caused oxidation degradation of UHMWPE. Under appropriate irradiation condition, the processability of UHMWPE could be improved substantially while most of its excellent properties could be kept. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Innovative technologies in the control of lipid oxidation

Transition metal promoted oxidative degradation reactions impact quality, shelf‐life, and nutritional content of many packaged foods. When trace metals are present in packaged foods, they can initiate degradation of nutritional compounds such as unsaturated fatty acids, carotenoids, antioxidants, phytosterols, and many vitamins. These reactions occur at metal concentrations naturally occurring in foods (often in the low parts per billion range) therefore complete metal removal is not a practical solution to inhibit these reactions. Chelators such as EDTA can be added to inhibit metal‐promoted oxidation, however there is significant consumer and industry demand to eliminate EDTA from product formulations. Other natural chelators such as citric acid are ineffective in many foods and in some cases can actually increase oxidation rates by increasing metal solubility. An alternate approached to control transition metal reactivity is to utilize active packaging technologies. However, current approaches to antioxidant active packaging can impact packaging film mechanical properties and often exhibit low antioxidant activity. This review article surveys and critically reviews advances in the control of lipid oxidation, paying particular attention to novel advances in both food product formulation (e. g. additives, food microstructure) as well as food packaging. We introduce a new concept of active packaging in which metal ion chelation by non‐migratory active packaging materials may enable removal of synthetic food additives from product formulations while maintaining product quality and shelf‐life.     

High temperature melted,radiation cross-linked,vitamin E stabilized oxidation resistant UHMWPE with low wear and high impact strength

In a previous communication we showed improvement in the wear resistance and toughness of cross-linked ultrahigh molecular weight polyethylene (UHMWPE) for total joint implants by radiation cross-linking after high temperature melting (HTM). In this study, we hypothesized that introduction of vitamin E into UHMWPE before high temperature melting could improve the oxidative stability of these UHMWPEs with low wear and high toughness. Vitamin E was blended with UHMWPE powder at concentrations of 0.1 and 0.2 wt% and consolidated, followed by melting at 300 and 320 °C for 5 h, and subsequent irradiation with electron beam to 150 kGy. These vitamin E/UHMWPE blends showed improved tensile and impact toughness and good wear resistance in comparison with the radiation cross-linked vitamin E/UHMWPE blends. Aggressive accelerated aging with or without pro-oxidant lipids showed that vitamin E-blended, high temperature melted and subsequently irradiated UHMWPE had good oxidation resistance.     

Multi-walled carbon nanotubes acting as free radical scavengers in gamma-irradiated ultrahigh molecular weight polyethylene composites

Multi-walled carbon nanotubes (MWCNTs) were incorporated in ultrahigh molecular weight polyethylene (UHMWPE), which is a polymer used in industrial and orthopedic applications. The composites were prepared by ball milling and thermo-compression processes at concentrations up to 3 wt.% and subsequently gamma irradiated at 90 kGy. Electrical conductivity measurements showed a low percolation threshold of 0.5 wt.%. Electron spin resonance detection of the radiation-induced radicals proved the radical scavenger behavior of MWCNTs: when the nanotube concentration increased, the number of radicals generated by the gamma irradiation process decreased. Allyl radicals seem to be the radicals most affected by the presence of nanotubes in this polymeric matrix. Fourier transformed infrared spectroscopy measurements and an accelerated ageing protocol were performed to ascertain the influence of the irradiation on the oxidation index. The results pointed to the positive contribution of the MWCNTs in increasing the oxidative stability of the composite compared to pure UHMWPE. Crosslinking density induced by gamma irradiation was obtained by swelling measurements. The findings showed that, despite the radical scavenger performance, MWCNTs are capable of maintaining the efficiency of the crosslinking density, unlike the other antioxidants, which inhibit radiation crosslinking.     

Effects of calcium stearate addition of ultrahigh molecular weight polyethylene in direct compression molding

The effects of calcium stearate addition in molding of ultrahigh molecular weight polyethylene (UHMWPE) were investigated by tensile testing, scanning electron microscope (SEM), Fourier transform infrared (FT‐IR) spectroscopy, and elemental analysis. Four types of UHMWPE specimens with varying contents of calcium stearate (<5, 50, 100, and 1000 ppm) were used in this study. SEM observation revealed that calcium stearate added specimens have smoother and more homogeneous microstructures. After accelerated aging, subsurface oxidative degeneration was observed in all specimens; however, calcium stearate added specimens had less oxidative degeneration in comparison with specimens without additives. Specimens showed better mechanical properties with increasing content of calcium stearate. Though all specimens aggravated their mechanical properties due to oxidation after accelerated aging, the specimens of 100 ppm of calcium stearate showed better properties at 3.7 MPa larger yield strength and four times larger value of elongation at fracture than the specimens without additives. These results indicate that calcium stearate addition produces dense packing of UHMWPE particles, which brings about stronger fusion among the particles and fewer structural defects, and results in better mechanical properties and better resistance to oxidative degeneration. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 1602–1609, 2003     

Catalytic action of metallic salts in autoxidation and polymerization. VI. The inhibitive effects of transition-metal N,N-diethyldiselenocarbamates on the thermal oxidative degradation of isotactic polypropylene

Transition-metal (Zn, Ni, Pd, Cu, Cr, Co) N,N-diethyldiselenocarbamates were prepared, and the inhibitive effects of these compounds on the thermal oxidative degradation of isotactic polypropylene, both in the presence and absence of copper stearate as oxidation accelerator, were examined by conventional oxygen uptake. In both cases, all metal selenocarbamates showed a pronounced inhibitive effect on the degradation of the polymer, especially Zn and Ni selenocarbamates. The inhibitive action of these metal selenocarbamates was discussed from the viewpoint of viscosity change and carbonyl and hydroperoxide contents.     

Gamma-radiation stabilization of polypropylene

Especially synthesized compounds, together with conventional antioxi-dants, were evaluated as radiation stabilizers of isotactic polypropylene. Electron spin resonance (ESR) determinations of free radical populations in stabilized and unstabilized samples were carried out after irradiation and at periods of up to 460 h. The same samples were mechanically tested and a correlation was found to exist between the concentration of trapped peroxy radicals and the radiation deterioration in the polymer. Post-irradiation effects were evaluated using accelerated aging at 70°C and carbonyl index determinations at periods of up to 110 days indicated that some of the stabilizers examined are efficient inhibitors of post-irradiation oxidation. The results are discussed in the light of the free radical mechanism of the radiation-induced auto-oxidative degradation of polymers.     

Chemiluminescence studies of the degradation and stabilization of polymers

In order to predict the safe service life of a polymer from its rate of oxidation, a detailed understanding of degradation and stabilization reactions in the induction period is required. The mechanism by which an oxidizing polymer emits weak visible light (chemiluminescence) is reviewed and the use of the technique to study the early stages of the oxidation of nylon 66 and polypropylene is considered. Steady-state chemiluminescence experiments are described to measure the activation energy of initiation of nylon 66 oxidation and to study the mechanism of the dark reaction of a hindered amine light stabilizer (and its nitroxyl radical) with polypropylene hydroperoxide. Non-stationary experiments, in which the steady state is perturbed by UV irradiation and gas switching, demonstrate the reactions of long lived alkyl radicals in the induction period. The observation of stress-induced chemiluminescence from nylon 66 shows the effect of even a low fiber load is to greatly increase the rate of oxidation.     

Effect of long‐term natural aging on the thermal,mechanical, and viscoelastic behavior of biomedical grade of ultra high molecular weight polyethylene

In the total joint prostheses, Ultra High Molecular Weight Polyethylene (UHMWPE) may undergo an oxidative degradation in the long term. The overall properties of UHMWPE are expected to be altered due to the oxidative degradation. The goal of this study is to investigate the effects of natural aging up to 6 years in air on the thermal, mechanical, and viscoelastic properties of UHMWPE that was used in total joint replacement. The changes in UHMWPE properties due to aging are determined using Differential Scanning Calorimetry (DSC), uniaxial tensile tests, and Dynamic Mechanical Analysis (DMA). The DSC results show that the lamellar thickness and degree of crystallinity of UHMWPE specimens increase by 38% and 12% due to aging. A small shoulder region in the DSC thermograms is remarked for aged specimens, which is an indication of formation of new crystalline forms within their amorphous region. The tensile properties of aged and nonaged UHMWPE specimens show a significant decrease in the elastic modulus, yield, fracture stresses, and strain at break due to aging. The DM testing results indicate that the storage modulus and creep resistance of UHMWPE specimens decrease significantly due to aging. Also, it is remarked that the α relaxation peak for aged UHMWPE specimens occurs at lower temperature compared to nonaged ones. The significant reduction in the strength and creep resistance of UHMWPE specimens due to aging would affect the long‐term clinical performance of the total joint replacement and should be taken into consideration during artificial joint design. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Thermo‐oxidative degradation behavior of recycled polypropylene

This study has been carried out to mimic the thermo‐oxidative degradation of polypropylene (co‐PP) during service life and recycling. Injection molded specimens were heat aged at 130°C for different times up to maximum of 300 h to simulate the degradation of co‐PP during the service life. These aged specimens were mixed with stabilizers in internal mixer and again heat aged up to 300 h. A small increase in melt flow rate (MFR) value was observed for aged co‐PP but it showed large increase after recycling. The presence of carbonyl peak at 1713 cm⁻¹ confirmed the oxidation of co‐PP during aging and it increases with aging time. Carbonyl index (CI) is increased in recycled sample with aging, whereas oxidation induction time (OIT) decreased. The stabilizers used during reprocessing are quite effective in controlling the thermo‐oxidative degradation of the polymer during processing and aging. The thermogravimetric analysis shows that the onset of degradation temperature starts at low temperature for recycled sample as compared to virgin co‐PP. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Electron spin resonance spectroscopy for determination of the oxidative stability of food lipids

Evaluation of the oxidative stability of food lipids based on the tendency of formation of radicals is shown to be possible using electron spin resonance (ESR) spectroscopy and the spin-trapping technique. Induction time can be determined for mildly accelerated conditions (50°C for lipid fraction from mayonnaise enriched with fish oil), and the length of the induction time decreases during storage and γ-tocopherol depletion. The protection by ethylenediaminetetraacetic acid against initiation of lipid oxidation is also detected in the new assay. For more oxidatively stable lipids (butter, rapeseed oil, dairy spread) the mildly accelerated conditions can be used in the assay, provided that difference in signal height for fixed times replaces determination of induction time. ESR spin trapping provides a sensitive method for evaluating the oxidative stability of food lipids. Detection of radicals in the lipid as an early event in oxidation allows mild conditions to be used, and future experiments should also include sensory evaluation in relation to determination of practical shelf life.     

Effect of simulated low earth orbit radiation on polyimides (UV degradation study)

UV degradation of polyimide films in air and vacuum were studied using UV-visible, ESR, FTIR, and XPS spectroscopies. The UV-visible spectra of polyimide films showed a blue shift in the absorption compared to Kapton. This behavior was attributed to the presence of bulky groups and kinks along the polymer chains which disrupt the formation of a charge-transfer complex. The UV-visible spectra showed also that UV irradiation of polyimides result extensively in surface degradation, leaving the bulk of the polymer intact. ESR spectra of polyimides irradiated in vacuum revealed the formation of stable carbon-centered radicals which give a singlet ESR spectrum, while polyimides irradiated in air produced an asymmetric signal shifted to a lower magnetic field, with a higher g value and line width. This signal was attributed to oxygen-centered radicals of peroxy and/or alkoxy type. The rate of radical formation in air was twofold higher than for vacuum irradiation and reached a plateau after a short time. This suggests a continuous depletion of radicals on the surface via an ablative degradation process. FTIR, XPS, and weight loss studies supported this postulate. An XPS study of the surface indicated a substantial increase in the surface oxidation after irradiation in air. The sharp increase in the C? O binding energy peak relative to the C? C peak was believed to be associated with an aromatic ring-opening reaction. © 1995 John Wiley & Sons, Inc.     

Weathering of low‐density polyethylene grafted with itaconic acid in laboratory tests

Polyethylene grafted with itaconic acid was subjected to weathering under laboratory accelerated conditions. The course of the photo‐oxidative degradation process of that material was studied by FTIR spectroscopy both through quantitative measurements of changes in absorbance values at selected wave numbers and through measurements of surface area values for absorption bands which were separated by means of deconvolution. The use of both those procedures of quantitative determinations resulted in a general conclusion that the oxidation process was initiated from the very first moment of irradiation, and it produced ketones, acids, esters (intramolecular and of acetate type), peracids, peresters, hydroperoxides, and alcohols. The molecular weight values and gel number values, which were established as well, pointed out that oxidation was accompanied by cracking of polymer macromolecules, and also by polymer crosslinking to a limited degree. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

The photooxidative gelation of cis-1,4- polybutadiene in solution

Irradiation of dilute solution of cis-1,4-polybutadiene in carbon tetrachloride with UV light in the presence of air causes fast formation of white precipitate—insoluble gel. It has been shown that carbon tetrachloride was effective photosensitizer for oxidation of cis-1,4-polybutadiene. Separated sol and gel fractions were analysed by infrared spectroscopy for better understanding of gelation process and structure of the gel. Three stages were detected in the process of oxidative photogelation of cis-1,4-polybutadiene in carbon tetrachloride solution: pre-gelation(sol-stage), gelation (sol/gel-stage) and post-gelation (gel-stage). In the first stage intensive photooxidative reactions between cis-1,4-polybutadiene, carbon tetrachloride and oxygen take place, giving products with high content of hydroperoxide and bounded chlorine. When hydroperoxide and chlorine content reached critical value, precipitation-gelation takes place. It is proposed sequence of free radical reactions which involves: photolysis of carbon tetrachloride to free radicals, addition of solvent radicals to the double bonds of rubber followed by combining of resulting radicals with oxigen to chlorinated polymeric peroxy radicals. Initially formed gel is peroxidic in nature, which photolyses to the more stabile ether gel by prolonged irradiation.     

Effect of Quasi‐nanometer zirconium carbide on the physical characterization of zirconium carbide/polyurethane composite films irradiated under ultraviolet light

We used quasi‐nanometer zirconium carbide (ZrC) and a polyurethane (PU) resin under roller pressure to form a composite film and found that the tensile strength at break, elongation at break, and modulus gradually decreased with increasing ultraviolet (UV)‐irradiation time for films of both PU and the PU/ZrC composite. However, this phenomenon was significantly higher for the PU film than for the ZrC/PU composite film. The construction of the PU film changed after UV irradiation, but that of the PU/ZrC composite film was almost unchanged. The degradation of PU molecules occurred in the absence of ZrC particles after irradiation with UV light but almost did not occur in the presence of ZrC particles. This was confirmed with Fourier transform infrared spectroscopy and gel permeation chromatography analyses. It was suggested that polymer radicals which formed through the photooxidation of UV irradiation and free radicals which formed through the photoreduction of nanometer ZrC/UV irradiation interacted to form a dead polymer to stop the degradation; simultaneously, the chemical bonding between polymer molecules could be re‐formed from free radicals created by photooxidation and photoreduction and thus reduce the mobility of PU molecules, thereby raising the glass‐transition and melting temperatures of the soft segment. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 4842–4849, 2006     

The oxidative inducation test applied to medical PVC and other polymers

We have examined the applicability of this simple and effective test to polymer systems widely used in the medical industry. First, it was found that not every polymer examined exhibited a distinct onset of autocatalytic oxidation detectable by DSC. However, for cases where distinct onsets are found, powerful insights can be obtained. These included activation energy of the degradation, thermal oxidative shelf life prediction, and correlation, with product performances. Actual examples are presented to illustrate the utility of the test.