Homogenization in supercritical carbon dioxide enhances the diffusion of vitamin E in ultrahigh‐molecular‐weight polyethylene

Vitamin E stabilization of radiation‐crosslinked ultrahigh‐molecular‐weight polyethylene (UHMWPE) joint implants was successfully introduced to improve long‐term oxidation resistance. Current clinically available vitamin E stabilized UHMWPE implants were prepared by the postirradiation diffusion of vitamin E into 100‐kGy‐irradiated UHMWPE by a two‐step process, which included doping in pure vitamin E at an elevated temperature below the melting point followed by an annealing step at an elevated temperature in inert gas to homogenize the antioxidant throughout components of desired thickness. We hypothesized that the diffusion of vitamin E could be enhanced with supercritical carbon dioxide (SC‐CO₂) during homogenization without an increase in the surface vitamin E concentration, which would thus result in faster homogenization. Our hypothesis tested positive; crosslinked UHMWPE doped with vitamin E at 120°C and homogenized in SC‐CO₂ at 10–12 MPa had a greater penetration of vitamin E than those homogenized in inert gas. We attributed the faster diffusion of vitamin E in irradiated UHMWPE in SC‐CO₂ to the dissolution of vitamin E in the supercritical fluid and a rate of diffusion that was closer to that of the supercritical fluid in the polymer. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

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     

Influence of two‐stage drawing conditions on ultradrawing behavior of gel films of ultrahigh‐molecular‐weight polyethylene and low‐molecular‐weight polyethylene blends

The influence of two‐stage drawing conditions on the ultradrawing behavior of the gel films of ultrahigh‐molecular‐weight polyethylene/low‐molecular‐weight polyethylene blends is reported in this article. The critical draw ratios (λ_c) of the gel films prepared near their critical concentrations were found to depend significantly on the draw ratio attained in the first drawing stage (D_1r) and on the temperature utilized in the second drawing stage (T_sec). After drawing the gel films to a fixed draw ratio in the first drawing stage, each two‐stage drawn gel film was made to exhibit a maximum λ_c (λ_cmax) by drawing the drawn gel film at its corresponding optimum T_sec. In addition, the optimum T_sec was found to increase significantly with the D_1r value of the drawn gel films. It is worth noting, on the other hand, that the λ_cmax of two‐stage drawn gel films increased consistently with an increasing D_1r until its value reached an optimum value of 160. These results clearly suggest that, as T_sec and D_1r are increased to their optimum values, the λ_cmax of the two‐stage drawn gel films can be improved further so as to be higher than those of the corresponding one‐stage drawn gel films. These interesting phenomena were investigated in terms of reduced viscosities of the solutions and by an analysis of the thermal, birefringence, and tensile properties of the drawn gel films. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 79: 1890–1901, 2001     

Effect of polyethylene glycol on the performance of ultrahigh‐molecular‐weight polyethylene membranes

Porous, flat membranes of ultrahigh‐molecular‐weight polyethylene (UHMWPE) were prepared by thermally induced phase separation, with mineral oil as a diluent and poly(ethylene glycol) with a weight‐average molecular weight of 20,000 (PEG20000) as an additive. Through the control of the rheological behavior, crystallite size, and pore structure, the influential factors, including the diluent, poly(ethylene glycol) (PEG) content, and cooling rate, were investigated. The results suggested that PEG could decrease the viscosity of UHMWPE/diluent apparently. The crystal density decreased when mineral oil was added, which made the melting point and crystallinity of UHMWPE lower. The crystallization rate and crystallinity also increased with the addition of PEG. However, the addition of excess PEG restrained crystal growth. PEG20000 in membranes could be extracted absolutely through the soaking of the membranes with fresh water for 7 days. With increasing PEG content, both porosity and pure water flux first increased and then decreased, reaching a maximum at a PEG mass fraction of 10%. The cooling rate had a direct effect the crystal structure. A slow cooling rate was good for crystal growth and diluent integration. Therefore, the pure water flux increased along with the temperature of the cooling medium, whereas porosity first increased and then decreased, reaching a maximum at 40°C. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Effect of the ultradrawing behavior of gel films of ultrahigh‐molecular‐weight polyethylene and low‐molecular‐weight polyethylene blends on their physical properties

This study examined the effect of the ultradrawing behavior of gel film specimens of ultrahigh‐molecular‐weight polyethylene (UHMWPE) and UHMWPE/low‐molecular‐weight polyethylene (LMWPE) blends on their physical properties. The concentration of a gel film approximated its critical concentration at a fixed drawing temperature; its achievable draw ratio was higher than that of other blend specimens with various concentrations. Noticeably, when about 5 wt % LMWPE was added to a UHMWPE/LMWPE gel film specimen, the achievable draw ratio of the gel film increased, and this contributed to an apparent promoting effect on its anticreeping properties and thermal stability. Therefore, when UL_B?0.9 was drawn to a draw ratio of 300, the anticreeping behavior was improved to less than 0.026%/day. Moreover, with respect to the thermal stability, when the same specimen was drawn to a draw ratio of 300, the retention capability of its storage modulus could resist a high temperature of 150°C, which was obviously much higher than the temperature of an undrawn gel film specimen (70°C). To study these interesting behaviors further, this study systematically investigated the gel solution viscosities, anticreeping properties, dynamic mechanical properties, thermal properties, molecular orientations, and mechanical properties of undrawn and drawn UHMWPE/LMWPE gel film specimens. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2008     

Highly crosslinked poly(styrene‐co‐divinylbenzene) microspheres prepared by precipitation polymerization: Effects of the polymerization parameters on the characteristics of the particles

Highly crosslinked poly(styrene‐co‐divinylbenzene) microspheres with a 1.0–2.5‐μm diameter were prepared by precipitation polymerization in neat acetonitrile. The effects of various polymerization parameters such as the monomer and initiator concentration, comonomer composition, and cosolvents on the properties of the resulting particles were studied. The particle diameter increased with the monomer concentration, whereas the particle size distribution remained almost constant. The resulting yield of the particles reached 41.1% when 6 wt % 2,2′‐azobisisobutyronitrile (based on the total monomer) was used as the initiator. The styrene fraction in the monomer composition and toluene fraction in the solvent mixture also significantly affected the morphology and size of the resulting particles. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Effect of the preparation conditions on the permeation of ultrahigh‐molecular‐weight polyethylene/silicon dioxide hybrid membranes

Porous ultrahigh‐molecular‐weight polyethylene/SiO₂ membranes were prepared by thermally induced phase separation (TIPS) with white mineral oil as the diluent and SiO₂ as an additive. Influential factors, including extraction method, SiO₂ content, and cooling rate, were investigated. The results suggest that the both porosity and pure water flux of the membranes by extraction of the solvent naphtha in the tension state with alcohol were the best among our research. With increasing SiO₂ content, the porosity, pure water flux, and pore diameter increased. However, with excessive SiO₂ content, defects formed easily. Moreover, SiO₂ improved the pressure resistance of the membranes. The cooling rate directly effected the crystal structure. A slow cooling rate was good for crystal growth and the integration of the diluent. Therefore, the porosity, pure water flux, and bubble‐point pore diameter increased with decreasing cooling rate. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Effect of crosslinkers on the preparation and properties of ETFE‐based radiation‐grafted polymer electrolyte membranes

This study concerns a comparative study of three crosslinkers, divinylbenzene (DVB), 1,2‐bis(p,p‐vinylphenyl)ethane (BVPE), and triallyl cyanurate (TAC) crosslinked poly(ethylene‐co‐tetrafluoroethylene) (ETFE)‐based radiation‐grafted membranes, which were prepared by radiation grafting of p‐methylstyrene onto ETFE films and subsequent sulfonation. The effect of the different types and contents of the crosslinkers on the grafting and sulfonation, and the properties such as water uptake, proton conductivity, and thermal/chemical stability of the resulting polymer electrolyte membranes were investigated in detail. Introducing crosslink structure into the radiation‐grafted membranes leads to a decrease in proton conductivity due to the decrease in water uptake. The thermal stability of the crosslinked radiation‐grafted membranes is also somewhat lower than that of the noncrosslinked one. However, the crosslinked radiation‐grafted membranes show significantly higher chemical stability characterized in the 3% H₂O₂ at 50°C. Among the three crosslinkers, the DVB shows a most pronounced efficiency on the crosslinking of the radiation‐grafted membranes, while the TAC has no significant influence; the BVPE is a mild and effective crosslinker, showing the moderate influence between the DVB and TAC crosslinkers. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 4565–4574, 2006     

Influence of processing parameters on the degradation of poly(L‐lactide) during extrusion

The influence of processing conditions during melt extrusion on the degradation of poly(L ‐lactide) (PLLA) has been investigated. PLLA polymer was processed by melt extrusion in a double screw extruder at 210 and 240°C. For each extrusion temperature, two screw rotation speeds, 20 and 120 rpm, were used. To investigate the influence of moisture on the thermal degradation during processing, the PLLA granules were dried at 100°C for 5 h and then either extruded directly or conditioned at 65% RH, 20°C for 24 h prior to extrusion. The results show that a decrease in molecular weight measured as number‐average (M_n) molecular weight occurs for all combinations of process parameters used. At processing temperature of 210°C, the change in molecular weight for the dry granules was shown to be dependent on the residence time (i.e., screw rotation speed) in the melt. By changing the screw rotation speed from 120 to 20 rpm at 210°C, M_n decreased from 33,600 to 30,200 g/mol. When the processing temperature was increased to 240°C, the dry granules showed an M_n of 25,600 and 13,600 g/mol when extruded at 120 and 20 rpm, respectively. M_n for the conditioned specimens extruded at 210°C was 18,400 g/mol when processed at 120 rpm and 12,300 g/mol at 20 rpm. When processed at 240°C, 20 rpm, M_n is independent of whether the granules were dry or moist prior to extrusion. It is probably due to the fact that the degradation at 240°C is so extensive that the presence of moisture in the polymer does not contribute further to the degradation process. The stress and strain at break decreased due to degradation and were dependent on the molecular weight of the samples. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 79: 2128–2135, 2001     

Preparation and characterization of polyacrylamide cryogels produced from a high‐molecular‐weight precursor. I. Influence of the reaction temperature and concentration of the crosslinking agent

A new type of cryogel was prepared through a reaction of high‐molecular‐weight polyacrylamide (viscosity‐average molecular weight ≈ 3 × 10⁶ Da) with glutaraldehyde in a moderately frozen aqueous medium. The influence of the crosslinking agent concentration and temperature of the reaction on the gel fraction yield, swelling characteristics, and morphology of the cryogels was investigated. The dependence of the gel fraction yield on the reaction temperature was bell‐shaped. The recognized regularities of the formation of this new type of polyacrylamide cryogel based on a high‐molecular‐weight precursor were very similar to those observed earlier for polyacrylamide cryogels synthesized through the cryopolymerization of monomeric precursors. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Influence of different sterilization procedures on the morphological parameters and mechanical properties of ultra‐high‐molecular‐weight polyethylene

The objectives of this study were to examine the effects of the processing conditions, sterilization, and thermal treatment on the morphological and mechanical properties of ultra‐high‐molecular‐weight polyethylene (UHMWPE) in medical applications by means of thermal analysis, Fourier transform infrared spectroscopy, and nanoindentation. It is well known that manufacturing, irradiation, and thermal treatments significantly alter the microstructure of materials, which results in changes in their mechanical properties. UHMWPE was found to be barely sensitive to processing conditions but strongly influenced by sterilization treatments. Great emphasis was given to the characterization of the so‐called first generation of highly crosslinked UHMWPE because the thermal history of this material differed from that of γ‐irradiated materials. The physical and mechanical properties of UHMWPE were influenced as a result of γ and electron‐beam irradiation and the remelting procedure. Lower crystallinity, different lamellar thickness distributions, and lower hardness and modulus values were estimated. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Effect of polyethylene‐graft‐maleic anhydride as a compatibilizer on the mechanical and tribological behaviors of ultrahigh‐molecular‐weight polyethylene/copper composites

Ultrahigh‐molecular‐weight polyethylene/copper (UHMWPE/Cu) composites compatibilized with polyethylene‐graft‐maleic anhydride (PE‐g‐MAH) were prepared by compression molding. The effects of the compatibilizer on the mechanical, thermal, and tribological properties of the UHMWPE/Cu composites were investigated. These properties of the composites were evaluated at various compositions, and worn steel surfaces and composite surfaces were examined with scanning electron microscopy and X‐ray photoelectron spectroscopy. The incorporation of PE‐g‐MAH reduced the melting points of the composites and increased their crystallinity to some extent. Moreover, the inclusion of the PE‐g‐MAH compatibilizer greatly increased the tensile rupture strength and tensile modulus of the composites, and this improved the wear resistance of the composites. These improvements in the mechanical and tribological behavior of the ultrahigh‐molecular‐weight‐polyethylene‐matrix composites with the PE‐g‐MAH compatibilizer could be closely related to the enhanced crosslinking function of the composites in the presence of the compatibilizer. Moreover, the compatibilizer had an effect on the transfer and oxidation behavior of the filler Cu particulates, which could be critical to the application of metallic‐particulate‐filled polymer composites in engineering. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 948–955, 2004     

Behavior of UV‐cured print inks on LDPE and PBAT/TPS blend substrates during curing,postcuring, and accelerated degradation

During radiation curing, a reactive formulation is converted into a highly crosslinked coating film by means of polymerization reactions. This three‐dimensional (3D) network is resistant to external degrading factors as it cannot be undone by any physical–chemical means. In this study, various ultraviolet (UV)‐curable ink formulations with different pigments were developed. The behavior of the UV‐curable inks was evaluated during UV curing in a photocalorimeter or in a UV tunnel. Inks were exposed to accelerated aging in an accelerated weathering chamber and their physical–chemical properties were investigated. The presence of residual fractions of unreacted species trapped in the 3D network formed during UV curing interferes with the degradation of the main structure during exposure in the weathering chamber. The ink formulations that did not easily absorb UV light increased in gloss and hardness, indicating that residual crosslinking is taking place at the same time that degradation is occurring. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 41116.     

A comprehensive study on the size exclusion chromatography of kappa‐carrageenan for the identification of after‐peaks

Aqueous size exclusion chromatography (SEC) of polysaccharides in general and carrageenans in particular is complicated by a number of factors. The chromatograms of carrageenans which are sulfated anionic natural polymers contain a number of after‐peaks depending on the occlusion, adsorption, or association of various ionic species either naturally present or evolved during their processing. A systematic SEC analysis of after‐peaks appearing in the chromatograms was made to identify the species responsible for their formation. The five after‐peaks constantly appearing in the aqueous (0.1M NaNO₃) SEC of kappa‐carrageenan are attributed to sulfate, chloride, and nitrate anions whereas the first three and the fourth are due to divalent cations, mostly, and the fifth appears to result from the unknown impurities. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

The effect of substitution levels on the luminescent and degradation properties of fluorescent poly(ester‐anhydride)s

In this work, two kinds of diacid monomers were synthesized by a convenient scheme, where 4‐hydroxy‐3‐methoxybenzoic acid (vanillic acid) or 4‐hydroxy‐3,5‐dimethoxybenzoic acid (syringic acid) directly condensated with succinic chloride. Corresponding polyanhydrides were obtained by melt polycondensation. Copolyanhydrides composed of the new monomers and sebacic acid (SA) were further prepared and characterized by NMR, DSC, and fluorometer. The two new kinds of polyanhydride emit strong fluorescence and have similar fluorescent spectra to poly(di(p‐carboxyphenyl) succinate anhydride) (P(dCPS)). The emission wavelength (λ_em) of the copolymers could be tuned by the excitation wavelength (λ_ex). Degradation rate of the copolyanhydrides decreased as dMOCPS or ddMOCPS fraction increased, and the degradation duration could be modulated from several days to more than 3 months. It addition, the copolyanhydrides displayed typical surface‐degradation characteristics. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 1214–1221, 2006     

The nature of polymer grafts and substrate shape on the surface degradation of poly(l‐lactide)

Surface grafting of functional polymers is an effective method to alter material properties and degradation behavior. Two different substrate shapes of poly(l ‐lactide) (PLLA), i.e., films and microparticles, were surface‐grafted with hydrophilic monomers, and their surface degradation was monitored. Surface grafting with a hydrophilic and acidic polymer graft [acrylic acid (AA)] induced large alterations in the surface morphology and topography of the films. In contrast, hydrophilic and neutral polymer grafts [acrylamide (AAm)] had no significant effect on the surface degradation behavior, while the PLLA reference and co‐monomeric (AA/AAm) polymer‐grafted samples exhibited intermediate surface degradation rates. The grafted PAA chains induced a local acidic environment on the surface of the substrates, which in turn catalyzed the surface degradation process. This effect was more pronounced in the films than in the microparticles. Thus, the nature of the grafted chains and substrate geometry were shown to affect the surface degradation behavior of PLLA substrates. © 2015 The Authors Journal of Applied Polymer Science Published by Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42736.     

Influence of oxygen ion implantation on the free volume parameters and electrical conductivity of a polymer‐based bakelite RPC detector material

We have investigated the effect of ion implantation on structural modification and the electrical conductivity of Bakelite‐resistive plate chamber (RPC) detector material used in high energy physics experiments. Samples of Bakelite polymer were exposed to 100 keV and 150 keV oxygen ions in the fluence of 10¹² to 10¹⁵ ions cm^?2. Ion implantation induced microstructural changes have been studied using positron annihilation lifetime spectroscopy, X‐ray diffraction and Fourier transform infrared techniques. Positron lifetime parameters viz., o ‐Ps lifetime and its intensity showed formation of radicals, secondary ions due to the creation of interior tracks by high‐energy ions followed by chain scission at lower fluence of 100 keV implantation. The decreased free volume size at 150 keV ion implantation is an indication of crosslinking and filling up of interior tracks by the implanted ions. Variation of ac conductivity with frequency obeys Jonscher power law at 100 keV and the conduction mechanism is explained by barrier hopping model. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134 , 44962.     

Influence of branch content,comonomer type,and crosshead speed on the mechanical properties of metallocene linear low‐density polyethylenes

The effects of branch content (BC) and comonomer type on the mechanical properties of metallocene linear low‐density polyethylene (m‐LLDPEs) were studied by means of a stress–strain experiment at room temperature. A total of 16 samples with different BCs and comonomer types were used. In addition, the effect of crosshead speed on the mechanical properties of m‐LLDPEs with different BCs was examined. The degree of crystallinity (X_t) of these copolymers was determined by differential scanning calorimetry. In addition, Ziegler–Natta linear low‐density polyethylenes (ZN‐LLDPEs) were also studied for comparison purposes. The increase in BC of m‐LLDPEs decreased X_t and the modulus. However, the ZN‐LLDPEs showed higher small‐strain properties but lower ultimate properties than the m‐LLDPEs with similar weight‐average molecular weights and BCs. In comparison with low‐BC resins, m‐LLDPEs with high BCs exhibited a stronger strain hardening during the stress–strain experiments. Strain hardening was modeled by a modified Avrami equation, and the order of the mechanically induced crystal growth was in the range of 1–2, which suggested athermal nucleation. The crosshead speed was varied in the range 10–500 mm/min. For low‐BC m‐LLDPEs, there existed a narrow crosshead speed window within which the maxima in modulus and ultimate properties were observed. The location of the maxima were independent of BC. The effect of the crosshead speed on the mechanical properties of the m‐LLDPEs was a strong function of BC. However, highly branched m‐LLDPE in this experiment showed a weak dependence on the crosshead speed. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 5019–5033, 2006     

Influence of cocatalyst on the structure and properties of polypropylene/poly (ethylene‐co‐propylene) in‐reactor alloys prepared by MgCl2/TiCl4/diester type Ziegler‐Natta catalyst

In this work, a series of polypropylene/poly(ethylene‐co‐propylene) (iPP/EPR) in‐reactor alloys were prepared by MgCl₂/TiCl₄/diester type Ziegler‐Natta catalyst with triethylaluminium/triisobutylaluminium (TEA/TIBA) mixture as cocatalyst. The influence of cocatalyst and external electron donor, e.g., diphenyldimethoxysilane (DDS) or dicyclopentyldimethoxysilane (D ‐donor), on the structure and mechanical properties of iPP/EPR in‐reactor alloys were studied and discussed. According to the characterization results, PP/EPR was mainly composed of random poly(ethylene‐co‐propylene), segmented poly(ethylene‐co‐propylene), and high isotactic PP. Using TEA/TIBA mixture as cocatalyst and DDS as external electron donor, as TEA/TIBA ratio increased, the impact strength of iPP/EPR in‐reactor alloys had an increasing trend. Using TEA/TIBA mixture as cocatalyst and D ‐donor as external electron donor, the impact strength of iPP/EPR in‐reactor alloy were dramatically improved. In this case, the iPP/EPR in‐reactor alloy prepared at TEA: TIBA = 4 : 1 was the toughest. The influence of cocatalyst and external electron donor on the flexural modulus and flexural strength could be ignored. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Headspace solid‐phase microextraction with gas chromatography/mass spectrometry reveals a correlation between the degradation product pattern and changes in the mechanical properties during the thermooxidation of in‐plant recycled polyamide 6,6

The increased susceptibility of in‐plant recycled polyamide 6,6 toward thermooxidation was shown by headspace solid‐phase microextraction with gas chromatography/mass spectrometry (HS‐SPME/GC‐MS), tensile testing, differential scanning calorimetry (DSC), and Fourier transform infrared spectroscopy (FTIR). A correlation between the deterioration in mechanical properties and the formation of degradation products due to thermooxidation was found, and the most prominent decrease in mechanical properties coincided with the largest increase in the abundance of degradation products. The recycled materials had a shorter induction period toward oxidation, and their mechanical properties deteriorated faster than the mechanical properties of virgin material. The same trend was observed with HS‐SPME/GC‐MS because degradation products were found for recycled materials after oxidation times shorter than those for virgin material. Furthermore, larger amounts of degradation products were formed in the recycled materials. The high sensitivity of HS‐SPME/GC‐MS as an analytical tool was demonstrated because it was able to detect changes caused by oxidation considerably earlier than the other methods. Unlike DSC and FTIR, it could also show differences between samples recycled for different times. Four groups of degradation products—cyclic imides, pyridines, chain fragments, and cyclopentanones—were identified in thermooxidized polyamide 6,6. After 1200 h of thermooxidation, 1‐pentyl‐2,5‐pyrrolidinedione was the most abundant degradation product. Approximately four times more 1‐pentyl‐2,5‐pyrrolidinedione was formed in polyamide recycled three times than in virgin polyamide. Pyridines and chain fragments behaved toward oxidation and repeated processing like cyclic imides; that is, their amounts increased during oxidation, and larger amounts were formed in recycled materials than in virgin material. The cyclopentanone derivatives were present already in unaged material, and their amounts decreased during oxidation. Cyclopentanones were not formed because of the thermooxidation of polyamide 6,6. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 3396–3407, 2002