Ultra-high Molecular Weight Polyethylene Chains Research Articles

Thermo-Oxidative Aging Effect on Charge Transport in Polypropylene/Ultra-High Molecular Weight Polyethylene Nanocomposites

This study investigates the impact of magnesium oxide (MgO) nanoparticles on the thermo-oxidative aging behavior of blends of polypropylene (PP) and ultra-high molecular weight polyethylene (UHMWPE). The samples, both unfilled and filled with MgO, were aged at 120 °C for varying durations of up to 672 h. The observed structural changes are not monotonic; recrystallization leads to the increased crystallinity and melting temperature of UHMWPE until 336 h. Beyond this, the consumption of the antioxidant leads to chain scission which, in turn, results in decreased crystallinity. The presence of carbonyl groups indicates chemical changes and, as such, the carbonyl index is used as an indicator of aging, with subsequent changes to charge transport. During thermal aging, the interaction between PP and UHMWPE chains at interfaces is enhanced, leading to improved compatibility and the emergence of a new single crystallization peak in PP/UHMWPE blends. Although MgO does not show evidence of elevating the crystallization temperature, implying the absence of enhanced nucleation, it acts as a compatibilizer, improving interfacial interaction compared with the unfilled blend counterparts. MgO hinders the breakage of molecular structures and impedes the diffusion of oxygen. This, in turn, results in nanocomposites filled with MgO having reduced their charge accumulation and conductivity, thus delaying the aging process compared to PP/UHMWPE blends without nanofiller.

Enhancing Chain Mobility of Ultrahigh Molecular Weight Polyethylene by Regulating Residence Time under a Consecutive Elongational Flow for Improved Processability

Improving the processability of ultrahigh molecular weight polyethylene (UHMWPE) and understanding the effect of the polymeric chain mobility has long been a challenging task. Herein, we show that UHMWPE without any processing aids can be processed at a lower temperature of 180 °C compared to conventional processing temperatures (~250 °C) under a continuous elongational flow (CEF) by using an eccentric rotor extruder (ERE). By probing the effect of the residence time of UHMWPE samples under a CEF on the morphology, rheological behavior and molecular orientation, we find that the long polymer chains of UHMWPE are apt to orientate under a consecutive volume elongational deformation, thereby leading to a higher residual stress for the extruded sample. Meanwhile, the residence time of samples can regulate the polymeric chain mobility, giving rise to the simultaneous decrease of the melting defects and residual stress as well as Hermans orientation function with increasing residence time from 0 to 60 s. This also engenders the enhanced diffusion of UHMWPE segments, resulting in a defect-free morphology and higher entanglement with lower crystallinity but without causing obvious thermal oxidative degradation of UHMWPE. This interesting result could originate from the fast chain entanglement and particle welding enabled by a desirably short residence time, which could be explained by the empirical, entropy-driven melting explosion mechanism.

Insights into Oxidation of the Ultrahigh Molecular Weight Polyethylene Artificial Joint Related to Lipid Peroxidation.

Oxidative degradation of ultrahigh molecular weight polyethylene (UHMWPE) bearings is one of the main factors that deteriorates their mechanical properties and abrasive wear resistance, which further results in the failure of total joint replacements. Absorption and diffusion of synovial fluids have been considered as causes of the oxidation of UHMWPE bearings. However, the role of synovial fluids in oxidation of UHMWPE remains elusive. In this work, we aimed to reveal the oxidation mechanism of UHMWPE joints with respect to squalene (a representative component of the synovial fluid). The UHMWPE doped in squalene showed slight oxidation, while severe oxidation was observed when squalene doped UHMWPE was exposed to oxygen atmosphere. Squalene manifested lipid peroxidation with notable oxidation products and oxygen-derived free radicals during thermo-oxidative aging. Lipid peroxidation was deduced to follow two routes including autoxidation and thermal oxidation. The aggressive free radicals of squalene abstracted hydrogen atoms from the UHMWPE chains, initiating the oxidation of UHMWPE artificial joints. These findings not only provide evidence for comprehending the process of squalene-induced UHMWPE oxidation but also are instructive to develop highly oxidative-resistant UHMWPE.

Phase structure and mechanical properties of disentangled ultra-high molecular weight polyethylene/polyhedral oligomeric silsesquioxane nanocomposites in a solid state

Ultra-high molecular weight polyethylene (UHMWPE)/disilanolisobutyl polyhedral oligomeric silsesquioxane (POSS) nanocomposites in a disentangled state were synthesized by in situ ethylene polymerization. This is the first report of a detailed study on the phase structure and mechanical properties of disentangled UHMWPE/ POSS nanocomposites in a solid state. The phase structure and chain dynamics of UHMWPE nanocomposites were characterized using wide-line proton NMR and 13C cross-polarization/magic-angle spinning (CP/MAS) solid-state nuclear magnetic resonance (NMR). The results showed that a strong interaction between the POSS and nascent UHMWPE matrix occurred in a solid state, especially in the intermediate and monoclinic crystalline phases. This strong interaction between POSS particles and UHMWPE chains may result in improved melt recovery properties. Mechanical testing indicated that the lowest friction coefficients and highest breaking strength were achieved when 1 wt% loading of POSS was incorporated. The influence of the microstructure on lubrication and mechanical properties was also studied.

Disentangled UHMWPE/POSS nanocomposites prepared by ethylene in situ polymerization

[3-t-Bu-2-O-C6H3CHN(C6F5)]2TiCl2 catalyst (FI catalyst) was immobilized on disilanolisobutyl POSS to synthesize disentangled ultra-high molecular weight polyethylene (UHMWPE)/POSS nanocomposites during ethylene in situ polymerization. The presence of POSS significantly influenced the polymerization properties of the FI catalyst active centers. It was shown that the characteristic of “living” polymerization of the FI catalyst was retarded. Furthermore, disilanolisobutyl POSS is dispersed uniformly in the UHMWPE matrix with particles size of only several tens nanometers. Interestingly, the incorporation of the POSS into nascent UHMWPE matrix led to a strong interaction between the POSS particles and the UHMWPE chains, resulting in an increased density of entangled chains, as reflected by rheological test. Moreover, the crystallinity and the lamellae thickness of nascent UHMWPE increased upon increasing POSS loading, as observed by differential scanning calorimetry. It suggested that the POSS particles would be presented as a nucleating agent. Finally, the thermal stability and the hydrophilic property of the nanocomposites were improved due to the incorporation of POSS particles.

Pattern abrasion of ultra-high molecular weight polyethylene: Microstructure reconstruction of worn surface

Abstract The friction and wear behavior of ultra-high molecular weight polyethylene (UHMWPE) sliding against bearing steel (AISI 52100) in a ring-on-block contact mode under the lubrication of aqueous solution of 3.5% NaCl was evaluated. The worn polymer surfaces were analyzed by means of three dimensional profiling, atomic force microscopy, Polarized Raman microanalysis, field emission scanning electron microscopy, and nanoindentation testing. It was found that unusual wavelike abrasion patterns were formed on the worn surface of UHMWPE under properly selected sliding conditions. In the presence of plowing effect, the molecular chains of UHMWPE and short-rod like microcrystalline grains of abrasion pattern were both further oriented along the plowing direction and became tiny and dense owing to microstructure reconstruction. Resultant microstructurally reconstructed worn surface of UHMWPE had a higher nanoindentation hardness and modulus as well as increased wear resistance.

The effect of polypyrrole coatings on the adhesion and structure properties of UHMWPE fiber

To improve the adhesion between ultrahigh molecular weight polyethylene (UHMWPE) fiber and polymer matrix, pyrrole is oxidatively polymerized on the UHMWPE fiber surface continuously. The micro-composite of polypyrrole (PPy)-coated fiber/epoxy was prepared and the fiber was studied by interfacial shear strength (IFSS) through a single fiber pull-out method. Compared with the UHMWPE fiber as-received, the mean value of IFSS between PPy-coated UHMWPE and epoxy increased from 1.06 MPa to 5.72 MPa. In addition, the surface morphology and structure of PPy-coated UHMWPE fiber were studied by SEM, FT-IR, DSC and DMA. The results showed that PPy-coated UHMWPE fiber surface was observed with some particles attached. Although there is no chemical interaction between PPy and UHMWPE chains, PPy has some interaction with UHMWPE molecular chains according to the results of DMA. The PPy coatings have an effect on the adhesion may be associated with the roughened surface of the fiber and upon intermolecular interaction.

Gelation mechanism of ultra-high-molecular-weight polyethylene (UHMWPE) chains in dispersion solutions containing multiwall carbon nanotubes (MWNTs) analyzed in terms of liquid-liquid phase separation

Abstract Gelation mechanisms of ultra-high-molecular-weight polyethylene (UHMWPE) in dispersion solutions containing multiwall carbon nanotubes (MWNTs) were investigated in terms of liquid-liquid phase separation mechanisms. When an incident beam of He-Ne gas laser was directed to the dispersion solution quenched to a desired temperature, the logarithm of scattered intensity increased linearly with elapsing time and tended to deviate from this linear relationship. The two different increasing behaviors of the scattered intensity were termed as initial and latter stages, respectively, of the phase separation. The linear increase in logarithmic light-scattered intensity was analyzed within the framework of the linear theory of spinodal decomposition in terms of the viewpoint that the quenched solution becomes thermodynamically unstable and tends to incur phase separation to resolve the unstable state. The growth rate of the concentration fluctuation of neat UHMWPE solution (without MWNTs) calculated from the slope of linear increase was faster than that of the dispersion solution. In spite of the rapid growth rate, however, the gelation time of the dispersion solution was much shorter than that of the neat UHMWPE solution and the gelation and quasi-spinodal temperatures were slightly higher. These phenomena were in contradiction with the result of the concentration fluctuation. This contradiction was thought to be due to the fact that diffused UHMWPE chains in the dispersion solution were gelled easily on the MWNT surface rather than the gelation by self-coagulation.

Studies on surface modification of UHMWPE fibers via UV initiated grafting

In this research, the surface of ultra high molecular weight polyethylene (UHMWPE) fiber was modified by high energy ultraviolet (UV) initiated grafting reactions and acrylamide groups were grafted onto UHMWPE chains. The initiating and grafting mechanism of the reactions was studied. Some important factors influencing the grafting effect, e.g. crystallinity of UHMWPE fiber, concentration of the initiating reagent, grafting time and the concentration of grafting monomer (acrylamide) were discussed. Fourier transform infrared (FTIR) was used to manifest the mechanism of the grafting reaction. Scanning electron microscopy (SEM) was used to show the morphology changing of the fiber surface. Single fiber pull-out strength and ILSS tests of the composite showed that acrylamide grafted onto the surface of the fiber could improve the interfacial adhesion between treated fibers and matrices.

Morphology and mechanical properties of ultra-high molecular weight polyethylene-poly(tetrafluoroethylene) blend films

This paper deals with the morphology and mechanical properties of blend films for polytetrafluoroethylene (PTFE) and ultra-high molecular weight polyethylene (UHMWPE) prepared by kneading techniques. This experiment was carried out for blend films, prepared with different compositions of PTFE and UHMWPE to improve thermal properties of PE. In spite of the incompatibility of the two polymers, the blend film with the PTFE/UHMWPE composition =75/25 was maintained under the measurement of complex modulus at temperature higher than 300°C. This indicates that the UHMWPE chains dispersed in PTFE fibrous texture were not separated by the melting flow of UHMWPE at 300°C. To check the origin of this interesting phenomenon, the morphology of the blend films was investigated by using scanning electron microscopy, X-ray diffraction, and13C nuclear magnetic resonance.