Wear‐Resistant Ultra High Molecular Weight Polyethylene/Zirconia Composites Prepared by in situ Ziegler‐Natta Polymerization

Summary: Ultra high molecular weight polyethylene (UHMWPE)/zirconia composite has been prepared by in situ polymerization of ethylene using a Ti‐based Ziegler‐Natta catalyst supported on the surface of zirconia. Comparison of mechanical and tribological properties has been carried out between the in situ polymerized and mechanically blended composites. Microscopic observations of filled composites revealed that the polymerized composite had more uniform dispersion of zirconia and enhanced interfacial properties than the mechanically blended composite. The polymerized composite showed in a tensile test a remarkable increase in elastic modulus and yield strength, in a tensile test, but a loss in elongational properties was insignificant. In a ring‐on‐block type wear test, the polymerized composite displayed superior wear resistance to the blended composite as well as to neat UHMWPE. At 43 wt.‐% of zirconia content, the polymerized composite showed about one fourth of the 1wear rate of neat UHMWPE. Observations of wear surfaces revealed that the abrasive wear, which are observed in unfilled UHMWPE, are greatly suppressed in filled composites. In polymerized composite, moreover, micro‐cracks were also significantly reduced in comparison to the blended composite, which eventually led to an additional decrease in the wear rate.

SEM image of powdery polymerized composite (zirconia content: 15%) obtained from the in situ polymerization.     

Tyrosine-derived polycarbonate-silica xerogel nanocomposites for controlled drug delivery

Biodegradable polymer–ceramic composites offer significant potential advantages in biomedical applications where the properties of either polymers or ceramics alone are insufficient to meet performance requirements. Here we demonstrate the highly tunable mechanical and controlled drug delivery properties accessible with novel biodegradable nanocomposites prepared by non-covalent binding of silica xerogels and co-polymers of tyrosine–poly(ethylene glycol)-derived poly(ether carbonate). The Young’s moduli of the nanocomposites exceed by factors of 5–20 times those of the co-polymers or of composites made with micron scale silica particles. Increasing the fraction of xerogel in the nanocomposites increases the glass transition temperature and the mechanical strength, but decreases the equilibrium water content, which are all indicative of strong non-covalent interfacial interactions between the co-polymers and the silica nanoparticles. Sustained, tunable controlled release of both hydrophilic and hydrophobic therapeutic agents from the nanocomposites is demonstrated with two clinically significant drugs, rifampicin and bupivacaine. Bupivacaine exhibits an initial small burst release followed by slow release over the 7 day test period. Rifampicin release fits the diffusion-controlled Higuchi model and the amount released exceeds the dosage required for treatment of clinically challenging infections. These nanocomposites are thus attractive biomaterials for applications such as wound dressings, tissue engineering substrates and stents.     

Investigation of nanocomposites based on semi-interpenetrating network of [L-poly (epsilon-caprolactone)]/[net-poly (epsilon-caprolactone)] and hydroxyapatite nanocrystals

In this paper the semi-interpenetrating network (semi-IPN) technique was used for the first time to prepare bone implant composites containing hydroxyapatite (HAP) nanocrystals. The prepared nanocomposites are expected to combine several property advantages including good mechanical strength, modified degradation rate and excellent osteoconductivity. The semi-IPN matrix based on the linear poly (epsilon-caprolactone) (L-PCL) and the network poly (epsilon-caprolactone) (net-PCL) structures are revealed to be phase separation structures. The morphology of net-PCL is featured by intracrosslinked microdomains (1-10 microm) that further interconnect with each other to form the network over the whole sample. The net-PCL component is totally amorphous at room temperature for the nanocomposites containing HAP up to 12.3 wt%. Further, the crystallinity of L-PCL is greatly decreased due to the presence of net-PCL as compared with that for pure L-PCL. The incorporation of L-PCL into the net-PCL network could significantly improve the mechanical properties of pure net-PCL. A great improvement in mechanical properties is observed for the nanocomposites if the HAP content is increased to 15.8 wt%. This transition is in agreement with that the net-PCL component changes from amorphous state to crystalline state at this composition.     

Composites of poly(lactide-co-glycolide) and the surface modified carbonated hydroxyapatite nanoparticles

To improve the mechanical properties of the composites of poly(lactide-co-glycolide) (PLGA, LA/GA = 80/20) and the carbonate hydroxyapatite (CHAP) particles, the rice-form or claviform CHAP particles with 30-40 nm in diameter and 100-200 nm in length were prepared by precipitation method. The uncalcined CHAP particles have a coarse surface with a lot of global protuberances, which could be in favor of the interaction of the matrix polymer to the CHAP particles. The nanocomposites of PLGA and surface grafted CHAP particles (g-CHAP) were prepared by solution mixing method. The structure and properties of the composites were subsequently investigated by the emission scanning electron microscopy, the tensile strength testing, and the cell culture. When the contents of g-CHAP were in the range of 2-15 wt %, the PLGA/g-CHAP nanocomposites exhibited an improved elongation at break and tensile strength. At the 2 wt % content of g-CHAP, the fracture strain was increased to 20% from 4-5% for neat PLGA samples. Especially at g-CHAP content of 15 wt %, the tensile strength of PLGA/g-CHAP composite was about 20% higher than that of neat PLGA materials. The tensile moduli of composites were increased with the increasing of filler contents, so that the g-CHAP particles had both reinforcing and toughening effects on the PLGA composites. The results of biocompatibility test showed that the higher g-CHAP contents in PLGA composite facilitated the adhesion and proliferation properties of osteoblasts on the PLGA/g-CHAP composite film.     

Functional Silica and Carbon Nanocomposites Based on Polybenzoxazines

The preparation of organic/inorganic hybrid materials comprising a polybenzoxazine (PBZ) matrix incorporating silicon‐based species (e.g., polydimethylsiloxane [PDMS], layered silicates [clays], and polyhedral oligomeric silsesquioxanes [POSS]) and carbon‐based materials (e.g., carbon black, carbon fibers, carbon nanotubes, and graphene) has received much attention in recent years because these composites display low water absorption, low surface free energy, low dielectric constants, flame‐retardancy, and excellent thermal and mechanical properties. This short review article describes the chemical and physical approaches that are used to prepare PBZs incorporating silica and carbon nanocomposites. In addition, recent reports of their physical properties are discussed, covering their dielectric constants and dynamic mechanical, thermal, electrical, and surface properties.     

Tungsten disulfide nanotubes reinforced biodegradable polymers for bone tissue engineering

In this study, we have investigated the efficacy of inorganic nanotubes as reinforcing agents to improve the mechanical properties of poly(propylene fumarate) (PPF) composites as a function of nanomaterial loading concentration (0.01–0.2 wt.%). Tungsten disulfide nanotubes (WSNTs) were used as reinforcing agents in the experimental group. Single- and multi-walled carbon nanotubes (SWCNTs and MWCNTs) were used as positive controls, and crosslinked PPF composites were used as the baseline control. Mechanical testing (compression and three-point bending) shows a significant enhancement (up to 28–190%) in the mechanical properties (compressive modulus, compressive yield strength, flexural modulus and flexural yield strength) of WSNT-reinforced PPF nanocomposites compared to the baseline control. In comparison to the positive controls, significant improvements in the mechanical properties of WSNT nanocomposites were also observed at various concentrations. In general, the inorganic nanotubes (WSNTs) showed mechanical reinforcement better than (up to 127%) or equivalent to that of carbon nanotubes (SWCNTs and MWCNTs). Sol fraction analysis showed significant increases in the crosslinking density of PPF in the presence of WSNTs (0.01–0.2 wt.%). Transmission electron microscopy (TEM) analysis on thin sections of crosslinked nanocomposites showed the presence of WSNTs as individual nanotubes in the PPF matrix, whereas SWCNTs and MWCNTs existed as micron-sized aggregates. The trend in the surface area of nanostructures obtained by Brunauer–Emmett–Teller (BET) surface area analysis was SWCNTs > MWCNTs > WSNTs. The BET surface area analysis, TEM analysis and sol fraction analysis results taken together suggest that chemical composition (inorganic vs. carbon nanomaterials), the presence of functional groups (such as sulfide and oxysulfide) and individual dispersion of the nanomaterials in the polymer matrix (absence of aggregation of the reinforcing agent) are the key parameters affecting the mechanical properties of nanostructure-reinforced PPF composites and the reason for the observed increases in the mechanical properties compared to the baseline and positive controls.     

Injectable in situ cross-linkable nanocomposites of biodegradable polymers and carbon nanostructures for bone tissue engineering

This study investigates the effects of nanostructure size and surface area on the rheological properties of un-cross-linked poly(propylene fumarate) (PPF) nanocomposites and the mechanical properties of cross-linked nanocomposites as a function of the nanostructure loading. Three model carbon nanostructures were examined, C₆₀ fullerenes, ultra-short single-walled carbon nanotubes (US-tubes) and single-walled carbon nanotubes (SWNTs). Rheological measurements showed that C₆₀ and US-tube un-cross-linked nanocomposites exhibited viscous-like characteristics with the complex viscosity independent of frequency for nanostructure concentrations up to 1 wt%. Compressive and flexural mechanical testing demonstrated significant mechanical reinforcement of US-tube and SWNT nanocomposites as compared to cross-linked polymer alone, with an up to twofold increase in the mechanical properties. Scanning electron microscopy examination of the fracture surface of cross-linked US-tube nanocomposite revealed lack of aggregation of US-tubes. Although sol fraction studies did not provide any evidence of additional cross-linking, due to the presence of US-tubes in the nanocomposites, transmission electron microscopy studies suggested the crystallization of PPF on the surface of US-tubes which can contribute to the mechanical reinforcement of the US-tube nanocomposites. These results demonstrate that the rheological properties of un-cross-linked nanocomposites depend mainly on the carbon nanostructure size, whereas the mechanical properties of the cross-linked nanocomposites are dependent on the carbon nanostructure surface area. The data also suggest that US-tube nanocomposites are suitable for further consideration as injectable scaffolds for bone tissue engineering applications.     

Synthesis of hairy acrylic core‐shell particles as toughening agents for epoxy networks

Hairy poly(butyl acrylate) (PBuA) core‐shell particles with a crosslinked shell were prepared by soap‐free emulsion polymerization. The incorporation of the hairy structure was obtained either by surface polymerization of a methacrylate (MMA) terminated poly(ethylene oxide) (PEO), or by physical adsorption of poly(ethylene oxide)‐poly(propylene oxide) (PPO)‐poly(ethylene oxide) triblock copolymers. The particle shell was crosslinked during the synthesis so as to keep the integrity and morphology of the particle upon curing the epoxy network. Particle sizes and size distributions were determined both by quasi‐elastic light scattering and transmission electron microscopy. Particle morphology was investigated by electron and atomic force microscopies. The presence of the poly(ethylene oxide) layer was evidenced by direct analysis of the latexes by means of ¹H NMR spectroscopy. Mixing of the core shell rubber particles with the reactive epoxy and processing of the toughened‐epoxy networks are described. The influence of the hairy layer (with regards to density and PEO chain length) on particle dispersion within the epoxy network, the resulting rheological behaviour of the core‐shell (CS)/prepolymer epoxy blends, and mechanical properties of the modified epoxy were examined and discussed.     

Injectable in situ cross-linkable nanocomposites of biodegradable polymers and carbon nanostructures for bone tissue engineering

This study investigates the effects of nanostructure size and surface area on the rheological properties of un-cross-linked poly(propylene fumarate) (PPF) nanocomposites and the mechanical properties of cross-linked nanocomposites as a function of the nanostructure loading. Three model carbon nanostructures were examined, C(60) fullerenes, ultra-short single-walled carbon nanotubes (US-tubes) and single-walled carbon nanotubes (SWNTs). Rheological measurements showed that C60 and US-tube un-cross-linked nanocomposites exhibited viscous-like characteristics with the complex viscosity independent of frequency for nanostructure concentrations up to 1 wt%. Compressive and flexural mechanical testing demonstrated significant mechanical reinforcement of US-tube and SWNT nanocomposites as compared to cross-linked polymer alone, with an up to twofold increase in the mechanical properties. Scanning electron microscopy examination of the fracture surface of cross-linked US-tube nanocomposite revealed lack of aggregation of US-tubes. Although sol fraction studies did not provide any evidence of additional cross-linking, due to the presence of US-tubes in the nanocomposites, transmission electron microscopy studies suggested the crystallization of PPF on the surface of US-tubes which can contribute to the mechanical reinforcement of the US-tube nanocomposites. These results demonstrate that the rheological properties of un-cross-linked nanocomposites depend mainly on the carbon nanostructure size, whereas the mechanical properties of the cross-linked nanocomposites are dependent on the carbon nanostructure surface area. The data also suggest that US-tube nanocomposites are suitable for further consideration as injectable scaffolds for bone tissue engineering applications.     

Crystalline Structure and Properties of Carbon Nanofiber Composites Prepared by Melt Extrusion

The effects of carbon nanofibers (CNFs) on the microstructure and properties of semi‐crystalline polymers were studied based on the preparation of poly(propylene) (PP) nanocomposites by a twin screw extrusion method. The crystallization behavior and morphology, as well as the thermal and mechanical properties of the CNF/PP nanocomposites, were characterized. Studies using differential scanning calorimetry (DSC) and wide angle X‐ray diffraction (WAXD) indicated that the CNFs promoted heterogeneous nucleation. The relative amount, crystallite size and distribution of different crystallites in PP varied because of the addition of CNFs, which affected the final properties of the nanocomposites. Meanwhile, the degree of crystallinity of the PP exhibited an increasing trend with the addition of CNFs, followed by moderate decreases at higher content. The dynamic mechanical analysis (DMA) test showed that the stiffness of the PP was enhanced as a result of the addition of CNFs. With increasing of CNF content, the flexural strength and modulus of the nanocomposites were enhanced continuously. Scanning electron microscopy (SEM) observations indicated that the CNFs were uniformly dispersed in the PP matrix. The effect of CNFs on the thermal stability was analyzed by comparing the thermogravimetric analysis (TGA) curves of the neat PP and CNF/PP composites. The thermal stability of PP composites at high temperature increased with enhanced CNF content.

     

Mechanical properties and three-body wear of veneering composites and their matrices

Fatigue as one of the major factors affecting three-body wear of resin composites is influenced by mechanical properties of the resin matrix. The aim of this in vitro study was to determine three-body wear (ACTA methodology), fracture strength, and Young's modulus of four veneering composites (Artglass old and new formula, Vita Zeta LC Composite, Targis) and one direct restorative composite (Z 100). Furthermore, three-body wear of the pure matrices of the materials was tested. The wear results were compared to Amalgam as reference material. It should be computed whether there exists a correlation between the wear results of resin composite and matrix alone. Wear of the veneering composites was significantly higher than of Z100 (13 microm) and Amalgam (14 microm; p < 0.01, Mann-Whitney U-test). Mean fracture strengths of indirect composites ranged from 127.5 MPa (Targis) to 71.6 MPa (Vita Zeta LC). The elastic moduli of the composites were between 2.9 and 12.8 GPa. The matrix wear rates did not differ significantly. Three-body wear results of complex resin composites are highly influenced by their filler content, filler particle size distribution, kind of filler particles, shape, and their silanization to the matrix. Due to this fact, three-body wear testing is an essential testing method and cannot be replaced by testing single material components.     

Long-term mechanical durability of dental nanocomposites containing amorphous calcium phosphate nanoparticles

Half of all dental restorations fail within 10 years, with secondary caries and restoration fracture being the main reasons. Calcium phosphate (CaP) composites can release Ca and PO(4) ions and remineralize tooth lesions. However, there has been no report on their long-term mechanical durability. The objective of this study was to investigate the wear, thermal-cycling, and water-aging of composites containing amorphous calcium phosphate nanoparticles (NACP). NACP of 112-nm and glass particles were used to fabricate four composites: (1) 0% NACP+75% glass; (2) 10% NACP+65% glass; (3) 15% NACP+60% glass; and (4) 20% NACP+50% glass. Flexural strength and elastic modulus of NACP nanocomposites were not degraded by thermal-cycling. Wear depth increased with increasing NACP filler level. Wear depths of NACP nanocomposites after 4 × 10(5) cycles were within the range for commercial controls. Mechanical properties of all the tested materials decreased with water-aging time. After 2 years, the strengths of NACP nanocomposites were moderately higher than the control composite, and much higher than the resin-modified glass ionomers. The mechanism of strength loss for resin-modified glass ionomer was identified as microcracking and air-bubbles. NACP nanocomposites and control composite were generally free of microcracks and air-bubbles. In conclusion, combining NACP nanoparticles with reinforcement glass particles resulted in novel nanocomposites with long-term mechanical properties higher than those of commercial controls, and wear within the range of commercial controls. These strong long-term properties, plus the Ca-PO(4) ion release and acid-neutralization capability reported earlier, suggest that the new NACP nanocomposites may be promising for stress-bearing and caries-inhibiting restorations.     

Surface micromechanics of ultrahigh molecular weight polyethylene: Microindentation testing,crosslinking, and material behavior

The wear behavior of ultrahigh molecular weight polyethylene (UHMWPE) is critical to the success of total joint replacements. Recent attempts to modify the wear behavior of UHMWPE by processing, in particular, crosslinking UHMWPE have shown promise to increase wear resistance, but concerns persist regarding other mechanical properties. It is also unclear what specific surface mechanical properties govern the wear resistance seen in these materials. The goal of this study was to demonstrate a custom-built surface mechanical test system and method that measures the micromechanical response of microtomed UHMWPE surfaces to depth-sensing microindentation tests. The surface structure of these UHMWPE materials was also examined using scanning electron microscopy and atomic force microscopy. A custom designed microindentation test system assessed the microindentation behavior of three UHMWPE resins: 1. Hylamertrade mark, 2. GUR-1020 CMS, and 3. Marathontrade mark-a lightly crosslinked material. The effects of material and indentation depth were studied. Microindentation tests were performed with indentation depths ranging from 2 to 45 microm. Four different measurements of surface micromechanical behavior were obtained including the surface modulus, microhardness, hysteresis energy (irreversible work done to the sample per unit cycle) and its associated energy dissipation factor, and loading slope. Statistically significant differences in each of these parameters were found for each material. Generally, Hylamer had the largest values for these parameters, followed by the GUR resin and then the Marathon. Surface modulus was independent of depth of testing and found to be 651 MPa for Marathon, 738 MPa for GUR, and 1015 MPa for Hylamer (Modulus for bulk UHMWPE is 540 MPa for Hylamer, 620 for GUR, and 1380 for Hylamer). The microhardness varied between 67 and 162 MPa depending on material and depth of testing. Surface structural characterization shows that the microtoming process for surface preparation generated distinct surface features that varied between materials. Intermittent drawn ribbons of polymer with oriented crystals were observed in both scanning electron microscopy and atomic force microscopy. The surface density and size of these features were characteristic of the materials with the Hylamer having the fewest, but largest ribbons, followed by GUR and then Marathon.     

Filler features and their effects on wear and degree of conversion of particulate dental resin composites

Based on the incomplete understanding on how filler features influence the wear resistance and monomer conversion of resin composites, this study sought to evaluate whether materials containing different shapes and combinations of size of filler particles would perform similarly in terms of three-body abrasion and degree of conversion. Twelve experimental monomodal, bimodal or trimodal composites containing either spherical or irregular shaped fillers ranging from 100 to 1500 nm were examined. Wear testings were conducted in the OHSU wear machine (n = 6) and quantified after 10(5) cycles using a profilometer. Degree of conversion (DC) was measured by FTIR spectrometry at the surface of the composites (n = 6). Data sets were analyzed using one-way Anova and Tukey's test at a significance level of 0.05. Filler size and geometry was found to have a significant effect on wear resistance and DC of composites. At specific sizes and combinations, the presence of small filler particles, either spherical or irregular, may aid in enhancing the wear resistance of composites, without compromising the percentage of reacted carbon double bonds.     

Distinct Mechanical Properties of Polymer/Polymer‐Grafting‐Graphene Nanocomposites

A nonequilibrium deformation technique based on the dissipative particle dynamics is employed to investigate the mechanical properties of polymer nanocomposites reinforced by graphene‐based nanosheets. Hierarchically packed network structure, (small‐length‐scale 2D network structure of graphene nanosheets)‐in‐(large‐length‐scale 3D network structure of homogeneously dispersed graphene nanosheets), is observed, which plays an important role in governing the mechanical properties of polymer nanocomposites. The improvements in tensional modulus over near polymer bulk (n‐P) are about 23% and 61% for polymer/pristine‐graphene blends (P/n‐Gr) and polymer/polymer‐grafting‐graphene nanocomposites (P/g‐Gr), respectively. In addition to higher tensile strength, the P/g‐Gr also exhibit higher tensile strength and yield strength. The strain hardening behaviors at larger deformation are discovered in the polymer/polymer‐grafting‐graphene nanocomposites when the polymer length is relatively larger, which does not appear in n‐P and P/n‐Gr. It is further found that the strain hardening behaviors mainly benefit from the stretching behaviors of the polymers grafting to graphene nanosheets. The results reveal the principles of diverse mechanical properties for polymer nanocomposites reinforced by graphene‐based nanosheets and may provide useful information for preparing polymer nanocomposites with excellent performance.     

Wear performance of ultrahigh molecular weight polyethylene/quartz composites

Ultrahigh molecular weight polyethylene (UHMWPE)/quartz composites were compression molded in the presence of organosiloxane, and then hydrolyzed. The used organosiloxane is vinyl tri-ethyloxyl silane. The gelation, the melting behavior, the crystallinity, the mechanical properties and the wear resistance of UHMWPE/quartz composites were investigated. The results showed that organosiloxane can act as a cross-linking agent for UHMWPE matrix and serve as a coupling agent for improving the bonding between the quartz particles and the UHMWPE matrix. The correlation between the various properties and the morphology of the composites has been discussed. At about 0.5phr organsiloxane while the degree of crystallinity of the composite is at the peak value of 57%, the mechanical properties and the wear resistance of UHMWPE/quartz composites reaches their maximum.     

Preparation,mechanical property and cytocompatibility of poly(l-lactic acid)/calcium silicate nanocomposites with controllable distribution of calcium silicate nanowires

How to accurately control the microstructure of bioactive inorganic/organic nanocomposites still remains a significant challenge, which is of great importance in influencing their mechanical strength and biological properties. In this study, using a combined method of electrospinning and hot press processing, calcium silicate hydrate (CSH) nanowire/poly(l-lactide) (PLLA) nanocomposites with controllable microstructures and tailored mechanical properties were successfully prepared as potential bone graft substitutes. The electrospun hybrid nanofibers with various degrees of alignment were stacked together in a predetermined manner and hot pressed into hierarchically structured nanocomposites. The relationship between the microstructure and mechanical properties of the as-prepared nanocomposites were systematically evaluated. The results showed that CSH nanowires in a PLLA matrix were able to be controlled from completely randomly oriented to uniaxially aligned, and then hierarchically organized with different interlayer angles, leading to corresponding nanocomposites with improved mechanical properties and varied anisotropies. It was also found that the bending strength of nanocomposites with 5 wt.% CSH nanowires (130 MPa) was significantly higher than that of pure PLLA (86 MPa) and other composites. The addition of CSH nanowires greatly enhanced the hydrophilicity and apatite-forming ability of PLLA films, as well as the attachment and proliferation of bone marrow stromal cells. The study suggested that a combination of electrospinning and hot pressing is a viable means to control the microstructure and mechanical properties, and improve the mineralization ability and cellular responses, of CSH/PLLA nanocomposites for potential bone repair applications.     

Electrically Insulated Epoxy Nanocomposites Reinforced with Synergistic Core–Shell SiO2@MWCNTs and Montmorillonite Bifillers

With unique physicochemical properties, multiwalled carbon nanotubes (MWCNTs) have enabled major achievement in polymer composites as reinforcing fillers. Nevertheless, high conductivity of raw MWCNTs (R‐MWCNTs) limits their wider applications in certain fields, which require outstanding thermal conductivity, mechanical, and insulation properties simultaneously. In this article, silica (SiO₂) coated MWCNTs core–shell hybrids (SiO₂@MWCNTs) and organically modified montmorillonite (O‐MMT) are employed to modify epoxy (EP) simultaneously. The epoxy‐clay system is cured by using anhydride curing agent. The impact strength and flexural strength of final nanocomposites are greatly improved. Meanwhile, the final composites remain in high electrical insulation. Compared to mixed acid treated MWCNTs (C‐MWCNTs) (0.5 wt%)/EP nanocomposites, the volume resistivity of the O‐MMT(4 wt%)/SiO₂@MWCNTs(0.5 wt%)/EP nanocomposites increases more than six orders of magnitude. Synergistic toughening effect occurs when using core–shell SiO₂@MWCNTs and MMT bifillers. The electrical insulation is attributed to the suppressed electron transport effect by SiO₂ layer on the CNTs surface, and the blocked conductive CNTs network by the buried 2D structural O‐MMT. The SiO₂@MWCNTs core–shell hybrids also benefit to decrease the dielectric constant and dielectric loss of CNTs/EP composites. This work provides guidance to using CNTs as reinforcement fillers to toughen the polymers for electric insulating applications.     

Poly(2-methacryloyloxyethyl phosphorylcholine) grafting and vitamin E blending for high wear resistance and oxidative stability of orthopedic bearings

The ultimate goal in manipulating the surface and substrate of a cross-linked polyethylene (CLPE) liner is to obtain not only high wear resistance but also high oxidative stability and high-mechanical properties for life-long orthopedic bearings. We have demonstrated the fabrication of highly hydrophilic and lubricious poly(2-methacryloyloxyethyl phosphorylcholine) (PMPC) grafting layer onto the antioxidant vitamin E-blended CLPE (HD-CLPE(VE)) surface. The PMPC grafting layer with a thickness of 100 nm was successfully fabricated on the vitamin E-blended CLPE surface by using photoinduced-radical graft polymerization. Since PMPC has a highly hydrophilic nature, the water wettability and lubricity of the PMPC-grafted CLPE and HD-CLPE(VE) surfaces were greater than that of the untreated CLPE surface. The PMPC grafting contributed significantly to wear reduction in a hip-joint simulator wear test. Despite high-dose gamma-ray irradiation for cross-linking and further UV irradiation for PMPC grafting, the substrate modified by vitamin E blending maintained high-oxidative stability because vitamin E is an extremely efficient radical scavenger. Furthermore, the mechanical properties of the substrate remained almost unchanged even after PMPC grafting or vitamin E blending, or both PMPC grafting and vitamin E blending. In conclusion, the PMPC-grafted HD-CLPE(VE) provided simultaneously high-wear resistance, oxidative stability, and mechanical properties.     

Influence of Graphene Oxide on Crystallization Behavior and Chain Folding Surface Free Energy of Poly(vinylidenefluoride‐co‐hexafluoropropylene)

Graphene oxide (GO) filled poly(vinylidene fluoride‐co‐hexafluoropropylene) (PVDF‐HPF) copolymer nanocomposites as promising piezoelectric materials are developed, and their crystallization behavior and chain folding free energy are examined. Appropriate distribution of GO nanoparticles in the copolymer is confirmed by transmission electron microscopic analysis. The crystalline structure of nanocomposites is analyzed by wide‐angle X‐ray scattering and Fourier transform infrared spectroscopy. The results show an increase in the β‐phase content of PVDF‐HPF copolymer in the presence of GO. Non‐isothermal crystallization kinetics of the neat polymer and corresponding nanocomposites are studied by a multiple heating rate differential scanning calorimetry using modified Avrami–Jeziorny and Liu models. Moreover, barrier energy of crystallization is calculated by Friedman and Kissinger models. It is found that addition of GO to the copolymer increases nucleation activity of the nanocomposites. Investigation on linear crystal growth via Hoffman's theorem indicates an enhanced nucleation activity upon increasing GO content. The surface folding free energy of the neat polymer is changed from 5.79 × 10⁻² to 7.27 × 10⁻² J m⁻² upon addition of 5 wt% of GO. A bundle‐like mechanism is proposed, which can explain the crystallite growth. Analysis based on Vyazovkin theorem reveals that the crystallization activation energy is independent of GO at elevated temperatures.