Surface modification of ultra‐high‐molecular‐weight polyethylene. II. Effect on the physicomechanical and tribological properties of ultra‐high‐molecular‐weight polyethylene/poly(ethylene terephthalate) composites

We performed surface modification of ultra‐high‐molecular‐weight polyethylene (UHMWPE) through chromic acid etching, with the aim of improving the performance of its composites with poly(ethylene terephthalate) (PET) fibers. In this article, we report on the morphology and physicomechanical and tribological properties of modified UHMWPE/PET composites. Composites containing chemically modified UHMWPE had higher impact properties than those based on unmodified UHMWPE because of improved interfacial bonding between the polymer matrix and the fibers and better dispersion of the fibers within the modified UHMWPE matrix. Chemical modification of UHMWPE before the introduction of PET fibers resulted in composites exhibiting improved wear resistance compared to the base material and compared to unmodified UHMWPE/PET composites. On the basis of the morphological studies of worn samples, microploughing and fatigue failure associated with microcracking were identified as the principle wear mechanisms. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci, 2006     

Introducing four different branch structures in PET by reactive processing––A rheological investigation

Chain extension/branching by reactive processing is a well-known method to enhance the rheological properties of polymers. In this study, pyromellitic dianhydride, poly(glycolic acid), triglycidyl isocyanurate, and bisphenol A diglycidyl ether were used as chain extender/branching agents to produce branched Polyethylene terephthalate (PETs) with four different molecular structures. According to the linear rheological characterizations, the storage modulus and complex viscosity of modified PET samples enhanced significantly after branching. The shear viscosities of modified PET show a pronounced shear-thinning behavior and a remarkable increase at low frequencies, which can be an indication of the existence of long-chain branches (LCBs) in the molecular structure of polymer and broadening the molecular weight distribution. Fourier transform infrared (FTIR) and differential scanning calorimetry (DSC) analysis were used to investigate the effect of branching agents on the chemical structure and thermal properties of PET, respectively. DSC results show that higher amounts of LCBs lead to lower melting and crystallization temperatures.     

Surface modification of ultra‐high‐molecular‐weight polyethylene. I. Characterization and sintering studies

We performed surface modification of ultra‐high‐molecular‐weight polyethylene (UHMWPE) through chromic acid etching with the aim of improving the performance of UHMWPE's composites with poly(ethylene terephthalate) fibers. In part I of this study, we evaluated the effects of chemical modification on the surface properties of UHMWPE with X‐ray photoelectron spectroscopy (XPS), Fourier transform infrared spectroscopy (FTIR), and contact angle measurements. The thermal properties, rheology, and sintering behavior of the modified UHMWPE were compared to those of the base material. XPS and FTIR analysis confirmed the presence of carboxyl and hydroxyl groups on the surface of the modified powders. The substitution of polar groups into the backbone of the polymer decreased its contact angles with water and hexadecane and increased its surface energy, as evidenced by contact angle measurements. The modified UHMWPE was more crystalline than the base resin and less prone to thermal degradation. Although the rheological properties were virtually identical, the modified powders sintered more readily, presumably due to their higher surface energy, which suggested enhanced processability by compression molding. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci, 2006     

Preparation and properties of antibacterial,biocompatible core–shell fibers produced by coaxial electrospinning

Coaxial electrospinning is a method for producing fibrous mats with optional features, such as antibacterial properties, controllable release, and hydrophobicity based on shell materials. Because these features are important in biomedical applications, in this study, biocompatible hydrophobic polymer (polycaprolactone) and hydrophilic polymer [poly(vinyl alcohol)] with silver nanoparticles loaded in the core solution were coaxially electrospun. The effect of silver addition on the conductivity and viscosity of the solutions, chemical structure of the fiber mats, mechanical properties, porosity, hydrophobicity, water vapor transmission rate (WVTR), silver release, and antibacterial properties were investigated. Fibers with silver exhibited less porosity and a lower WVTR and a greater contact angle than the fibers without silver. Furthermore, the core–shell fibers reduced the burst release of silver and successfully prevented the growth of Escherichia coli and Staphylococcus aureus bacteria. Therefore, it seems that these fibers are suitable for providing electrospun mats with long‐term antibacterial properties. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44979.     

TPU/PCL/nanomagnetite ternary shape memory composites: studies on their thermal, dynamic-mechanical, rheological and electrical properties

Shape memory polymer composites based on a blend of thermoplastic polyurethane (TPU) segmented block copolymer and poly(ε-caprolactone) (PCL) with weight ratio of 70/30 and various nanomagnetite contents (0–5 wt%) were prepared by melt blending of TPU and PCL, together with a masterbatch of TPU/nanomagnetite. The samples were compounded for 10 min at 200 °C using an internal mixer. Synthesized nanomagnetite powder was introduced to the masterbatch via a solution mixing method using a high-intensity ultrasonic horn. Subsequently, thermal, mechanical, rheological and electrical properties of the TPU/PCL/nanomagnetite shape memory composites were investigated through various tests. The degree of crystallization of the PCL component in the composite structure was inspected by differential scanning calorimetry (DSC) and X-ray diffraction measurements. The results revealed that the percentage of crystallinity and the melting temperature of the PCL component changed in the presence of magnetite nanoparticles, which was related to the nanoparticles acting as nucleants. Observing a single glass transition temperature (T _g) in DSC thermograms of the samples was indicative of good compatibility of the TPU and PCL components in the composite structure. This was also confirmed by dynamic-mechanical analysis in which the loss modulus curves showed a single glass transition temperature. Moreover, the loss modulus peak at glass transition was lowered and broadened by addition of nanomagnetite, by which it was assumed that introducing nanoparticles into the system changed the mechanism of glass transition due to particle–matrix interactions. The dynamic rheological and electrical resistivity experiments verified the existence of a low percolation threshold at about 2 wt% nanomagnetite. The state of nanomagnetite dispersion in the masterbatch and the microstructure of the ternary composites were characterized by scanning electron microscopy. Finally, adding nanomagnetite led to weakening of shape recovery of the polymer blend, with shape recovery dropping to 70 % at 5 % of nanomagnetite.     

Thermal properties,rheology and sintering of ultra high molecular weight polyethylene and its composites with polyethylene terephthalate

The addition of polyethylene terephthalate (PET) fibers in ultra high molecular weight polyethylene (UHMWPE) may be a promising approach to achieve improved wear properties in artificial joints. Since UHMWPE/PET composites are processed by compression molding, which involves compaction and sintering of polymeric powders, this article investigates their rheology, thermal properties, and sintering behavior to aid in the identification and selection of optimum processing conditions. Isothermal crystallization kinetics studies have revealed that crystallization of UHMWPE proceeds via heterogeneous nucleation and is governed by two‐dimensional growth. The crystallization rates of the composites were lower than those of the neat material, whereas their ultimate crystallinities were higher. The UHMWPE/PET composites had higher viscosity and elasticity than the neat resin. In the presence of PET fibers the onset of sintering took place at higher temperatures but proceeded at substantially higher rates as compared with pure UHMWPE. A marked discrepancy between the Eshelby‐Frenkel model and experimental sintering data suggests that viscous flow is not the prevailing mechanism for coalescence but rather that enhanced surface area, attributed to the highly developed internal morphology of UHMWPE particles, is the controlling factor. POLYM. ENG. SCI., 45:678–686, 2005. © 2005 Society of Plastics Engineers     

One-Step Synthesis of Zirconia and Magnetite Nanocomposite Immobilized Chitosan for Micro-Solid-Phase Extraction of Organophosphorous Pesticides from Juice and Water Samples Prior to Gas Chromatography/Mass Spectroscopy

In this research, a magnetic sorbent was prepared by immobilizing zirconia and magnetite (Fe₃O₄) nanoparticles in chitosan, which is characterized and used as an effective nanosorbent in magnetic dispersive micro-solid-phase extraction (MDMSPE) of organophosphorous pesticides (OPPs) from juice and water samples prior to gas chromatography-mass detection (GC-MS). The properties and morphology of synthesized sorbent were characterized by scanning electron microscopy (SEM), Fourier transform-infrared spectroscopy (FT-IR), vibrating sample magnetometry (VSM), and differential scanning calorimetric (DSC) analysis. The main experimental parameters including pH level, extraction time, sorbent mass, salt concentration, and desorption conditions were investigated and optimized to maximize extraction efficiency. Under optimized conditions, the calibration curves were obtained in the concentration range of 0.1–500 ng mL^?1 with correlation coefficients between 0.9993 and 0.9999. The limits of detection (signal-to-noise ratio (S/N) = 3) and limits of quantification (S/N = 10) of the method ranged from 0.031 to 0.034 ng mL^?1 and 0.105–0.112 ng mL^?1, respectively. The intra-day and inter-day RSDs were 2.2–5.7 and 2.5–7.5%, respectively. The method was successfully applied to the analysis of OPPs in fruit juices (apple, peach, and cherry) and water (mineral, tap, and river) real samples, with recoveries in the range of 86.0–106.0% for the spiked juice and water samples. The results showed that with combination of high selectivity of zirconia and magnetic property of magnetite as well as immobilizing ability of chitosan, the fabricated sorbent exhibited exceptional extraction ability toward the OPPs.     

Comparative and competitive adsorption of Cu(II), Cd(II) and Pb(II) onto Sepia pharaonis endoskeleton biomass from aqueous solutions

In this research, the possibility of simultaneous removal of lead, cadmium and copper divalent ions from water samples through the use of Sepia pharaonis endoskeleton powder (SPEB) as bio‐material, was investigated. The bio‐sorbent was characterised by Fourier transform infrared spectrum (FT‐IR), atomic force microscopy (AFM) and X‐ray fluorescence (XRF). The different factors affecting the bio‐sorption process were studied. Langmuir and Freundlich isotherm models were applied to analyse the experimental data. The kinetic studies showed that the pseudo‐second order model kinetics were compatible with the investigated systems. It was found that under optimal conditions, this bio‐sorbent was efficient in the uptake of these heavy metal ions from both mono and multi‐metal solutions, and high removal percentages were achieved. This study verified the potential ability of SPEB as an efficient natural adsorbent for removal of Pb(II), Cd(II) and Cu(II) ions from river, tap and mineral water samples.     

Structural analysis of poly(ethylene terephthalate) modified by polypropylene-graft-maleic anhydride from rheological data

During some investigations on compatibilizing poly(ethylene terephthalate) (PET) blends by maleic anhydride–grafted polyolefins (PO-g-MA), the reaction between PET and PO-g-MA and the formation of PO-g-PET were proposed. However, the effect of PO-g-MA on the rheological properties of PET has not been the aim of any specific study. In our study, polypropylene (PP)-g-MA was melt reacted with PET, and the effects of its content and grafting degree on the intrinsic viscosity and linear viscoelastic properties of PET were investigated. The results reveal that the addition of PP-g-MA leads to increasing intrinsic viscosity, which confirms the reaction between PP-g-MA and PET. Rheological measurements suggest that the addition of PP-g-MA improves the elastic behavior and increases the complex viscosity of PET. No shear thinning behavior was observed for any samples, indicating that branching is not widespread. The increase in PP-g-MA content or grafting degree leads to increases in the intrinsic and complex viscosities and improves the elastic behavior. Furthermore, we reported the unusual observation of an increasing viscosity with frequency in modified sa"mples due to the transesterification phenomenon. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 46896.