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  1. Abstract

    Managing water resources has become one of the most pressing concerns of scientists in both academia and industry. Broadening access to nontraditional water feedstocks, such as brackish water, seawater and wastewater, requires a robust pretreatment process to prolong the lifetime and improve the efficiency of reverse osmosis treatment processes. Herein, pretreatment membranes with tunable hydrophilic characteristics and mechanical properties were developed through a facile and scalable technique. Specifically, poly(vinyl alcohol) (PVA) and poly(vinyl chloride) (PVC) were electrospun at various PVA‐to‐PVC mass ratios and then crosslinked with a poly(ethylene glycol) diacid. Fiber diameters and morphologies were characterized using scanning electron microscopy (SEM); Fourier transform infrared spectroscopy and confocal fluorescence microscopy further confirmed the presence of both polymers. Moreover, a rigorous analysis to map the PVA/PVC concentration was established to accurately determine the relative concentrations of the two polymers on the co‐spun mat. The crosslinking reaction noted above tuned the membrane porosity from 500 to 80 nm, as seen using SEM, and the mechanical properties were probed using tensile testing. The data revealed that the PVC content controlled the mechanical strength; moreover, higher PVA contents were expected to increase water permeation by enhancing the hydrophilicity, but the higher degree of crosslinking in these materials actually reduced water permeation. This work introduces a facile, scalable route for the manufacture of pretreatment membranes with tunable porosity, mechanical properties and water permeation behavior. © 2021 Society of Industrial Chemistry.

     
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  5. Nanocomposites integrate functional nanofillers into viscoelastic matrices for electronics, lightweight structural materials, and tissue engineering. Herein, the effect of methacrylate-functionalized (MA-SiO 2 ) and vinyl-functionalized (V-SiO 2 ) silica nanoparticles on the thermal, mechanical, physical, and morphological characteristics of poly(ethylene glycol) (PEG) nanocomposites was investigated. The gel fraction of V-SiO 2 composites decreases upon addition of 3.8 wt% but increases with further addition (>7.4 wt%) until it reaches a plateau at 10.7 wt%. The MA-SiO 2 induced no significant changes in gel fraction and both V-SiO 2 and MA-SiO 2 nanoparticles had a negligible impact on the nanocomposite glass transition temperature and water absorption. The Young's modulus and ultimate compressive stress increased with increasing nanoparticle concentration for both nanoparticles. Due to the higher crosslink density, MA-SiO 2 composites reached a maximum mechanical stress at a concentration of 7.4 wt%, while V-SiO 2 composites reached a maximum at a concentration of 10.7 wt%. Scanning electron microscopy, transmission electron microscopy, and small-angle X-ray scattering revealed a bimodal size distribution for V-SiO 2 and a monomodal size distribution for MA-SiO 2 . Although aggregates were observed for both nanoparticle surface treatments, V-SiO 2 dispersion was poor while MA-SiO 2 were generally well-dispersed. These findings lay the framework for silica nanofillers in PEG-based nanocomposites for advanced manufacturing applications. 
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  6. Aryl chlorides (ArCl) or aryl fluorides (ArF) were used in polycondensation reactions to form poly(arylene ether sulfone)s (PAES). Interestingly, the kinetics of the ArF reaction fit a third-order rate law, which is attributed to the activation of the carbon–fluorine bond by two potassium cations (at least one bound to phenolate), which form a three-body complex. The ArCl monomer follows a second-order rate law, where a two-body complex forms at the initial state of the aromatic nucleophilic substitution (S N Ar) pathway. These metal cation-activated complexes act as intermediates during the attack by the nucleophile. This finding was reproduced with either the potassium or the sodium counterion (introduced via potassium carbonate or sodium carbonate). Through a combination of experimental analysis of reaction kinetics and computational calculations with density functional theory (DFT) methods, the present work extends the fundamental understanding of polycondensation mechanisms for two aryl halides and highlights the importance of the CX–metal interaction(s) in the S N Ar reaction, which is translational to other ion-activated substitution reactions. 
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