Fullerene-like Re-Doped MoS2 Nanoparticles as an Intercalation Host with Fast Kinetics for Sodium Ion Batteries

Sodium ion batteries (SIBs) are considered as a promising alternative to threaten the reign of lithium ion batteries (LIBs) among various next-generation rechargeable energy storage systems, including magnesium ion, metal air, and metal sulfur batteries. Since both sodium and lithium are located in Group 1 of the periodic table, they share similar (electro)chemical properties with regard to ionization pattern, electronegativity, and electronic configuration; thus the vast number of compounds developed from LIBs can provide guidance to design electrode materials for SIBs. However, the larger ionic radius of the sodium cation and unique (de)sodiation processes may also lead to uncertainties in terms of thermodynamic or kinetic properties. Herein, we present the first construction of SIBs based on inorganic fullerene-like (IF) MoS₂ nanoparticles. Closed-shell-type structures, represented by C₆₀ fullerene, have largely been neglected for studies of alkali-metal hosting materials due to their inaccessibility for intercalating ions into the inner spaces. However, IF-MoS₂, with faceted surfaces, can diffuse sodium ions through the defective channels, thereby allowing reversible sodium ion intercalation/deintercalation. Interestingly, Re-doped MoS₂ showed good electrochemical performances with fast kinetics (ca. 74 mA h g⁻¹ at 20 C). N-type doping caused by Re substitution of Mo in IF-MoS₂ revealed enhanced electrical conductivity and an increased number of diffusion defect sites. Thus, chemical modification of fullerene-like structures through doping is proven to be a promising synthetic strategy to prepare improved electrodes.     

Polypropylene random copolymer/MWCNT nanocomposites: Isothermal crystallization kinetics,structural, and morphological interpretations

This article describes the crystallization process of polypropylene random copolymer (PPCP) under isothermal conditions in presence of varying amounts of multiwalled carbon nanotubes (MWCNT) ranging from 0.5 to 4.0% w/w. Increase in the crystallization temperature under dynamic conditions confirmed the nucleating behavior of MWCNTs, which was also corroborated by crystallization studies under isothermal conditions. The crystallization kinetics was analyzed using Avrami equation and the parameters such as Avrami exponent, the equilibrium melting temperature and fold surface energy for the crystallization of PPCP chains in nanocomposites were obtained from the calorimetric data in order to determine the effect of MWCNTs on these parameters. Spherulitic growth of PPCP crystals was also investigated as a function of time and MWCNT content using hot stage polarizing microscope. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41734.     

Ethylene polymerization with homogeneous and heterogeneous catalysts based on bis(4‐fluorophenyl)methyl‐substituted bis(imino)pyridyliron complexes

A series of bis(4‐fluorophenyl)methyl‐substituted bis(imino)pyridyliron chloride complexes were immobilized on oxide supports. The kinetics of ethylene polymerization by both homogeneous and heterogeneous systems was followed, the catalysts mostly demonstrating high activities. The effect of the ligands nature and reaction conditions on the catalytic activities and molecular weights of the resultant polyethylenes was examined. In contrast to homogeneous systems, the supported iron complexes were found to exhibit high and stable activity upon activation with triisobutyl aluminium, producing high‐molecular‐weight polyethylene with good morphology. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42674.     

Influence of polymer morphology on the adsorption behaviors of molecularly imprinted polymer‐methacrylic acid functionalized β‐cyclodextrin

The influence of molecularly imprinted polymer‐methacrylic acid functionalized β‐cyclodextrin (MIP(MAA‐β‐CD)) morphology on the adsorption behavior studies towards benzylparaben (BzP) was explored. The effects of time, concentration, and temperature towards BzP uptake were extensively evaluated. The adsorption performance of MIP(MAA‐β‐CD) was compared with that on the molecularly imprinted polymer‐methacrylic acid (MIP(MAA)) synthesized without β‐CD. The MIP(MAA‐β‐CD) was synthesized to obtain a spherical and spongy‐porous texture with a broad pore size distribution. The MIP(MAA‐β‐CD) showed fast kinetic and the intra‐particle diffusion model demonstrated a three step (surface and pore) adsorption process. The Koble‐Corrigan isotherm was the most suitable model for data fitting, which indicated that MIP(MAA‐β‐CD) had homogeneous and heterogeneous surfaces. This finding clearly demonstrated that the large uptake and strong affinity of MIP(MAA‐β‐CD) did not only probably result from the monomer‐template interactions, but also due to the morphological MIP(MAA‐β‐CD) structure. In contrary to MIP(MAA‐β‐CD), MIP(MAA) synthesized with uniform morphology and narrow pore size distribution had lower adsorption capacities and its kinetic data fitted the pseudo‐second order diffusion model, indicating a two‐step (surface only) adsorption process. The MIP(MAA) adsorption process followed the Langmuir isotherm model referred to solely homogeneous uptake. The calculated thermodynamic parameters showed that the BzP uptake was exothermic, spontaneous, and physisorption process onto MIPs, which supported the results of kinetics and isotherm adsorption data. This study clearly revealed that the presence of β‐CD improved the morphology of synthesized MIP, and automatically enhanced the adsorption behavior of MIP. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42720.     

Multilayer‐coated NPK compound fertilizer hydrogel with controlled nutrient release and water absorbency

A novel trilayered controlled‐release nitrogen, phosphorous, and potassium (NPK) fertilizer hydrogel was prepared by dipping the NPK fertilizer granules sequentially in 7% w v^?1 poly(vinyl alcohol) (PVA) and 2% w v^?1 chitosan (CS) solutions and then cross‐linking the CS layer (cross‐CS) via glutaraldehyde vapor deposition. Different NPK fertilizer hydrogels were then synthesized by inverse suspension polymerization of the dried PVA/cross‐CS bilayer‐coated fertilizer granules in various molar ratios of acrylamide (AM) and acrylic acid (AA) monomers, and polymerization with varying molar ratios of ammonium persulfate, N,N,N′,N′‐tetramethylethylenediamine and N,N′‐methylenebisacrylamide (N‐MBA). The water dissolution time of the obtained PVA/cross‐CS/poly (AA‐co‐AM) trilayer‐coated NPK fertilizer hydrogel granules was prolonged, while the water absorbency increased with increasing AA contents, and decreased with increasing N‐MBA contents in the outer poly(AA‐co‐AM) coating. The optimal trilayer‐coated NPK fertilizer hydrogel obtained released 84 ± 18, 63 ± 12, and 36 ± 15% of the N, P, and K nutrients, respectively, after a 30‐day immersion in water. The release phenomena of the N, P, and K nutrients of the fertilizer hydrogel obeyed both the Korsmeyer‐Peppas and Ritger‐Peppas models with a pseudo‐Fickian diffusion mechanism. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41249.     

Effects of different ionizable groups on the thermal properties of waterborne polyurethanes used in bulletproof composites

The thermal stability of the resin matrix is an important factor affecting the safety performance of fiber‐reinforced bulletproof composites (FRBCs) during their service period. In this study, two kinds of waterborne polyurethanes based on polyester diol (PEDL218) and isophorone diisocyanate were synthesized; these were used as the matrix of para‐aramid FRBCs. Their thermal stability and thermal decomposition behaviors in a nitrogen atmosphere were studied by dynamic thermogravimetric analysis techniques. The kinetic parameters, including the activation energy (E) and pre‐exponential factor (A), were calculated by the Flynn–Wall–Ozawa, Kissinger–Akahira–Sunose, Kissinger, and ?atava–?esták methods. The results show that the cationic waterborne polyurethane with quaternary ammonium groups has better thermal stability than the anionic waterborne polyurethane with carboxylate groups. Their nonisothermal decomposition mechanisms were studied, and the kinetic parameters were also calculated; this will offer theoretical reference for the manufacturing and application of FRBCs based on waterborne polyurethane. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42374.     

A new method for estimating the isothermal devitrification and crystallization of mold powder slags from non-isothermal DSC data

The rate of formation of crystalline phases from liquid and glassy mold powder slags is of foremost importance in the performance of molds used for continuous casting of steel. This study shows how the Induction Period (of Šimon and Kolman) and the Kissinger methods can be combined in a kinetic model to evaluate the isothermal rate of formation of crystalline phases from thermo-analytical data – onset temperature, T_i, peak maximum temperature, T_m, shape index, S, and conversion at peak maximum, x_m – collected at various linear heating and cooling rates. The diagram of the extent of isothermal transformation as a function of time calculated for a commercial mold powder, used for casting low carbon steels, shows good agreement with the degree of transformation observed in photomicrographs of glass disks devitrified isothermally, at several temperatures for different times. Additionally, qualitative and quantitative X-ray diffraction results obtained at room-temperature from glass powder samples treated isothermally and quenched also show good accord with the degree of transformation predicted with the kinetic model developed in this work.