Direct Amide Synthesis from Alcohols and Amines by Phosphine‐Free Ruthenium Catalyst Systems

Amides are synthesized directly from alcohols and amines in high yields using an in situ generated catalyst from easily available ruthenium complexes such as the (p‐cymene)ruthenium dichloride dimer, [Ru(p‐cymeme)Cl₂]₂, or the (benzene)ruthenium dichloride dimer, [Ru(benzene)Cl₂]₂, an N‐heterocyclic carbene (NHC) ligand, and a nitrogen containing L‐type ligand such as acetonitrile. The phosphine‐free catalyst systems showed improved or comparable activity compared to previous phosphine‐based catalytic systems. The in situ generated catalyst from [Ru(benzene)Cl₂]₂, an NHC ligand, and acetonitrile showed excellent activity toward reactions with cyclic secondary amines such as piperidine and morpholine.     

Thermal properties of field-assisted-sintered SiCN–Y2O3 composites

Polymer-derived amorphous SiCN has excellent high-temperature stability and properties. To reduce the shrinkage during pyrolysis and to improve the high-temperature oxidation resistance, Y₂O₃ was added as a filler. In this study, polymer-derived SiCN–Y₂O₃ composites were fabricated by mixing a polymeric precursor of SiCN with Y₂O₃ submicron powders in different ratios. The mixtures were cross-linked and pyrolyzed in argon. SiCN–Y₂O₃ composites were processed using field-assisted sintering technology at 1350°C for 5 min under vacuum. Dense SiCN–Y₂O₃ composite pellets were successfully made with relative density higher than 98% and homogeneous microstructure. Due to low temperature and short time of the heat-treatment, the grain growth of Y₂O₃ was substantially inhibited. The Y₂O₃ grain size was ∼1 μm after sintering. The composites’ heat capacity, thermal diffusivity, and thermal expansion coefficients were characterized as a function of temperature. The thermal conductivity of the composites ceramics decreased as the amount of amorphous SiCN increased and the coefficient of thermal expansion (CTE) of the composites increased with Y₂O₃ content. However, the thermal conductivity and CTE did not follow the rule of mixture. This is likely due to the partial oxidation of SiCN and the resultant impurity phases such as Y₂SiO₅, Y₂Si₂O₇, and Y_4.67(SiO₄)₃O.     

Dielectric relaxation studies of low thermal expansion polymer composites

The results of temperature‐dependent dielectric and rheological measurements are reported on polymer‐ceramic composite films, poly(methyl methacrylate) (PMMA) : lead titanate (PbTiO₃). Analyses of relaxational processes of the PMMA host matrix have been investigated using temperature‐dependent dielectric and rheological measurements. It is found that the α‐relaxation is more significantly affected by the addition of filler in comparison to β‐relaxation. The composite films are found to have much lower dielectric constants in comparison to the pure ceramic material. Suitable models have been used to explain the observed dielectric constant of the composite films. Using rheological measurements, occurrence of reinforcement in these composite films due to the addition of ceramic filler has also been observed and the results are discussed in the article. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Contribution of organomodified clay on hybrid microstructures and properties of epoxidized natural rubber‐based nanocomposites

Influence of organic modifying agent of clay on dispersion, distribution, hybrid microstructure formation, and associated performance properties of epoxidized natural rubber‐based composites was evaluated. Binary and ternary composites of carbon black (CB) and two organomodified layered silicates (i.e., nanomer I30E and Cloisite 30B) were prepared and characterized based on small angle X‐ray scattering, transmission electron microscopy, hydrodynamic swelling, tensile measurement, and dynamic mechanical analyses. Greater extent of exfoliation and “nanounit” formation was noted in ternary composites containing nanomer I30E, which was reflected in higher interfacial roughness (d_s = 2.82) and lower radius of gyration (R_g = 205 Å). Morphological observations suggested higher nanomer I30E–CB interactions than that of Cloisite 30B–CB. The interplatelet distance in Cloisite 30B (d = 1.83 nm) stacks was lower than that of nanomer I30E (d = 2.26 nm). These two factors jointly contributed in higher breakdown of nanomer I30E stacks by CB than that of Cloisite 30B stacks. Greater exfoliation and nanounit formation in I30E–CB‐filled nanocomposite was also reflected in increased degree of crosslinking (n = 20 × 10^?5%), tensile modulus/strength, half height width of damping peak (20.3°C), and filler effectiveness (C = 0.33). POLYM. ENG. SCI., 2013. © 2012 Society of Plastics Engineers     

STUDIES ON THE ADSORPTION OF FURFURAL FROM AQUEOUS SOLUTION ONTO LOW-COST BAGASSE FLY ASH

The present study deals with the sorptive removal of furfural from aqueous solution by carbon-rich bagasse fly ash (BFA). Batch studies were performed to evaluate the influence of various experimental parameters, namely, initial pH (p H ₀), adsorbent dose, contact time, initial concentration, and temperature on the removal of furfural. Optimum conditions for furfural removal were found to be p H ₀ ≈ 5.5, adsorbent dose ≈4 g/L of solution, and equilibrium time ≈4 h. The adsorption followed pseudo-second-order kinetics. The effective diffusion coefficient of furfural is of the order of 10^?13 m²/s. Equilibrium adsorption data on BFA was analyzed by Freundlich, Langmuir, Dubnin-Radushkevich, Redlich-Peterson, and Temkin isotherm equations using regression and error analysis. The Redlich-Peterson isotherm was found to best represent the data for furfural adsorption onto BFA. Adsorption of furfural on BFA is favorably influenced by a decrease in the temperature of the operation. Values of the change in entropy (ΔS ⁰) and heat of adsorption (ΔH ⁰) for furfural adsorption on BFA were negative. The high negative value of change in Gibbs free energy (ΔG ⁰) indicates the feasible and spontaneous adsorption of furfural on BFA.     

Catalytic Activity of Cu/SBA‐15 for Peroxidation of Pyridine Bearing Wastewater at Atmospheric Condition

In this study, Cu‐loaded Santa Barbara amorphous (SBA)‐15 catalysts were synthesized by impregnation method and further used for catalytic wet peroxidation (CWPO) of pyridine from aqueous solution using hydrogen peroxide as oxidant. The synthesized catalysts have been characterized by Brunauer–Emmett–Teller surface area: temperature‐programmed reduction, H₂‐chemisorption, Fourier transform infrared spectroscopy, and field emission scanning electron microscopy. Characterization results indicate good dispersion of Cu species inside the porous structure of SBA‐15. The effect of various parameters such as Cu loading on SBA‐15, pH, catalyst dose, H₂O₂ concentration, and temperature have been studied for their effect on CWPO of pyridine. More than 97% pyridine removal and 92% total organic carbon removal was achieved at optimum condition. Cu/SBA‐15 showed stable performance during reuse for six cycles with negligible copper leaching. © 2013 American Institute of Chemical Engineers AIChE J, 59: 2577–2586, 2013     

Effect of PES on the morphology and properties of proton conducting blends with sulfonated poly(ether ether ketone)

Development of alternate materials to Nafion, based on ionically conducting polymers and their blends is important for the wider applications of proton exchange membrane fuel cells. In this work, blends of sulfonated poly(ether ether ketone) (SPEEK) with poly(ether sulfone) (PES) are investigated. SPEEK with various ion exchange capacity (IEC) was prepared and blended with PES, which is nonionic and hydrophobic in nature. A comparative study of the water uptake, proton conductivity, and thermo‐mechanical characteristics of SPEEK and the blend membranes as a function of the IEC is presented. Addition of PES decreases the water uptake and conductivity of SPEEK. Chemical and thermal stability and mechanical properties of the membrane improve with the addition of PES. The effect of water content on the thermo‐mechanical properties of membranes was also studied. The morphology of blend membranes was studied using SEM to understand the microstructure and miscibility of the components. On the basis of the results, a plausible microstructure of the blends is presented, and is shown to be useful in understanding the variation of different properties with blending. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Synthesis of alkyne‐terminated xanthate RAFT agents and their uses for the controlled radical polymerization of N‐vinylpyrrolidone and the synthesis of its block copolymer using click chemistry

Two new alkyne‐terminated xanthate reversible addition‐fragmentation chain‐transfer (RAFT) agents: (S)‐2‐(Propynyl propionate)‐(O‐ethyl xanthate) (X₃) and (S)‐2‐(Propynyl isobutyrate)‐(O‐ethyl xanthate) (X₄) were synthesized and characterized and used for the controlled radical polymerization of N‐vinylpyrrolidone (NVP). X₃ showed better chain transfer ability in the polymerization at 60°C. Molecular weight of the resulted polymer increased linearly with the increase in monomer loading. Kinetics study with X₃ showed the pseudo‐first order kinetics up to 67% monomer conversion. Molecular weight (M_n) of the resulting polymer increased linearly with the increase in the monomer conversion up to around 67%. With the increase in the monomer conversion, polydispersity of the corresponding poly(NVP)s initially decreased from 1.34 to 1.32 and then increased gradually to 1.58. Chain‐end analysis of the resulting polymer by ¹H‐NMR and FTIR showed clearly that polymerization started with radical forming out of xanthate RAFT agent. Living nature of the polymerization was also confirmed from the successful homo‐chain extension experiment and the hetero‐chain extension experiment involving synthesis of poly(NVP)‐b‐polystyrene amphiphilic diblock copolymer. Formed alkyne‐terminated poly(NVP) also allowed easy conjugation to azide‐terminated polystyrene by click chemistry to prepare well‐defined poly(NVP)‐b‐polystyrene block copolymers. Resulting polymers were characterized by GPC, ¹H‐NMR, FTIR, and thermal study. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Size Distribution and Morphology of Liposome Aerosols Generated By Two Methodologies

Pulmonary delivery of sustained release formulations needs drug encapsulation in a suitable matrix, as well as the generation of aerosols with high lung penetration and suitable release characteristics. Nanometer sized liposomes offer the potential for biocompatibility, controlled release and easy internalization in the lung. For uniform dose delivery and drug release kinetics, it is of interest to understand generation techniques to obtain aerosols containing nearly monodispered nanometer sized dry particles. Two aerosolization techniques, air-jet atomization and electrohydrodynamic atomization (EHDA) were studied to identify conditions under which the inclusion of one-liposome-per-drop could be achieved. In air-jet atomization, low lipid concentrations resulted in a unimodal aerosol with a median mobility diameter of 94 (± 3.5) nm, while higher concentrations led to larger median diameters, implying possible inclusion of multiple liposomes per drop. In EHDA, tuning drop sizes in the range of 130 to 200 nm, as well as the use of high lipid concentrations, resulted in a bimodal aerosol distribution, with peaks at 35 and 100 nm mobility diameters. TEM images of the liposome aerosol from EDHA showed fused liposomes, resulting in cylindrical structures with different physical diameters. It was hypothesized that deformation of liposomes to cylindrical structures in the micro-capillary liquid tip of the electrospray, and interactions along the axial or cross sectional surfaces led to dry particles with different mobility sizes.