Fabrication of Fe-doped ZnO/nanocellulose nanocomposite as an efficient photocatalyst for degradation of methylene blue under visible light

Cellulose - In this work, a photocatalytic nanocomposite, Fe-doped ZnO/nanocellulose, was synthesized using an in-situ method and examined for methylene blue (MB) degradation. For this purpose,...     

MgO nanopowders catalyzed synthesis of pyrano[4,3-d]thiazolo[3,2-a]pyrimidine derivatives

A cubic phase of pure MgO nanopowders was prepared in an aqueous solution containing freshly squeezed orange juice with pulp and characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), energy-dispersive X-ray spectroscopy (EDS), and Fourier transform infrared (FT-IR) spectroscopic techniques. The catalytic potential of MgO nanopowders was evaluated in preparation of pyrano[4,3-d]thiazolo[3,2-a]pyrimidine and chromeno[4,3-d]thiazolo[3,2-a]pyrimidines derivatives using the three simple methods including thermal, ultrasonic irradiation, and high-speed ball milling (HSBM) technique under solvent-free conditions. All products were successfully formed in high yields.     

Preparation of highly exfoliated polyester-clay nanocomposites: process-property correlations

A large number of polyester nanocomposite batches featuring different kinds of nanoclay surface modifiers and up to 6 wt % nanoclay were manufactured using a solvent-based technique. Montmorillonite platelets modified with ammonium ions of different chemical architectures were examined to study the effect of ammonium ions on the extent of surface reactions with long-chain fatty acids. The ammonium montmorillonite was first dispersed and suspended in acetone. This suspension was further esterificated with dotriacontanoic (lacceroic) acid to form high density brushes on the clay surface. This led to achieving higher basal plane spacing of the montmorillonite platelets due to the reduction of electrostatic interactions holding them. The outcome of the surface esterification was analyzed by Fourier transform infrared spectroscopy (FTIR) and X-ray diffraction (XRD). The esterificated ammonium-modified clays were then mixed by five different mixing strategies based on the use of a three-roll mill mixer (TRM) and/or ultrasonication (US) to obtain the desired polyester-nanoclay dispersion, intercalation, and exfoliation. The dispersion states of the modified nanoclay in polymer were characterized from XRD, scanning electron microscopy (SEM), and low and high magnification transmission electron microscopy (TEM). Mechanical, thermal, and barrier properties of the resulting composites were experimentally characterized. The Mori-Tanaka method along with an orientation distribution function was used to verify the experimental effective stiffness of the polyester nanocomposite systems. The aspect ratio of nanoclays and their level of intercalation and/or exfoliation after mixing were also confirmed by the comparison of the experimental diffusivity results with those of Fick's diffusion model. Systems having 4 and 6 wt % esterificated ammonium nanoclay and prepared according to a combined TRM/US mixing procedure showed optimal performance with balanced properties and processing ease, thereby showing potential for use in the automotive, transportation, and packaging industries.     

Experimental Investigation of Heat Transfer Coefficient from the Impingement of a Slot Jet Using Conjugate Gradient Method with Adjoint Equation

The convective heat transfer coefficients resulting from a slot jet on a plane surface have been estimated by using the real measured temperatures in the plate and inverse method. In this study, the inverse method used the conjugate gradient method with an adjoint equation. Distributions of the local heat transfer coefficient on the impingement surface were determined for various Re and H/Dh. It was found the heat transfer coefficients generally tended to decrease with increasing separation distance and to increase with an increase in Reynolds number. This presented method is able to estimate the variation of the local Nusselt number with time.     

Investigating the interaction of x-ray free electron laser radiation with grating structure

The interaction of free electron laser pulses with grating structure is investigated using 4.6±0.1 nm radiation at the FLASH facility in Hamburg. For fluences above 63.7±8.7 mJ/cm², the interaction triggers a damage process starting at the edge of the grating structure as evidenced by optical and atomic force microscopy. Simulations based on solution of the Helmholtz equation demonstrate an enhancement of the electric field intensity distribution at the edge of the grating structure. A procedure is finally deduced to evaluate damage threshold.     

Ab Initio Study of the Various Pathways of the Decomposition ([2+2]elimination) of 2-Chloroethyltrichlorosilane

Abstract

The decomposition of 2-chloroethyltrichlorosilane (1) to ethylene-tetrachlorosilane (2), hydrogen chloride-ethylenetrichlorosilane (3), and ethylenechloride-trichlorosilane (4) was investigated using ab initio Molecular Orbital (MO) and Density Functional Theory (DFT). Study on the HF/6-31G level of theory revealed that the required energy for the decomposition of compound 1 to 2, 3, and 4 is 59.86, 101.13, and 63.29 kcal mol^?, respectively. MP2/6-31G*//HF/6-31G* calculated barrier height for the decomposition of compound 1 to 2, 3, and 4 is 60.59, 94.04, and 66.91 kcal mol^?1, respectively. Also, B3LYP/6-31G*//HF/6-31G* results indicate that the barrier height for the decomposition of compound 1 to 2, 3, and 4 is 51.71, 85.38, and 53.74 kcal mol^?1, respectively. Among the three methods, which have been used to calculate the barrier height of the decomposition of compound 1 to 2–4, B3LYP/6-31G**//HF/6-31G** is in good agreement with the reported experimental data. Contrary to the previously evaluated experimental values for the decomposition of compoun 1 to 3 and 4, all three methods predict a higher energy barrier for these reactions.     

A two‐scale approach to electron correlation in multiconfigurational perturbation theory

We present a new approach for the calculation of dynamic electron correlation effects in large molecular systems using multiconfigurational second‐order perturbation theory (CASPT2). The method is restricted to cases where partitioning of the molecular system into an active site and an environment is meaningful. Only dynamic correlation effects derived from orbitals extending over the active site are included at the CASPT2 level of theory, whereas the correlation effects of the environment are retrieved at lower computational costs. For sufficiently large systems, the small errors introduced by this approximation are contrasted by the substantial savings in both storage and computational demands compared to the full CASPT2 calculation. Provided that static correlation effects are correctly taken into account for the whole system, the proposed scheme represent a hierarchical approach to the electron correlation problem, where two molecular scales are treated each by means of the most suitable level of theory. © 2014 Wiley Periodicals, Inc.     

Estimation of monomer reactivity ratios in free‐radical solution copolymerization of lauryl methacrylate–isobutyl methacrylate

Copolymers of isobutyl methacrylate (i‐BMA) and lauryl methacrylate (LMA) were prepared by free‐radical solution copolymerizations at 70 °C with azobisisobutyronitrile (AIBN) as an initiator. The synthesis of these copolymers was investigated over a wide composition range both at low and high conversion levels. Copolymer compositions were determined from the %C, %H, and %O contents of copolymer by elemental analysis. Monomer reactivity ratios were estimated by analyzing composition data with nonlinear least‐squares (NLLS) models based on Marquardt optimization and van Herk methods. The point estimates, 95% individual confidence intervals and 95% joint confidence intervals are obtained from differential and integral approaches. Even though no explicit integral form for penultimate unit model (PUM) is available, a numerical approach is developed for integral estimation of reactivity ratios from PUM. A simulator program was developed which upon coupling of experimental data, NLLS analysis, and D‐optimal criteria calculates the best optimized values of monomer reactivity ratios and monomer feed compositions in a sequential and iterative order for terminal and penultimate unit models. Moreover, the simulator has the capibilities to calculate all features of van Herk method, maximum compositional drift in each monomer feed composition, and data reconciliation. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 112–129, 2004