Peroxide‐mediated crosslinking of poly(ethylene oxide)

The crosslinking of poly(ethylene oxide) (PEO) with a difunctional peroxide such as 2,5‐bis(tert‐butylperoxy)‐2,5‐dimethylhexane (Luperox 101) may proceed through at least two different pathways. Thus, the thermally formed alkoxy radicals abstract hydrogen from PEO, and the resulting PEO radicals may combine or react with the peroxide radicals to give ether or acetal crosslinks. However, these reactions also produce noncrosslinking acetals and vinyl ethers. The acetals may react further with peroxy or other radicals and yield orthoesters and ketene acetals. These and similar groups, in the presence of dilute acids, are susceptible to acid hydrolysis, leading to the disintegration of the gels. The gels, upon swelling in dilute acids, undergo a slow degradation process that is not observed for unmodified PEO. The acid hydrolysis is confirmed by a combination of size exclusion chromatography and dynamic mechanical analysis. IR analysis shows the presence of hydroxyl end groups and the presence of carboxylates rather than aldehyde groups, this is consistent with orthoesters and ketene acetal intermediates. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 3021–3026, 2002     

Fluidized Bed Polyethylene Reactor Modeling in Condensed Mode Operation

Summary: Modeling of fluidized bed reactor for polyethylene production in the condensed mode operation is proposed in this paper. A two-phase model including the emulsion and bubble phases with the constant bubble size is employed to describe hydrodynamic behavior of the reactor. The kinetics of Ziegler-Natta polymerization is also modeled with a two active site model. The phase behavior and solubility of low molecular weight components in polyethylene are estimated with the Sanchez-Lacombe equation of state. The validation of the model is carried out with industrial data for an ethylene and 1-butene copolymerization with the isopentane as a condensable component. The simulation results are in good agreement with industrial data. The model is also used to study quantitatively the effect of the inlet stream temperature to the reactor and isopentane concentration in the reactor on the production rate. For instance, in a typical process, when the inlet stream temperature changes 10 °C, the production rate will alter about 40%. Furthermore, the change of the isopentane concentration around 1 mole percentage leads to a variation of production rate about 14%.     

Synthesis of amides from imines using Et3SiH/Zn system

A simple and efficient approach for the synthesis of amides by the reaction of imines and acyl chlorides in the presence of Et₃SiH/Zn system in THF at ambient temperature is reported. Mild reaction conditions, good yields of products, short reaction time and operational simplicity are the advantages of this procedure. Copyright © 2012 John Wiley & Sons, Ltd.     

Effects of structural factors on filtering operation of photonic band gap air bridges with circular and square shape holes

Applying the finite element analysis on the photonic band-gap materials with a cavity at the center for two types of structures, circular and square shape holes with the same cross section, filtering operation of these structures is simulated and compared. Any variations in the structure parameters, such as cavity length, period and hole dimensions, change the transmission peak and frequency bandwidth of these structures. The effects of rotation of square holes and ellipticity of circular holes on filtering operation are studied. Other new structures such as tapered, shortened and non-uniform rotated structures are proposed and filtering characteristics of them are discussed. It is found that, by rotating the square holes around their axis, it is possible to have a blue-shift in the transmission peak wavelength without notable variations in the filter peak and bandwidth. It is concluded that the increase of elliptical holes diameters length causes the decrease of transmission peak and increase of bandwidth with blueshift of the peak wavelength. This shift is larger for one of the elliptical diameter values considered that is along the waveguide length.     

Green Synthesis of Ag Nanoparticles by Callicarpa Maingayi: Characterization and Its Application with Graphene Oxide for Enzymeless Hydrogen Peroxide Detection

A facile green synthesis of silver nanoparticles (AgNPs) was achieved using aqueous leaf extract of Callicarpa Maingayi as a reducing and stabilizing agent during the synthesis from its salt solutions. The synthesized silver nanoparticles were analyzed with transmission electron microscopy (TEM), X‐ray diffraction (XRD) and energy dispersive spectrometer (EDS). XRD study shows that the particles are crystalline in nature with face centered cubic geometry. The crystallite size obtained from XRD is about 15 nm which is in agreement well with the TEM results. A new nanostructure sensor was constructed by immobilizing silver nanoparticles and graphene oxide (AgNPs‐GO) composite film on a glassy carbon electrode (AgNPs‐GO/GCE). It was found that the AgNPs‐GO composite exhibits good catalytic activity toward the reduction of hydrogen peroxide (H₂O₂), leading to an enzymeless sensor with a fast amperometric response time of less than 5 s, high selectivity, good reproducibility and stability. The linear range was 5.0 μM to 700 μM with a detection limit of 0.6 μM (S/N = 3).