Catalytic properties of dispersed iron oxides Fe2O3/MO2 (M = Zr,Ce, Ti and Si) for sulfuric acid decomposition reaction: Role of support

Supported iron oxides have been established as an important class of catalyst for high temperature sulfuric acid decomposition. With an objective to elucidate the role of support in modifying the overall catalytic properties of dispersed iron oxide catalysts, a series of supported iron oxide based catalysts, Fe₂O₃ (15 wt%)/MO₂ (M = Zr, Ce, Ti and Si), synthesized by adsorption-equilibrium method, is investigated for sulfuric acid decomposition reaction. The structure of dispersed iron oxide phases largely depended on the nature of the support oxide as revealed by the XRD and Mössbauer studies. α-Fe₂O₃ is found to be present as a major phase on ZrO₂ and CeO₂ support while ε-Fe₂O₃ was the major phase on silica supported iron oxide. On the other hand, presence of mixed oxide Fe₂TiO₅ was revealed over TiO₂ support. Strong dispersed metal oxide-support interactions inhibited the total reduction of the dispersed phase on SiO₂ and TiO₂ as compared to complete reduction of dispersed iron oxide on CeO₂ and ZrO₂ supports during temperature programmed reduction upto 1000 °C. The order of catalytic activity at a temperature of ～750 °C is observed as Fe₂O₃/SiO₂ > Fe₂TiO₅/TiO₂ > Fe₂O₃/ZrO₂ > Fe₂O₃/CeO₂, while at higher temperatures of ～900 °C the SO₂ yield is found to be comparable for all catalysts. A relationship between the rate of sulfate decomposition and catalytic activity is established through detailed TG-DTA investigations of sulfated catalyst and support. Considerable influence of the support oxide on the composition, structure, redox properties, morphology and catalytic activities of the active iron oxide dispersed phase has been observed. Thus, the support oxides operate as a critical component in the complex supported metal oxide catalysts and these findings might influence the design and development of future high temperature sulfuric acid decomposition catalysts.     

Multiple-band large-signal characterization of millimeter-wave double avalanche region transit time diode

A large-signal method based on non-sinusoidal voltage excitation model is used to study the DC and RF characteristics of Double Avalanche Region (DAR) Silicon Transit Time diode. A large-signal simulation program based on drift-diffusion model is developed for this study. The simulation results show the existence of several distinct negative conductance bands in the admittance characteristics separated by positive conductance. Thus the DAR device is capable of delivering RF power not only at the design frequency but also at several frequency bands higher than the design frequency band in the mm-wave regime. A comparative study with DDR Si device designed to deliver RF power at a particular mm-wave frequency band shows that DAR Si device is capable of delivering significantly higher RF power not only at the designed mm-wave frequency band, but also at higher frequency bands.     

Effect of Polysaccharides on the Properties of the Mucoadhesive Poly(Vinyl Alcohol) Multicore–Shell Microparticles

This study discusses about the effect of polysaccharides (agar, gum tragacanth, and guar gum) on the properties of the core (organogel)–shell [poly(vinyl alcohol)] microparticles. The size, swelling, and mucoadhesive properties of the poly(vinyl alcohol) microparticles were altered in the presence of the polysaccharides. Thermal analysis confirmed the presence of organogels within the microparticles. Fourier transform infrared spectroscopy confirmed the presence of the polysaccharides within the microparticles. The microparticles were biocompatible in nature. Drug release indicated that an alteration in the shell composition can be used for altering drug release. Ciprofloxacin-loaded microparticles showed sufficient antimicrobial efficiency.     

Studies on sulfur vulcanization of natural rubber accelerated combinedly with 2-mercaptobenzothiazole and diphenylguanidine both in presence and absence of dicumyl peroxide

Sulfuration of natural rubber (NR) by the binary accelerator 2-mercaptobenzothiazole (MBT) and diphenylguanidine (DPG) both in presence and in absence of ZnO and stearic acid with or without dicumylperoxide (DCP) was studied in detail. It was observed that the rate of decomposition of DCP in presence of both MBT and DPG is quite similar to that with MBT alone. The reduction of crosslinking depends also on MBT only. Through DPG has no influence on the decomposition rate, it reacts with MBT during the vulcanization process and suppresses the retardation caused by MBT on the DCP vulcanization. In accordance with the initial additiveness of crosslinking in systems containing DCP, the free sulfur decrease, and the rapidity of crosslink formation the vulcanization process of MBT-DPG-S-NR systems was interpreted in terms of a polar mechanism induced by the complex MSH₂NR′R″. In mixtures containing DCP together with sulfur, MBT, DPG, ZnO, and stearic acid, the initial stage of crosslinking is additive as indicated by a mixed reaction as well as by a methyl iodide treatment of the vulcanizates. Comparison with single accelerators shows a pronounced synergistic effect. This is because of the enhanced activity of the MBT-ZnO-stearic acid complex due to DPG which also induces polar sulfuration of NR by forming the active complex MSH₂NR′R″. In presence of ZnO and stearic acid, DCP cannot increase the net crosslink density but suppresses the reversion so much pronounced in its absence.     

Impact of electrically formed interfacial layer and improved memory characteristics of IrOx/high-κx/W structures containing AlOx,GdOx, HfOx,and TaOx switching materials

Improved switching characteristics were obtained from high-κ oxides AlO_x, GdO_x, HfO_x, and TaO_x in IrO_x/high-κ_x/W structures because of a layer that formed at the IrO_x/high-κ_x interface under external positive bias. The surface roughness and morphology of the bottom electrode in these devices were observed by atomic force microscopy. Device size was investigated using high-resolution transmission electron microscopy. More than 100 repeatable consecutive switching cycles were observed for positive-formatted memory devices compared with that of the negative-formatted devices (only five unstable cycles) because it contained an electrically formed interfacial layer that controlled ‘SET/RESET’ current overshoot. This phenomenon was independent of the switching material in the device. The electrically formed oxygen-rich interfacial layer at the IrO_x/high-κ_x interface improved switching in both via-hole and cross-point structures. The switching mechanism was attributed to filamentary conduction and oxygen ion migration. Using the positive-formatted design approach, cross-point memory in an IrO_x/AlO_x/W structure was fabricated. This cross-point memory exhibited forming-free, uniform switching for >1,000 consecutive dc cycles with a small voltage/current operation of ±2 V/200 μA and high yield of >95% switchable with a large resistance ratio of >100. These properties make this cross-point memory particularly promising for high-density applications. Furthermore, this memory device also showed multilevel capability with a switching current as low as 10 μA and a RESET current of 137 μA, good pulse read endurance of each level (>10⁵ cycles), and data retention of >10⁴ s at a low current compliance of 50 μA at 85°C. Our improvement of the switching characteristics of this resistive memory device will aid in the design of memory stacks for practical applications.