Oxygen-release/storage properties of Ce0.5M0.5O2 (M = Zr, Hf) oxides: interplay of crystal chemistry and electronic structure

Fluorite-type Ce0.5Zr0.5O2 and Ce0.5Hf0.5O2 have been synthesized by a solution combustion route, and their oxygen release and reduction have been investigated up to 850 degrees C. On reduction, the zirconium system forms two pyrochlore phases, Ce2Zr2O7 (pyrochlore-I) and Ce2Zr2O6.2 (pyrochlore-II), while the hafnium system forms only a disordered fluorite phase with the composition Ce0.5Hf0.5O1.77, under the same experimental conditions. The crystal structures of the reduction products have been characterized by powder X-ray diffraction and Rietveld refinement, and their electronic structures have been investigated by photoelectron spectroscopy and electrical conductivity measurements. Pyrochlore-I (a = 10.6727(4) A) is a semiconductor, while pyrochlore-II (a = 10.6463(8) A) is a good conductor (with a nearly temperature independent resistivity of approximately 2.5 ohm.cm in the 400-1000 K range). X-ray photoelectron spectroscopy (XPS) shows an admixture of Ce(5d,6s) with Zr(4d) and O(2p) and a significant density of states near EF in the highly reduced pyrochlore-II phase. The changes have been rationalized in terms of a qualitative energy band scheme that brings out the special role of zirconium vis-à-vis hafnium in the reduction/oxygen release properties of Ce0.5Zr0.5O2 and Ce0.5Hf0.5O2.     

5 MeV Proton irradiation effects on 200 GHz silicon–germanium heterojunction bipolar transistors

The total dose effects of 5?MeV proton and Co-60 gamma irradiation in the dose range from 1 to 100?Mrad on advanced 200?GHz Silicon–Germanium heterojunction bipolar transistors (SiGe HBTs) are investigated. The SRIM simulation study was conducted to understand the energy loss of 5?MeV proton ions in SiGe HBT structure. Pre- and post-radiation DC figure of merits such as forward- and inverse-mode Gummel characteristics, excess base current, DC current gain and output characteristics were used to quantify the radiation tolerance of the devices. The results show that the proton creates a significant amount of damages in the surface and bulk of the transistor when compared with gamma irradiation. The SiGe HBTs shows robust ionizing radiation tolerance even up to a total dose of 100?Mrad for both radiations.     

Oxidative degradation and deamination of atenolol by diperiodatocuprate(III) in aqueous alkaline medium: A mechanistic study

The kinetics of oxidation of atenolol (ATN) by diperiodatocuprate(III) (DPC) in aqueous alkaline medium at a constant ionic strength of 0.10 mol dm⁻³ was studied spectrophotometrically. The reaction between DPC and ATN in alkaline medium exhibits 1:2 stoichiometry (ATN:DPC). The reaction is of first order in [DPC] and has less than unit order in both [ATN] and [alkali]. However, the order in [ATN] and [alkali] changes from first order to zero order as their concentration increase. Intervention of free radicals was observed in the reaction. Increase in periodate concentration decreases the rate. The oxidation reaction in alkaline medium has been shown to proceed via a monoperiodatocuprate(III)–ATN complex, which decomposes slowly in a rate-determining step followed by other fast steps to give the products. The main oxidative products were identified by spot test, IR, NMR and LC–ESI-MS studies. The reaction constants involved in the different steps of the mechanism are calculated. The activation parameters with respect to slow step of the mechanism are computed and discussed, and thermodynamic quantities are also determined.     

Voltammetric oxidation and determination of cinnarizine at glassy carbon electrode modified with multi-walled carbon nanotubes

We discovered a novel method to prepare a protein-based hydrogel, that is, a “Three-Dimensional Nanostructured Protein Hydrogel (3D NPH)”, which is composed of protein–polymer hybrid nanoparticles. In this study, we propose a novel protein microarray whose 3D NPH spots were prepared by dispensing a small volume of the solution of protein–polymer mixture on a substrate. The dispensed solution had a short time for cross-linking before its drying-up and the resulting 3D NPH had loosely cross-linked, thin spongy structure. Therefore, the reaction ratio between ligands and analytes was drastically improved in this system compared with the large volume system for Surface Plasmon Resonance (SPR) protein microarray.     

Design and synthesis of new donor-acceptor type conjugated copolymers derived from thiophenes

A new series of donor-acceptor type poly(thiophene) derivatives (P1-P3) were synthesized starting from thiodiglycolic acid and diethyl oxalate through multistep reactions. In the final step, the polymerization was carried out using Wittig reaction. This is a good synthetic route for the preparation of any desired p- and n-type copolymers. The optical and potential charge-transporting properties of the copolymers were investigated by UV-vis, fluorescence emission spectroscopy and cyclic voltammetry. The copolymers exhibited bluish-green/green fluorescence in their thin film forms. Cyclic voltammetry experiments showed that these copolymers have low-lying LUMO energy levels ranging from −2.98 to −3.11 eV and high lying HOMO energy levels ranging from −5.45 to −5.65 eV. The optical and electrochemical studies reveal that new copolymers are new promising materials for the development of efficient polymer light emitting diodes.     

Boiling induced nanoparticle coating and its effect on pool boiling heat transfer on a vertical cylindrical surface using CuO nanofluids

Experiments were performed to study boiling induced nanoparticle coating and its influence on pool boiling heat transfer using low concentrations of CuO- nanofluid in distilled water at atmospheric pressure. To investigate the effect of the nanoparticle coated surface on pool boiling performance, two different concentrations of CuO nanofluids (0.1 and 0.5?g/l) were chosen and tests were conducted on a clean heater surface in nanofluid and nanoparticle coated surface in pure water. For the bare heater tested in CuO nanofluid, CHF was enhanced by 35.83 and 41.68?% respectively at 0.1 and 0.5?g/l concentration of nanofluid. For the nanoparticle coated heater surface obtained by boiling induced coating using 0.1 and 0.5?g/l concentration of nanofluid and tested in pure water, CHF was enhanced by 29.38 and 37.53?% respectively. Based on the experimental investigations it can be concluded that nanoparticle coating can also be a potential substitute for enhancing the heat transfer in pure water. Transient behaviour of nanofluid was studied by keeping heat flux constant at 1,000 and 1,500?kW/m² for 90?min in 0.5?g/l concentration. The boiling curve shifted to the right indicating degradation in boiling heat transfer due to prolonged exposure of heater surface to nanofluid. Experimental outcome indicated that pool boiling performance of nanofluid could be a strong function of time and applied heat flux. The longer the duration of exposure of the heater surface, the higher will be the degradation in heat transfer.     

Electrofabrication of multilayer Fe–Ni alloy coatings for better corrosion protection

Electrofabrication of multilayer Fe–Ni alloy coatings were accomplished successfully on mild steel and their corrosion behaviors were studied. Multilayer comprised of alternatively formed ‘nano-size’ layers of Fe–Ni alloy of different composition have been produced from a single bath having Fe²⁺and Ni²⁺ ions using modulated (i.e. periodic pulse control) current density (cd). The deposition conditions were optimized for both composition and thickness of individual layers for best performance of the coatings against corrosion. The deposits were analyzed using scanning electron microscopy (SEM), powder X-ray diffraction (PXRD), Hardness Tester, electrochemical AC and DC methods respectively. The multi layered deposits showed better corrosion resistances compared to the monolayer Fe–Ni (CR = 3.77 mm year^?1) coating deposited using DC from the same bath; the maximum corrosion resistance being shown by the coating having 300 layers, deposited at cyclic cathodic current densities of 2.0 and 4.0 A dm^?2 (CR = 0.03 mm year^?1). Drastic improvement in the corrosion performance of multilayer coatings were explained in the light of changed kinetics of mass transfer at cathode and increased surface area due to modulation and layering.     

Quantification of Major Bioactive Withanolides in Withania somnifera (Ashwagandha) Roots by HPTLC for Rapid Validation of Ayurvedic Products

JPC – Journal of Planar Chromatography – Modern TLC - The high-performance thin-layer chromatography (HPTLC) method has been developed for the simultaneous quantification of withaferine...     

Determination of thorium concentrations in soil and sand samples using instrumental neutron activation analysis

Thorium along with its daughter products present in the soil is one of the major contributors to the external gamma dose in the environment. To establish the dose levels, quantification of thorium contents in soil samples is very important. As a part of pre-operational environmental radiological surveillance, a total of 23 soil and six sand samples were collected from different locations around the proposed nuclear power plant site of Jaitapur, Maharashtra. Thorium concentrations in these samples were determined by instrumental neutron activation analysis (INAA). Samples were irradiated with neutrons in Apsara reactor at a neutron flux of?~5?×?10¹¹ cm^?2 s^?1 and radioactive assay was carried out using high resolution gamma ray spectrometry. Relative method of INAA was used for quantification of thorium utilizing 311.9?keV gamma ray of ²³³Pa, the daughter product of ²³³Th. The concentrations of thorium in the soil and sand samples were in the ranges of 4.0?C18.8 and 1.2?C6.2?mg?kg^?1 respectively.     

Separation of uranium from iron in ground water samples using ion exchange resins

Uranium determination in environmental samples is faced with problems due to presence of iron and other major elements. Iron is also used many a times for pre-concentration of uranium and actinides. Separation of milligram quantity of Fe from microgram quantity of uranium becomes essential during the estimation step. A simple two step procedure has been standardized for separating uranium and iron using anion exchange in 0.025 M H₂SO₄. Quantitative recovery of uranium was obtained as well as good separation from iron. This method was applied for estimation of uranium in water samples.