Thermodynamics of TmRhO3, Phase Equilibria, and Chemical Potentials in the System Tm-Rh-O

Phase equilibria in the system Tm-Rh-O at 1200 K is established by isothermal equilibration of selected compositions and phase identification after quenching to room temperature. Six intermetallic phases (Tm3Rh, Tm7Rh3, Tm5Rh3, Tm3Rh2, TmRh, TmRh2 +/-delta) and a ternary oxide TmRhO3 are identified. Based on experimentally determined phase relations, a solid-state electrochemical cell is devised to measure the standard free energy of formation of orthorhombic perovskite TmRhO3 from cubic Tm2O3 and beta-Rh2O3 in the temperature range from (900 to 1300) K. The results can be summarized as: Delta G(f,ox)(o) +/- 104/J.mol(-1) = -46474 + 3.925(T/K). Invoking the Neumann-Kopp rule, the standard enthalpy of formation of TmRhO3 from its constituent elements at 298.15 K is estimated as -1193.89 (+/- 2.86) kJ.mol(-1). The standard entropy of TmRhO3 at 298.15 K is evaluated as 103.8 (+/- 1.6) J.mol(-1).K-1. The oxygen potential-composition diagram and three-dimensional chemical potential diagram at 1200 K and temperature-composition diagrams at constant partial pressures of oxygen are computed from thermodynamic data. The compound TmRhO3 decomposes at 1688 (+/- 2) K in pure oxygen and at 1583 (+/- 2) K in air at standard pressure.

Structural, EPR, optical and magnetic properties of alpha-Fe2O3 nanoparticles

alpha-Fe2O3 nanoparticles were synthesized by a low temperature solution combustion method. The structural, magnetic and luminescence properties were studied. Powder X-ray diffraction (PXRD) pattern of alpha-Fe2O3 exhibits pure rhombohedral structure. SEM micrographs reveal the dumbbell shaped particles. The EPR spectrum shows an intense resonance signal at g approximate to 5.61 corresponding to isolated Fe3+ ions situated in axially distorted sites, whereas the g approximate to 2.30 is due to Fe3+ ions coupled by exchange interaction. Raman studies show A(1g) (225 cm(-1)) and E-g (293 and 409 cm(-1)) phonon modes. The absorption at 300 nm results from the ligand to metal charge transfer transitions whereas the 540 nm peak is mainly due to the (6)A(1) + (6)A(1) —> T-4(1)(4G) + T-4(1)(4G) excitation of an Fe3+-Fe3+ pair. A prominent TL glow peak was observed at 140 C at heating rate of 5 degrees C s(-1). The trapping parameters namely activation energy (E), frequency factor (s) and order of kinetics (b) were evaluated and discussed. (C) 2012 Elsevier B.V. All rights reserved.

Borocarbonitrides, BxCyNz

Various forms of carbon, especially the nanocarbons, have received considerable attention in recent years. There has also been some effort to investigate borocarbonitrides, BxCyNz, comprising besides carbon, the two elements on either side. Although uniformly homogeneous compositions of borocarbonitrides may be difficult to generate, there have been attempts to prepare them by solid state as well as gas phase reactions. Some of the products so obtained show evidence for the presence of BCN networks. Then, there are composites (G-BN) containing hexagonal BN (h-BN) and graphene (G) domains, G(1-x)(BN)(x), in varying proportions. Nanotubes of BxCyNz have been reported by several workers. The borocarbonitrides exhibit some interesting electronic and gas adsorption properties. Thus, some of the preparations show selective CO2 adsorption. They also exhibit excellent characteristics for supercapacitor applications. In order to understand the nature of these understudied materials, it is necessary to examine the results from first-principles calculations. These calculations throw light on the variation in the band gap of G-BN with the concentration of h-BN, for different geometries of the domains and their boundaries. The possibility of formation of Stone-Wales (SW) defects at the interfaces of graphene and h-BN has been studied and the estimates of the formation energies of SW defects at the interfaces are similar to 4 to 6 eV. The presence of such defects at the interfaces influences the electronic structure near the band gap and the associated properties. For example, adsorption of CH4 and CO2 occurs with significantly stronger binding at the interfacial defects.

Synthesis and characterization of porous flowerlike alpha-Fe2O3 nanostructures for supercapacitor application

Porous flower-like alpha-Fe2O3 nanostructures synthesized by an ethylene glycol mediated self-assembly process are crystalline and porous with BET surface area of 64.6 m(2) g(-1). The discharge capacitance is 127 F g(-1) when the electrodes are cycled in 0.5 M Na2SO3 at a current density of 1 A g(-1). Capacitance retention after 1000 cycles is about 80% of the initial capacitance. The high discharge capacitance and its retention are attributed to high surface area and porosity of the iron oxide. As the iron oxides are inexpensive, the nano alpha-Fe2O3 is expected to be of potential use for supercapacitor application.

H/F isosteric substitution to attest different equi-energetic molecular conformations in crystals

The sequential replacement of aromatic H-atoms by F-atoms in 1,6-bis(phenylcarbonate) hexa-2,4-diyne allows access to its possible iso-energetic ``syn'', ``gauche'' and ``anti'' conformations.

New rock salt-related oxides Li3M2RuO6 (M=Co, Ni): Synthesis, structure, magnetism and electrochemistry

We describe the synthesis, crystal structure, magnetic and electrochemical characterization of new rock salt-related oxides of formula, Li3M2RuO6 (M=Co, Ni). The M=Co oxide adopts the LiCoO2 (R-3m) structure, where sheets of LiO6 and (Co-2/Ru)O-6 octahedra are alternately stacked along the c-direction. The M=Ni oxide also adopts a similar layered structure related to Li2TiO3, where partial mixing of Li and Ni/Ru atoms lowers the symmetry to monoclinic (C2/c). Magnetic susceptibility measurements reveal that in Li3Co2RuO6, the oxidation states of transition metal ions are Co3+ (S=0), Co2+ (S=1/2) and Ru4+ (S=1), all of them in low-spin configuration and at 10 K, the material orders antiferromagnetically. Analogous Li3Ni2RuO6 presents a ferrimagnetic behavior with a Curie temperature of 100 K. The differences in the magnetic behavior have been explained in terms of differences in the crystal structure. Electrochemical studies correlate well with both magnetic properties and crystal structure. Li-transition metal intermixing may be at the origin of the more impeded oxidation of Li3Ni2RuO6 when compared to Li3CO2RuO6. Interestingly high first charge capacities (between ca. 160 and 180 mAh g(-1)) corresponding to ca. 2/3 of theoretical capacity are reached albeit, in both cases, capacity retention and cyclability are not satisfactory enough to consider these materials as alternatives to LiCoO2. (C) 2013 Elsevier Inc. All rights reserved.

Dinuclear zinc bis(thiosemicarbazone) complexes: Synthesis, in vitro anticancer activity, cellular uptake and DNA interaction study

Four dinucleating bis(thiosemicarbazone) ligands and their zinc complexes have been synthesized and characterized by multinuclear NMR (H-1 and C-13), IR, UV-Vis, ESI-MS and fluorescence spectroscopic techniques. Their purity was assessed by elemental analysis. Cytotoxicity was tested against five human cancer cell lines using the sulphorhodamine B (SRB) assay, where one of the complexes, 1,3-bis{biacetyl-2'-(4 `'-N-pyrrolidinylthiosemicarbazone)-3'-(4 `'-N-pyrrolidinylthiosemicarbazone) zinc(II)} propane (6), was found to be quite cytotoxic against MCF-7 (breast cancer) and HepG2 (hepatoma cancer) cell lines, with a potency similar to that of the well known anticancer drug adriamycin. It is evident from the cellular uptake studies that the uptake is same for the active complex 6 and the inactive complex 8 (1,6-bis{biacetyl- 2'-(4 `'-N-pyrrolidinylthiosemicarbazone)-3'-(4 `'-N-pyrrolidinylthiosemicarbazone) zinc(II)} hexane) in MCF-7 and HepG2 cell lines. In vitro DNA binding and cleavage studies revealed that all complexes bind with DNA through electrostatic interaction, and cause no significant cleavage of DNA. (C) 2'13 Elsevier B. V. All rights reserved.

Seismic hazard analysis of Lucknow considering local and active seismic gaps

The Himalayas are one of very active seismic regions in the world where devastating earthquakes of 1803 Bihar-Nepal, 1897 Shillong, 1905 Kangra, 1934 Bihar-Nepal, 1950 Assam and 2011 Sikkim were reported. Several researchers highlighted central seismic gap based on the stress accumulation in central part of Himalaya and the non-occurrence of earthquake between 1905 Kangra and 1934 Bihar-Nepal. The region has potential of producing great seismic event in the near future. As a result of this seismic gap, all regions which fall adjacent to the active Himalayan region are under high possible seismic hazard due to future earthquakes in the Himalayan region. In this study, the study area of the Lucknow urban centre which lies within 350 km from the central seismic gap has been considered for detailed assessment of seismic hazard. The city of Lucknow also lies close to Lucknow-Faizabad fault having a seismic gap of 350 years. Considering the possible seismic gap in the Himalayan region and also the seismic gap in Lucknow-Faizabad fault, the seismic hazard of Lucknow has been studied based on deterministic and the probabilistic seismic hazard analysis. Results obtained show that the northern and western parts of Lucknow are found to have a peak ground acceleration of 0.11-0.13 g, which is 1.6- to 2.0-fold higher than the seismic hazard compared to the other parts of Lucknow.

Sputter Deposited High Capacity Li2-xMnO3-y Films for Thin Film Battery Application

Lithium manganese oxide (Li2-xMnO3-y) thin films have been deposited from activated Li2MnO3 powder by radio frequency magnetron sputtering for the first time in the literature and subjected to electrochemical characterization. Physicochemical characterization by X-ray diffraction has revealed the formation of the thin films with crystallographic phase identical to that of the powder target made of Li2-xMnO3-y. The Li:Mn atomic ratio for the powder and film are calculated by X-ray photoelectron spectroscopy and it is found to be 1.6:1.0. From galvanostatic charge discharge studies, a specific discharge capacity of 139 mu Ah mu m(-1) cm(-2) was obtained when cycled between 2.00 and 3.50 V vs Li/Li+. Additionally the rate capability of the thin film electrodes was studied by subjecting the cells to charge-discharge cycling at different current densities in the range from 10 mu A cm(-2) to 100 mu A cm(-2). (C) 2013 The Electrochemical Society. All rights reserved.

Digestive ripening facilitated atomic diffusion at nanosize regime: Case of AuIn2 and Ag3In intermetallic nanoparticles

Monodisperse colloidal gold-indium (AuIn2) intermetallic nanoparticles have been synthesized from Au and In colloids using the digestive ripening process. Formation of the intermetallic proceeds via digestive ripening facilitated atomic diffusion of Au and In atoms from the Au and In nanoparticles followed simultaneously by their growth in the solution. Optimization of the reaction temperature was found to be crucial for the formation of AuIn2 intermetallic from gold and indium nanoparticles. Transmission electron microscopy revealed the presence of nearly monodisperse nanoparticles of Au and AuIn2 with particle size distribution of 3.7 +/- 1.0 nm and 5.0 +/- 1.6 nm, respectively. UV-visible spectral studies brought out the absence of SPR band in pure AuIn2 intermetallic nanoparticles. Optical study and electron microscopy, in combination with powder X-ray diffraction established phase pure AuIn2 intermetallic nanoparticles unambiguously. The potential of such an unprecedented approach has been further exploited in the synthesis of Ag3In intermetallic nanoparticles with the dimension of less than 10 nm. (C) 2014 Elsevier B.V. All rights reserved.

t-Na-2(VO)P2O7: A 3.8 V Pyrophosphate Insertion Material for Sodium-Ion Batteries

Pyrophosphate oxyanionic framework compounds offer a great platform to investigate new battery materials. In our continuing effort to explore pyrophosphate cathodes for sodium-ion batteries, we report, for the first time, the synthesis and use of tetragonal Na-2(VO)P2O7 as a potential sodium-ion insertion material. This material can be easily prepared by using a conventional solid-state route at a relatively low temperature of 400 degrees C. Stabilizing as a tetragonal structure with an open framework, the material offers pathways for Na+ diffusion. The as-synthesized material, with no further cathode optimization, yields a reversible capacity (Q) approaching 80 mAh g(-1) (Q(Theoretical) = 93.4 mAh g(-1)) involving a one electron V5+/V4+ redox potential located at 3.8 V (vs. Na/Na+). Furthermore, the material exhibits decent rate kinetics and reversibility. Combining green synthesis and moderate electrochemical properties, t-Na-2(VO)P2O7 is reported as a new addition to the growing family of pyrophosphate cathodes for sodium-ion batteries.

Symmetric supercapacitor based on partially exfoliated and reduced graphite oxide in neutral aqueous electrolyte

The partially exfoliated and reduced graphite oxide (PE-RGO) is prepared by low temperature thermal exfoliation of graphite oxide under air atmosphere. A symmetric carbon/carbon supercapacitor is studied in a Na2SO4 aqueous electrolyte. The discharge capacitance is 92 F g(-1), when symmetric cell is cycled between the potential ranges from 0 to 1.6 V. This system demonstrates a stable charge/discharge cycle behavior up to 3000 cycles when the cell is operated at a voltage window of 1.6 V. The utilization ratio of potential window is 90% for this system is attributed to the more negative value of electrodes potential when the cell voltage is set to 0 V. The low-temperature exfoliation approach is convenient for mass production of graphenes at low cost and it can be used as electrode material for energy storage applications. (C) 2014 Elsevier Ltd. All rights reserved.

Iron-carbon hybrid capacitor: A proof-of-concept study

In the present study, cost-intensive Ni electrode is replaced by high surface-area activated carbon (AC) cathode and the possibility of the Fe anode, used in Ni-Fe battery, to function as Fe-C hybrid capacitor has been examined. The electrochemical properties of Fe-C hybrid capacitor assembly are studied using cyclic voltammetry (CV) and galvanostatic charge-discharge cycles. Over 100 galvanostatic charge-discharge cycles for Fe-C hybrid capacitor are carried out and a maximum capacitance of 24 F g(-1) is observed.

Study the effect of electrical and mechanical shock loading on liberation and milling characteristics of mineral materials

Milling is an energy intensive process and it is considered as one of the most energy inefficient processes. Electrical and mechanical shock loading can be used to develop a pre-treatment methodology to enhance energy efficiency of comminution and liberation of minerals. Coal and Banded Hematite Jasper (BHJ) Iron ores samples were taken for the study to know the effect of shock loading. These samples were exposed to 5 electric shocks of 300 kV using an electric shock loading device. A diaphragmless shock tube was used to produce 3 and 6 compressed air shocks of Mach number 2.12 to treat the coal and Iron ore samples. Microscopic, comminution and liberation studies were carried out to compare the effectiveness of these approaches. It was found that electric shock loading can comminute the coal samples more effectively and increases the yield of carbon by 40% at 1.6 gm/cc density over the untreated coal samples. Mechanical shock loading showed improved milling performance for both the materials and 12.90% and 8.1% reduction in the D-80 of the particles was observed during grinding for treated samples of coal and iron, respectively. Liberation of minerals in BHJ Iron ore was found unaffected due to low intensity of the mechanical shock waves and non conductivity of minerals. Compressed air based shock loading is easier to operate than electrical shock loading and it needs to be explored further to improve the energy efficacy of comminution. (C) 2014 Elsevier Ltd. All rights reserved.

Mercury exposure Aasessment in fish and humans from Sundarban Mangrove Wetland of India

Present study had documented total mercury levels in six commonly consumed fish species, and performed across-sectional study on local residents to gauge their intake of fish (via dietary survey) and mercury exposure (via hair biomarker analyses). Mean total mercury content in edible composites of locally-caught fishes (topse, hilsa, mackerel, topse, sardinella, khoira) was low and ranged from 0.01 to 0.11 mu g g(-1) mercury, dry weight. In a cross-sectional study of 58 area residents, the mercury content in hair ranged from 0.25 to 1.23 mu g g(-1), with a mean of 0.65 +/- 0.23 mu g g(-1), Flair mercury level was not influenced by gender, age, or occupation. Mean number of meals consumed per week was 3.1 +/- 1.1, and all participants consumed at least one fish meal per week. When related to fish consumption, a significant positive association was found between number of fish meals consumed per week and hair mercury levels.