Crystal co-ordination of the barium ion

A systematic study has been made of the crystal co-ordination of the barium ion in various compounds whose structures have been solved. Apart from the more common co-ordination polyhedra which are enumerated in text-books, a number of new polyhedra have been identified, particularly in cases where the co-ordination numbers are unusual, such as ten or eleven. According to the radius-ratio rule of Pauling, a co-ordination number of nine or ten is normally expected for the barium ion. The present investigations, however, reveal that it shows a variety of co-ordinations with ligancies from six up to twelve. Some of the factors that might possibly enter in explaining this wide range of co-ordination numbers are discussed. It appears as though the part played by the Ba2+ ion in deciding the structure is secondary, limiting itself only to occupying vacant spaces provided by other atoms in the crystal.

Dielectric properties of (100-x)Li2B4O7-x(Ba5Li2Ti2Nb8O30) glasses and glass nanocrystal composites

Transparent glasses of various compositions in the system (100 -x)(Li2B4O7)-x(Ba5Li2Ti2Nb8O30) (5 <= x <= 20, in molar ratio) were fabricated by splat quenching technique. The glassy nature of the as-quenched samples was established by differential thermal analyses (DTA). X-ray powder diffraction studies confirmed the as-quenched glasses to be amorphous and the heat-treated to be nanocrystalline. Controlled heat-treatment of the as-quenched glasses at 500 degrees C for 8 h yielded nanocrystallites embedded in the glass matrix. High Resolution Transmission Electron Microscopy (HRTEM) of these samples established the size of the crystallites to be in the nano-range and confirmed the phase to be that of Ba5Li2Ti2Nb8O30 (BLTN) which was, initially, identified by X-ray powder diffraction. The frequency, temperature and compositional dependence of the dielectric constant and the electrical conductivity of the glasses and glass nanocrystal composites were investigated in the 100 Hz to 10 MHz frequency range. Electrical relaxations were analyzed using the electric modulus formalisms. The imaginary part of electric modulus spectra was modeled using an approximate solution of Kohlrausch-Williams-Watts relation. The frequency dependent electrical conductivity was rationalized using Jonscher's power law. The activation energy associated with the dc conductivity was ascribed to the motion of Li+ ions in the glass matrix. The activation energy associated with dielectric relaxation was almost equal to that of the dc conductivity, indicating that the same species took part in both the processes. (C) 2010 Elsevier B.V. All rights reserved.

On the hardness and elastic modulus of bulk metallic glass matrix composites

The influences of the amorphous matrix and crystalline dendrite phases on the hardness and elastic moduli of Zr/Ti-based bulk metallic glass matrix composites have been assessed. While the moduli of the composites correspond to those predicted by the rule of mixtures, the hardness of the composites is similar to that of the matrix, suggesting that the plastic flow in the composites under constrained conditions such as indentation is controlled by the flow resistance of the contiguous matrix. (C) 2010 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

A study of cubic bismuth oxides of the type bi(26-X)m(X)O(40-delta) (m=ti, mn, fe, co, ni or pb) related to gamma-bi2O3

A structural investigation of cubic oxides (space group I23) of the formula Bi(26-x)M(x)O(40-delta) (M = Ti, Mn, Fe, Co, Ni and Pb) related to the Y-Bi2O3 phase has been carried out by the Rietveld profile analysis of high-resolution X-ray powder diffraction data in order to establish the cation distributions. Compositional dependence of the cation distribution has been examined in the case of Bi26-xCoxO40-delta (1 < x < 16). The study reveals that in Bi(26-X)M(X)O(40-delta) with M = Ti, Mn, Fe, Co or Pb, the M cations tend to occupy tetrahedral (2a) sites when x < 2 while the octahedral (24f) sites are shared by the excess Co or Ni cations with Bi atoms when x > 2. Also experimental magnetic moments of Mn, Co and Ni derivatives have been used to establish the valence state and distribution of these cations.

Preparation of the layered double hydroxide (LDH) LiAl2(OH)(7)center dot 2H(2)O, by gel to crystallite conversion and a hydrothermal method, and its conversion to lithium aluminates

A layered double hydroxide (LDH) with chemical composition LiAl2(OH)(7) . 2H(2)O was prepared via a wet chemical route of gel to crystallite (G-C) conversion at 80 degrees C involving the reaction of hydrated alumina gel, Al2O3.yH(2)O (80 < y < 120) with LiOH (Li2O/Al2O3 greater than or equal to 0.5) in presence of hydrophilic solvents such as ethanol under refluxing conditions. The hydrothermal synthesis was carried out using the same reactants by heating to less than or equal to 140 degrees C in a Teflon-lined autoclave under autogenerated pressure (less than or equal to 20 MPa). Transmission electron microscopy showed needle-shaped aggregates of size 0.04-0.1 mu m for the gel to crystallite conversion product, whereas the hydrothermal products consisted of individual lamellar crystallites of size 0.2-0.5 mu m with hexagonal morphology. The LDH prepared through the gel to crystallite conversion could be converted into LiAl(OH)(4) . H2O or LiAl(OH)(3)NO3 . H2O by imbibition of LiOH or LiNO3, respectively, under hydrothermal conditions. Thermal decomposition of LDH above 1400 degrees C gave rise to LiAl5O8 accompanied by the evaporation of Li2O. LiAl(OH)(4) . H2O and LiAl(OH)(3)NO3 . H2O decomposed in the temperature range 400-1000 degrees C to alpha- or beta-LiAlO2. The compositional dependence of the product, the intermediate phases formed during the heat treatment and the possible reactions involved are described in detail.

Role of La0.5Sr0.5COO3 template layers on dielectric and electrical properties of pulsed-laser ablated Pb(Nb2/3Mg1/3)O-3-PbTiO3 thin films

Relaxor ferroelectric thin films of 0.7Pb(Mg1/3Nb2/3)O-3-0.3PbTiO(3) (PMN-PT) deposited on platinized silicon substrates with and without template layers were studied. Perovskite phase (80% by volume) was obtained through proper selection of the processing conditions on bare Pt/Ti/SiO2/Si substrates. The films were initially grown at 300 degreesC using pulsed-laser ablation and subsequently annealed in a rapid thermal annealing furnace in the temperature range of 750-850 degreesC to induce crystallization. Comparison of microstructure of the films annealed at different temperatures showed change in perovskite phase formation and grain size etc. Results from compositional analysis of the films revealed that the films initially possessed high content of lead percentage, which subsequently decreased after annealing at temperature 750-850 degreesC. Films with highest perovskite content were found to form at 820-840 degreesC on Pt substrates where the Pb content was near stoichiometric. Further improvement in the formation of perovskite PMN-PT phase was obtained by using buffer layers of La0.5Sr0.5CoO3 (LSCO) on the Pt substrate. This resulted 100% perovskite phase formation in the films deposited at 650 degreesC. Dielectric studies on the PMN-PT films with LSCO template layers showed high values of relative dielectric constant (3800) with a loss factor (tan delta) of 0.035 at a frequency of 1 kHz at room temperature. (C) 2002 Elsevier Science B.V. All rights reserved.

The fluorescence of Nd3+ in lead borate and bismuth borate glasses with large stimulated emission cross section

The stimulated emission cross section σp for the 1060 nm transition of Nd3+ in lead borate and bismuth borate glasses has been determined from fluorescence measurements. The compositional dependence of σp, which has been evaluated using radiative transition probability, refractive index of the host glass, effective fluorescence linewidth, and position of the band, with PbO/Bi2O3 content is investigated. The σp values of the 1060 nm band of Nd3+ for lead borate and bismuth borate glasses are found to be in the range 2.6–5.7×10−20 cm2 at 298 K and 3.0–6.3×10−20 cm2 at 4.2 K. The σp values are comparatively large suggesting the possible utilization of these materials in laser applications.

Growth of silicon nanowires by electron beam evaporation using indium catalyst

For the first time silicon nanowires have been grown on indium (In) coated Si (100) substrates using e-beam evaporation at a low substrate temperature of 300 degrees C. Standard spectroscopic and microscopic techniques have been employed for the structural, morphological and compositional properties of as grown Si nanowires. The as grown Si nanowires have randomly oriented with an average length of 600 nm for a deposition time of 15 min. As grown Si nanowires have shown indium nanoparticle (capped) on top of it confirming the Vapor Liquid Solid (VLS) growth mechanism. Transmission Electron Microscope (TEM) measurements have revealed pure and single crystalline nature of Si nanowires. The obtained results have indicated good progress towards finding alternative catalyst to gold for the synthesis of Si nanowires. (C) 2011 Elsevier B.V. All rights reserved.

Effect of liquid precursor pyrolysis on phase selection in the MgO-MgAl2O4 system

Aqueous solutions of Al and Mg nitrates have been spray pyrolysed at 673 K to synthesize powders with compositions varying between MgO and MgAl2O4. This has been carried out with the aim of studying phase selection and phase evolution in this system. The powders have been subsequently heat treated and the sequence of phases characterised by X-ray diffraction and transmission electron microscopy. Metastable extensions of the different phase fields have been calculated based on functions which predict the equilibrium phase diagram accurately. The appearance of phases is closely related to the temperature and to the non-stoichiometry in different compositional ranges of the system. The sequence of phase evolution has been correlated to the thermodynamics of nucleation in the system.

Further results on geometric properties of a family of relative entropies

This paper extends some geometric properties of a one-parameter family of relative entropies. These arise as redundancies when cumulants of compressed lengths are considered instead of expected compressed lengths. These parametric relative entropies are a generalization of the Kullback-Leibler divergence. They satisfy the Pythagorean property and behave like squared distances. This property, which was known for finite alphabet spaces, is now extended for general measure spaces. Existence of projections onto convex and certain closed sets is also established. Our results may have applications in the Rényi entropy maximization rule of statistical physics.

Transmission electron microscopy study of Ni-rich, Ag-Ni nanowires

Present work provides an electrodeposition based methodology for synthesizing Ni-rich, Ag-Ni nanowires using an alumina template. Ag-Ni system shows negligible solid solubility in the bulk. Detailed structural and compositional characterization of as-synthesized nanowires using transmission electron microscopy technique revealed a two phase microstructure. Regions along and near the nanowire axis contained crystalline Ag-Ni solid solution phase with Ag-rich composition. Whereas, regions away from the axis and near the nanowire boundary predominantly contained nanocrystalline Ni-rich, Ni-Ag solid solution phase. (C) 2013 Elsevier B. V. All rights reserved.

Role of electrolyte chemistry on electronic and in vitro electrochemical properties of micro-arc oxidized titania films on Cp Ti

The primary objective of the present work was to study the electronic and in vitro electrochemical properties of micro-arc oxidized titania films on Cp Ti, fabricated independently in various electrolyte solutions consisting of anions such as phosphate (PO43-), borate (B4O72-), citrate (C6H5O73-) and silicate (SiO32-). Further the role of anions on the structural, morphological and compositional properties of the fabricated films was studied. All the titania films were developed by micro-arc oxidation (MAO) technique for a fixed treatment time of 8 min under constant current mode. The surface morphology, elemental distribution, composition and structural characteristics of the films were assessed by scanning electron microscope (SEM) equipped with energy dispersive spectroscopy (EDS) and X-ray diffraction (XRD) techniques. The thermodynamic and kinetic corrosion properties of the films were studied under simulated body fluid (SBF) conditions (pH 7.4 and 37 degrees C) by conducting chronopotentiometric and potentiodynamic polarization tests. Electrochemical impedance spectroscopy (EIS) coupled with equivalent circuit modelling was carried out to analyse the frequency response and Mott-Schottky analysis was performed to study the semiconducting (electronic) properties of the films. Salt spray fog accelerated corrosion test was conducted for 168h as per ASTM B117 standard to corroborate the corrosion and semiconducting properties of the samples based on the visual examination. The XRD results showed that the transformation from the metastable anatase phase to the thermodynamically stable rutile phase and the crystalline growth of the respective phases were strongly influenced by the addition of anions. The SEM-EDS results demonstrated that the phosphorous (P) content in the films varied from 2.4 at% to 5.0 at% indicating that the amount of P in the films could be modified by adding an appropriate electrolyte additive. The electrochemical corrosion test results showed that the film fabricated in citrate (C6H5O73-) containing electrolyte is thermodynamically and kinetically more stable compared to that of all the others. The results of the Mott-Schottky analysis indicated that all the fabricated films showed an n-type semiconducting behaviour and the film developed in citrate (C6H5O73-) containing electrolyte exhibited the lowest donor concentration and the most negative flat band potential that contributed to its highest corrosion resistance in SBF solution. The results of the salt spray accelerated corrosion tests were in agreement with those obtained from the electrochemical and Mott-Schottky analysis.

Compositional hierarchical monitoring automaton construction for LTL

In this paper we give a compositional (or inductive) construction of monitoring automata for LTL formulas. Our construction is similar in spirit to the compositional construction of Kesten and Pnueli [5]. We introduce the notion of hierarchical Büchi automata and phrase our constructions in the framework of these automata. We give detailed constructions for all the principal LTL operators including past operators, along with proofs of correctness of the constructions.

Rapid determination of main constituents of packed juices by reverse phase-high performance liquid chromatography: an insight in to commercial fruit drinks

The present work reports the compositional analysis of thirteen different packed fruit juices using high performance liquid chromatography (HPLC). Vitamin C, organic acids (citric and malic) and sugars (fructose, glucose and sucrose) were separated, analyzed and quantified using different reverse phase methods. A new rapid reverse phase HPLC method was developed for routine analysis of vitamin C in fruit juices. The precision results of the methods showed that the relative standard deviations of the repeatability and reproducibility were < 0.05 and < 0.1 respectively. Correlation coefficient of the calibration models developed was found to be higher than 0.99 in each case. It has been found that the content of Vitamin C was less variable amongst different varieties involved in the study. It is also observed that in comparison to fresh juices, the packed juices contain lesser amounts of vitamin C. Citric acid was found as the major organic acids present in packed juices while maximum portion of sugars was of sucrose. Comparison of the amount of vitamin C, organic acids and sugars in same fruit juice of different commercial brands is also reported.

Self Catalytic Growth of Indium Oxide (In2O3) Nanowires by Resistive Thermal Evaporation

Self catalytic growth of Indium Oxide (In2O3) nanowires (NWs) have been grown by resistive thermal evaporation of Indium (In) in the presence of oxygen without use of any additional metal catalyst. Nanowires growth took place at low substrate temperature of 370-420 degrees C at an applied current of 180-200 A to the evaporation boat. Morphology, microstructures, and compositional studies of the grown nanowires were performed by employing field emission scanning electron microscopy (FESEM), X-Ray diffraction (XRD), transmission electron microscopy (TEM), energy dispersive X-ray spectroscopy (EDS) and X-ray photoelectron spectroscopy (XPS) respectively. Nanowires were uniformly grown over the entire Si substrate and each of the nanowire is capped with a catalyst particle at their end. X-ray diffraction study reveals the crystalline nature of the grown nanowires. Transmission electron microscopy study on the nanowires further confirmed the single crystalline nature of the nanowires. Energy dispersive X-ray analysis on the nanowires and capped nanoparticle confirmed that Indium act as catalyst for In2O3 nanowires growth. A self catalytic Vapor-Liquid-Solid (VLS) growth mechanism was responsible for the growth of In2O3 nanowires. Effect of oxygen partial pressure variation and variation of applied currents to the evaporation boat on the nanowires growth was systematically studied. These studies concluded that at oxygen partial pressure in the range of 4 x 10(-4), 6 x 10(-4) mbar at applied currents to the evaporation boat of 180-200 A were the best conditions for good nanowires growth. Finally, we observed another mode of VLS growth along with the standard VLS growth mode for In2O3 nanowires similar to the growth mechanism reported for GaAs nanowires.