Low temperature processing and chacterization of SrBi2Nb2O9 thin films grown by pulsed laser ablation

Ex-situ grown thin films of SrBi2Nb2O9 (SBN) were deposited on platinum substrates using laser ablation technique. A low substrate-temperature-processing route was chosen to avoid any diffusion of bismuth into the Pt electrode. It was observed that the as grown films showed an oriented growth along the 'c'-axis (with zero spontaneous polarization). The as grown films were subsequently annealed to enhance crystallization. Upon annealing, these films transformed into a polycrystalline structure, and exhibited excellent ferroelectric properties. The switching was made to be possible by lowering the thickness without losing the electrically insulating behavior of the films. The hysteresis results showed an excellent square-shaped loop with results (P-r = 4 muC/cm(2) E-c = 90 kV/cm) in good agreement with the earlier reports. The films also exhibited a dielectric constant of 190 and a dissipation factor of 0.02, which showed dispersion at low frequencies. The frequency dispersion was found to obey Jonscher's universal power law relation, and was attributed to the ionic charge hopping process according to earlier reports. The de transport studies indicated an ohmic behavior in the low voltage region, while higher voltages induced a bulk space charge and resulted in non-linear current-voltage dependence.

Dielectric properties of glasses prepared by quenching melts of superconducting Bi‐Ca‐Sr‐Cu‐O cuprates

Glasses obtained from quenching melts of superconducting bismuth cuprates of the formula Bi2(Ca,Sr)n+1CunO2n+4 with n=1 and 3 exhibit novel dielectric properties. They possess relatively high dielectric constants as well as high electrical conductivity. The novel dielectric properties of these cuprate glasses are likely to be of electronic origin. They exhibit a weak microwave absorption due to the presence of microcrystallites.

Crystal chemistry of a new solid solution in the BaO-Bi2O3-Nb2O5 system: Ba-5x/2-Bi(1-x)5/3Nb5O15

A solid solution of the type Ba5x/2Bi(1-x)5/3Nb5O15 has been identified in the BaO-Bi2O3-Nb2O5 system for the first time. The limits of the solid solution are within the range 0.52 <= x <= 0.80. The compositions x = 0.52, 0.60, 0.72, 0.77, 0.78, and 0.80 were synthesized by the solid-state technique from the starting materials in stoichiometric quantities. The powder X-ray patterns of all the phases in the domain indicate a structural similarity to tetragonal tungsten bronzes (TTBs). The compositions below x = 0.52 and those above x = 0.80 exhibit barium niobate and bismuth niobate impurities, respectively. Single crystals of the composition x = 0.77 were obtained by the melt cooling technique. The crystal structure of Ba3.85/2Bi1.15/3Nb5O15 (x = 0.77) was solved in the tetragonal space group P4bm (No. 100) with a = 12.4938 (14) angstrom, c = 3.9519 (2) A, V = 616.87 (10) angstrom(3), and Z = 2 and was refined to an R index of 0.034. Dielectric measurements on all the phases indicate a typical relaxor behavior with a broad phase transition at T-m approximate to 300 K.

A computer study of the miscibility limits of Sb-Te-Bi

The quaternary system Sb1bTe1bBi1bSe with small amounts of suitable dopants is of interest for the manufacture of thermoelectric modules which exhibit the Peltier and Seebeck effects. This property could be useful in the production of energy from the thermoelectric effect. Other substances are bismuth telluride (Bi2Te3) and Sb1bTe1bBi and compounds such as ZnIn2Se4. In the present paper the application of computer programs such as MIGAP of Kaufman is used to indicate the stability of the ternary limits of Sb1bTe1bBi within the temperature ranges of interest, namely 273 K to 300 K.

On the two-dimensional thermoelectric power in quantum wells of non-parabolic materials under magnetic quantization

We present a simplified theoretical formulation of the thermoelectric power (TP) under magnetic quantization in quantum wells (QWs) of nonlinear optical materials on the basis of a newly formulated magneto-dispersion law. We consider the anisotropies in the effective electron masses and the spin-orbit constants within the framework of k.p formalism by incorporating the influence of the crystal field splitting. The corresponding results for III-V materials form a special case of our generalized analysis under certain limiting conditions. The TP in QWs of Bismuth, II-VI, IV-VI and stressed materials has been studied by formulating appropriate electron magneto-dispersion laws. We also address the fact that the TP exhibits composite oscillations with a varying quantizing magnetic field in QWs of n-Cd3As2, n-CdGeAs2, n-InSb, p-CdS, stressed InSb, PbTe and Bismuth. This reflects the combined signatures of magnetic and spatial quantizations of the carriers in such structures. The TP also decreases with increasing electron statistics and under the condition of non-degeneracy, all the results as derived in this paper get transformed into the well-known classical equation of TP and thus confirming the compatibility test. We have also suggested an experimental method of determining the elastic constants in such systems with arbitrary carrier energy spectra from the known value of the TP. (C) 2010 Elsevier Ltd. All rights reserved.

Thermal and electrical switching studies on Ge20Se80-xBix (1 <= x <= 13) ternary chalcogenide glassy system

Alternating Differential Scanning Calorimetric (ADSC) and electrical switching studies have been undertaken on Ge20Se80-xBix glasses (1 <= x <= 13), to understand the effect of topological thresholds on thermal properties and electrical switching behavior. It is found that the compositional dependence of glass transition temperature (Tg), crystallization temperature (T-c1) and thermal stability (AT) of Ge20Se80-xBix glasses show anomalies at a composition x= 5, the rigidity percolation/stiffness threshold of the system. Further, unusual variations are also observed in different thermal properties, such as T-g, T-c1, Delta T, Delta C-p and Delta H-NR, at the composition x= 10, which indicates the occurrence of chemical threshold in these glasses at this composition. Electrical switching studies indicate that Ge20Se8o_RBig glasses with 5 11 exhibit threshold switching behavior and those with x = 12 and 13 show memory switching. A sharp decrease has been noticed in the switching voltages with bismuth concentration, which is due to the more metallic nature of bismuth and the presence of Bi+ ions. Further, a saturation is seen in the decrease in V-T around x = 6, which is related to bismuth phase percolation at higher concentrations of Bi. (C) 2010 Elsevier B.V. All rights reserved.

Microstructural changes induced by ternary additions in a hypo-eutectic titanium-silicon alloy

Hypo-eutectic Ti-6.5 wt % Si alloy modified by separate additions of misch metal and low surface tension elements (Na, Sr, Se and Bi) has been examined by microscopic study and thermal analysis. Addition of third element led to modification of microstructure with apparently no significant enhancement of tensile ductility, with the exception of bismuth. Bismuth enhanced the ductility of the alloy by a factor of two and elastic-plastic fracture toughness to 9 MPa m–1/2 from a value of almost zero. The improved ductility of bismuth modified alloy is attributed to the reduced interconnectivity of the eutectic suicide, absence of significant suicide precipitation in the eutectic region and increase in the volume fraction of uniformly distributed dendrites. These changes are accompanied by a decrease in the temperature of eutectic solidification.

Photoemission study of the high-Tc superconductor Bi1.8Pb0.4Sr2Ca2.2Cu3O10

Ultraviolet and X-ray photoemission spectroscopic (UPS and XPS) studies to characterize the electronic structure of bismuth cuprate superconductor with nominal composition of Bi1.8Pb0.4Sr2Ca2.2Cu3O10 have been carried out. The data clearly shows the metallic emission at the Fermi level (EF). The shoulder (-1.2 eV) near the EF is attributed to the Cu-O derived states. Cu satellite structures observed both in the UPS and XPS show the strongly correlated nature of the Cu 3d electrons. Core level shifts indicate that 3+ and 4+ are the main oxidation of Bi and Pb, respectively. The Pb core lines show two components indicating their inequivalent sites. Core level O 1s spectrum is deconvoluted to show the presence of structurally non-equivalent oxygen sites.

Growth of Orthorhombic SnS Nanobox Structures on Seeded Substrates

Tin sulfide (SnS) nanostructures have been synthesized using a simple and low temperature chemical solution method on seeded substrates, and their structural and optical properties have been investigated. The as-grown SnS nanostructures with well-defined facets exhibited good stoichiometry between constituent elements. These nanobox structures are preferentially oriented along the 010] direction by having 100] and 001] orientations as surrounding facets and exhibited Two distinguishable optical band gaps of 1.36 and 1.9 eV. The effect of solution concentration as well as seed layer on the morphology or SnS structures has also been studied, and finally, the growth mechanism of the regular SnS nanobox structures is proposed.

Functional Mimics of Glutathione Peroxidase: Bioinspired Synthetic Antioxidants

Oxidative stress is caused by an imbalance between the production of reactive oxygen species (ROS) and the biological system's ability to detoxify these reactive intermediates. Mammalian cells have elaborate antioxidant defense mechanisms to control the damaging effects of ROS. Glutathione peroxidase (GPx), a selenoenzyme, plays a key role in protecting the organism from oxidative damage by catalyzing the reduction of harmful hydroperoxides with thiol a ``catalytic triad'' with tryptophan and glutamine, which cofactors. The selenocysteine residue at the active site forms activates the selenium moiety for an efficient reduction of peroxides. After the discovery that ebselen, a synthetic organoselenium compound, mimics the catalytic activity of GPx both in vitro and in vivo, several research groups developed a number of small-molecule selenium compounds as functional mimics of GPx, either by modifying the basic structure of ebselen or by incorporating some structural features of the native enzyme. The synthetic mimics reported in the literature can be classified in three major categories: (i) cyclic selenenyl amides having a Se-N bond, (ii) diaryl diselenides, and (iii) aromatic or aliphatic monoselenides. Recent studies show that ebselen exhibits very poor GPx activity when aryl or benzylic thiols such as PhSH or BnSH are used as cosubstrates. Because the catalytic activity of each GPx mimic largely depends on the thiol cosubstrates used, the difference in the thiols causes the discrepancies observed in different studies. In this Account, we demonstrate the effect of amide and amine substituents on the GPx activity of various organoselenium compounds. The existence of strong Se ... O/N interactions in the selenenyl sulfide intermediates significantly reduces the GPx activity. These interactions facilitate an attack of thiol at selenium rather than at sulfur, leading to thiol exchange reactions that hamper the formation of catalytically active selenol. Therefore, any substituent capable of enhancing the nucleophilic attack of thiol at sulfur in the selenenyl sulfide state would enhance the antioxidant potency of organoselenium compounds. Interestingly, replacement of the sec-amide substituent by a tert-amide group leads to a weakening of Se ... 0 interactions in the selenenyl sulfide intermediates. This modification results in 10- to 20-fold enhancements in the catalytic activities. Another strategy involving the replacement of tert-amide moieties by tert-amino substituents further increases the activity by 3- to 4-fold. The most effective modification so far in benzylamine-based GPx mimics appears to be either the replacement of a tert-amino substituent by a sec-amino group or the introduction of an additional 6-methoxy group in the phenyl ring. These strategies can contribute to a remarkable enhancement in the GPx activity. In addition to enhancing catalytic activity, a change in the substituents near the selenium moiety alters the catalytic mechanisms. The mechanistic investigations of functional mimics are useful not only for understanding the complex chemistry at the active site of GPx but also for designing and synthesizing novel antioxidants and anti-inflammatory agents.

Temperature-dependent chirped coherent phonon dynamics in Bi2Te3 using high-intensity femtosecond laser pulses

Degenerate pump-probe reflectivity experiments have been performed on a single crystal of bismuth telluride (Bi2Te3) as a function of sample temperature (3 K to 296 K) and pump intensity using similar to 50 femtosecond laser pulses with central photon energy of 1.57 eV. The time-resolved reflectivity data show two coherently generated totally symmetric A(1g) modes at 1.85 THz and 3.6 THz at 296 K which blue-shift to 1.9 THz and 4.02 THz, respectively, at 3 K. At high photoexcited carrier density of similar to 1.7 x 10(21) cm(-3), the phonon mode at 4.02 THz is two orders of magnitude higher positively chirped (i.e the phonon time period decreases with increasing delay time between the pump and the probe pulses) than the lower-frequency mode at 1.9 THz. The chirp parameter, beta is shown to be inversely varying with temperature. The time evolution of these modes is studied using continuous-wavelet transform of the time-resolved reflectivity data. Copyright (C) EPLA, 2010

On the exothermic peak during annealing of electrodeposited nanocrystalline nickel

Nanocrystalline metals frequently exhibit poor thermal stability, and the exothermic peak in differential scanning calorimetry is usually attributed to grain growth. We show from experiments on electrodeposited nano-Ni with varying levels of S, and tests with microcrystalline Ni and S powders, that the exothermic peak is associated with the formation of a nickel sulfide phase and concurrent grain growth. Analysis suggests that segregation plays a more important role in limiting grain growth than second-phase particles in nano-Ni. (C) 2010 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Electrical switching and thermal studies on bulk Ge-Te-Bi glasses

Bulk, melt quenched Ge18Te82-xBix glasses (1 <= x <= 4) have been found to exhibit memory type electrical switching behavior, which is in agreement with the lower thermal diffusivity values of Ge-Te-Bi samples. A linear variation in switching voltages (V-th) has been found in these samples with increase in thickness which is consistent with the memory type electrical switching. Also, the switching voltages have been found to decrease with an increase in temperature which happens due to the decrease in the activation energy for crystallization at higher temperatures. Further. V-th of Ge18Te82-xBix glasses have been found to decrease with the increase in Bi content, indicating that in the Ge-Te-Bi system, the resistivity of the additive has a stronger role to play in the composition dependence of V-th, in comparison with the network connectivity and rigidity factors. In addition, the composition dependence of crystallization activation energy has been found to show a decrease with an increase in Bi content, which is consistent with the observed decrease in the switching voltages. X-ray diffraction studies on thermally crystallized samples reveal the presence of hexagonal Te, GeTe, Bi2Te3 phases, suggesting that bismuth is not taking part in network formation to a greater extent, as reflected in the variation of switching voltages with the addition of Bi. SEM studies on switched and un-switched regions of Ge-Te-Bi samples indicate that there are morphological changes in the switched region, which can be attributed to the formation of the crystalline channel between two electrodes during switching. (C) 2010 Elsevier B.V. All rights reserved.

A modified sulphide capacity function

The sulphide capacity as originally defined by Fincham and Richardson is a strong function of composition in pseudobinary oxide melts of interest in extractive metallurgy. From an analysis of data available in the literature, it is shown that sulphide capacity is directly proportional to the activity of the basic oxide in the melt, within the uncertainty of experimental data. A single parameter is sufficient to describe the sulphide capacity of a binary slag system under isothermal and isobaric conditions. The correlation indicates that the activity coefficient of the sulphide ion or the neutral base metal sulphide dissolved in the melt is independent of composition in pseudobinary melts within experimental uncertainty. Structural variations in the melt with composition do not seem to affect the activity coefficient of the sulphide. A modified sulphide capacity function is defined which makes the treatment more elegant and greatly simplifies data storage and retrieval. The modified function is not based on any model for the melt.

Characterization of coprecipitated ferroelectric Bi2 VO5·5

Fine powders of orthorhombic bismuth vandate (Bi2VO5.5) have been synthesized by coprecipitation method. Powder X-ray diffraction and electron microscopic techniques have been used to characterize these samples. The formation of the monophasic Bi2VO5.5 was confirmed. The compacted powders sintered at 1070 K have been characterized for their dielectric properties as a function of both temperature (300-900 K) and frequency (100 Hz-10 MHz) and found to be superior to those obtained by the conventional solid-state reaction route.