A transmission electron microscopy and X-ray photoelectron spectroscopy study of annealing induced gamma-phase nucleation, clustering, and interfacial dynamics in reactively sputtered amorphous alumina thin films

Pure alpha-Al2O3 exhibits a very high degree of thermodynamical stability among all metal oxides and forms an inert oxide scale in a range of structural alloys at high temperatures. We report that amorphous Al2O3 thin films sputter deposited over crystalline Si instead show a surprisingly active interface. On annealing, crystallization begins with nuclei of a phase closely resembling gamma-Alumina forming almost randomly in an amorphous matrix, and with increasing frequency near the substrate/film interface. This nucleation is marked by the signature appearance of sharp (400) and (440) reflections and the formation of a diffuse diffraction halo with an outer maximal radius of approximate to 0.23 nm enveloping the direct beam. The microstructure then evolves by a cluster-coalescence growth mechanism suggestive of swift nucleation and sluggish diffusional kinetics, while locally the Al ions redistribute slowly from chemisorbed and tetrahedral sites to higher anion coordinated sites. Chemical state plots constructed from XPS data and simple calculations of the diffraction patterns from hypothetically distorted lattices suggest that the true origins of the diffuse diffraction halo are probably related to a complex change in the electronic structure spurred by the a-gamma transformation rather than pure structural disorder. Concurrent to crystallization within the film, a substantially thick interfacial reaction zone also builds up at the film/substrate interface with the excess Al acting as a cationic source. (C) 2015 AIP Publishing LLC.

Direct measurements of growing amorphous order and non-monotonic dynamic correlations in a colloidal glass-former

The transformation of flowing liquids into rigid glasses is thought to involve increasingly cooperative relaxation dynamics as the temperature approaches that of the glass transition. However, the precise nature of this motion is unclear, and a complete understanding of vitrification thus remains elusive. Of the numerous theoretical perspectives(1-4) devised to explain the process, random first-order theory (RFOT; refs 2,5) is a well-developed thermodynamic approach, which predicts a change in the shape of relaxing regions as the temperature is lowered. However, the existence of an underlying `ideal' glass transition predicted by RFOT remains debatable, largely because the key microscopic predictions concerning the growth of amorphous order and the nature of dynamic correlations lack experimental verification. Here, using holographic optical tweezers, we freeze a wall of particles in a two-dimensional colloidal glass-forming liquid and provide direct evidence for growing amorphous order in the form of a static point-to-set length. We uncover the non-monotonic dependence of dynamic correlations on area fraction and show that this non-monotonicity follows directly from the change in morphology and internal structure of cooperatively rearranging regions(6,7). Our findings support RFOT and thereby constitute a crucial step in distinguishing between competing theories of glass formation.

Use of Data Driven Techniques for Short Lead Time Streamflow Forecasting in Mahanadi basin

Streamflow forecasts at daily time scale are necessary for effective management of water resources systems. Typical applications include flood control, water quality management, water supply to multiple stakeholders, hydropower and irrigation systems. Conventionally physically based conceptual models and data-driven models are used for forecasting streamflows. Conceptual models require detailed understanding of physical processes governing the system being modeled. Major constraints in developing effective conceptual models are sparse hydrometric gauge network and short historical records that limit our understanding of physical processes. On the other hand, data-driven models rely solely on previous hydrological and meteorological data without directly taking into account the underlying physical processes. Among various data driven models Auto Regressive Integrated Moving Average (ARIMA), Artificial Neural Networks (ANNs) are most widely used techniques. The present study assesses performance of ARIMA and ANNs methods in arriving at one-to seven-day ahead forecast of daily streamflows at Basantpur streamgauge site that is situated at upstream of Hirakud Dam in Mahanadi river basin, India. The ANNs considered include Feed-Forward back propagation Neural Network (FFNN) and Radial Basis Neural Network (RBNN). Daily streamflow forecasts at Basantpur site find use in management of water from Hirakud reservoir. (C) 2015 The Authors. Published by Elsevier B.V.

Structural crossover from nonmodulated to long-period modulated tetragonal phase and anomalous change in ferroelectric properties in the lead-free piezoelectric Na1/2Bi1/2TiO3-BaTiO3

The highly complex structure-property interrelationship in the lead-free piezoelectric (x) Na1/2Bi1/2TiO3 - (1 - x) BaTiO3 is a subject of considerable contemporary debate. Using comprehensive x-ray, neutron diffraction, dielectric, and ferroelectric studies, we have shown the existence of a new criticality in this system at x = 0.80, i.e., well within the conventional tetragonal phase field. This criticality manifests as a nonmonotonic variation of the tetragonality and coercivity and is shown to be associated with a crossover from a nonmodulated tetragonal phase (for x < 0.8) to a long-period modulated tetragonal phase (for x > 0.80). It is shown that the stabilization of long-period modulation introduces a characteristic depolarization temperature in the system. While differing qualitatively from the two-phase model often suggested for the critical compositions of this system, our results support the view with regard to the tendency in perovskites to stabilize long-period modulated structures as a result of complex interplay of antiferrodistortive modes Bellaiche and Iniguez, Phys. Rev. B 88, 014104 ( 2013); Prosandeev, Wang, Ren, Iniguez, ands Bellaiche, Adv. Funct. Mater. 23, 234 (2013)].

Optical and dielectric study of strontium modified barium zirconium titanate ceramic prepared by high energy ball milling

Strontium modified barium zirconium titanate with general formula Ba1-xSrxZr0.05Ti0.95O3 ceramics have been prepared by solid state and high energy ball milling technique. The X-ray diffraction and Rietveld refinement studies show that all the compositions have single phase symmetry. The composition BaZr0.05Ti0.95O3 shows orthorhombic symmetric with space group Amm2. The structure changes from orthorhombic to tetragonal with strontium doping up to x = 0.3 and with further addition, changes to cubic. The scanning electron micrographs show that the grain size decreases with increase in strontium content. The temperature dependent dielectric behavior shows three phase transition in the parent material which merges with an increase in Sr content The transition temperature and dielectric constant decreases with an increase in Sr concentration. The phase transition becomes more diffused with increment in doping concentration. The ferroelectric behavior of the ceramics is studied by the hysteresis loop. The optical behavior is studied by the UV-visible spectroscopy and found that the optical band gap increases with Sr concentration. (C) 2015 Elsevier B.V. All rights reserved.

Electric field induced short range to long range structural ordering and its influence on the Eu+3 photoluminescence in the lead-free ferroelectric Na1/2Bi1/2TiO3

Eu+3 was incorporated into the lattice of a lead-free ferroelectric Na1/2Bi1/2TiO3 (NBT) as per the nominal formula Na0.5Bi0.5-xEuxTiO3. This system was investigated with regard to the Eu+3 photoluminescence (PL) and structural behaviour as a function of composition and electric field. Electric field was found to irreversibly change the features in the PL spectra and also in the x-ray diffraction patterns below the critical composition x = 0.025. Detailed analysis revealed that below the critical composition, electric field irreversibly suppresses the structural heterogeneity inherent of the host matrix NBT and brings about a long range ferroelectric state with rhombohedral (R3c) distortion. It is shown that the structural disorder on the nano-scale opens a new channel for radiative transition which manifests as a new emission line branching off from the main D-5(0)-> F-7(0) line along with a concomitant change in the relative intensity of the other crystal field induced Stark lines with different J values. The study suggests that Eu+3 luminescence can be used to probe the relative degree of field induced structural ordering in relaxor ferroelectrics and also in high performance piezoelectric alloys where electric field couples very strongly with the lattice and structural degrees of freedom. (C) 2015 AIP Publishing LLC.

Lead selection and characterization of antitubercular compounds using the Nested Chemical Library

Discovering new drugs to treat tuberculosis more efficiently and to overcome multidrug resistance is a world health priority. To find novel antitubercular agents several approaches have been used in various institutions worldwide, including target-based approaches against several validated mycobacterial enzymes and phenotypic screens. We screened more than 17,000 compounds from Vichem's Nested Chemical Library(TM) using an integrated strategy involving whole cell-based assays with Corynebacterium glutamicum and Mycobacterium tuberculosis, and target-based assays with protein kinases PknA, PknB and PknG as well as other targets such as PimA and bacterial topoisomerases simultaneously. With the help of the target-based approach we have found very potent hits inhibiting the selected target enzymes, but good minimal inhibitory concentrations (MIC) against M. tuberculosis were not achieved. Focussing on the whole cell-based approach several potent hits were found which displayed minimal inhibitory concentrations (MIC) against M. tuberculosis below 10 mu M and were non-mutagenic, non-cytotoxic and the targets of some of the hits were also identified. The most active hits represented various scaffolds. Medicinal chemistry-based lead optimization was performed applying various strategies and, as a consequence, a series of novel potent compounds were synthesized. These efforts resulted in some effective potential antitubercular lead compounds which were confirmed in phenotypic assays. (C) 2015 Elsevier Ltd. All rights reserved.

Hydrogen-induced mechanical properties of amorphous silicon thin films

Mechanical properties of thin films such as residual stress and hardness are of paramount importance from the device fabrication point of view. Intrinsic stress in sputtered films can be tensile or compressive as decided by the number density and the energy of the plasma species striking the growing film. In the presence of hydrogen we analyzed the applicability of idealized stress reversal curve for amorphous silicon thin films deposited by DC, pulsed DC (PDC) and RF sputtering. We are successfully able to correlate the microstructure with the stress reversal and hardness. We observed a stress reversal from compressive to tensile with hydrogen incorporation. It was found that unlike in idealized stress reversal curve case, though the energy of plasma species is less in DC plasma, DC deposited films exhibit more compressive stress, followed by PDC and RF deposited films. A tendency towards tensile stress from compressive stress was observed at similar to 13, 18 and 23 at%H for DC, PDC and RF deposited films respectively, which is in exact agreement with the vacancy to void transition in the films. Regardless of the sputtering power mode, the hardness of a-Si:H films is found to be maximum at C-H similar to 10 at%H. Enhancement in hardness with C-H (up to C-H similar to 10 at%H) is attributed to increase of Si-H bonds. Beyond C-H similar to 10 at%H, hardness starts falling. (C) 2015 Elsevier Ltd. All rights reserved.

Studies on 12 V substrate-integrated lead-carbon hybrid ultracapacitors

A cost-effective 12 V substrate-integrated lead-carbon hybrid ultracapacitor is developed and performance tested. These hybrid ultracapacitors employ flexible-graphite sheets as negative plate current-collectors that are coated amperometrically with a thin layer of conducting polymer, namely poly-aniline to provide good adhesivity to activated-carbon layer. The positive plate of the hybrid ultracapacitors comprise conventional lead-sheet that is converted electrochemically into a substrate-integrated lead-dioxide electrode. 12 V substrate-integrated lead-carbon hybrid ultracapacitors both in absorbent-glass-mat and polymeric silica-gel electrolyte configurations are fabricated and characterized. It is possible to realize 12 V configurations with capacitance values of similar to 200 F and similar to 300 F, energy densities of similar to 1.9 Wh kg(-1) and similar to 2.5 Wh kg(-1) and power densities of similar to 2 kW kg(-1) and similar to 0.8 kW kg(-1), respectively, having faradaic-efficiency values of similar to 90 % with cycle-life in excess of 100,000 cycles. The effective cost of the mentioned hybrid ultracapacitors is estimated to be about similar to 4 US$/Wh as compared to similar to 20 US$/Wh for commercially available ultracapacitors.

An organically modified exfoliated graphite electrode for the voltammetric determination of lead ions in contaminated water samples

This work presents a new electrode, 2-benzoylnaphtho 2,1-b]furan hydrazone exfoliated graphite paste electrode (B-EGPE) fabricated for the differential pulse anodic stripping voltammetric determination of lead (Pb). Under the optimal conditions, Pb2+ could be detected in the concentration range from 2.75 x 10(-7) to 1.5 x 10(-6) mol/L with the linear regression equation, y = 19.41 x 10(-6) x + 0.4249 x 10(-9) with R = 0.99. Interferences from other ions were investigated and the proposed method was further applied to the trace levels of Pb2+ detection in real samples with satisfactory results.

High Catalytic Activity of Amorphous Ir-Pi for Oxygen Evolution Reaction

Large-scale production of hydrogen gas by water electrolysis is hindered by the sluggish kinetics of oxygen evolution reaction (OER) at the anode. The development of a highly active and stable catalyst for OER is a challenging task. Electrochemically prepared amorphous metal-based catalysts have gained wide attention after the recent discovery of a cnbalt-phosphate (Co-Pi) catalyst: Herein, an amorphous iridium-phosphate (Ir-Pi) is investigated as an oxygen evolution catalyst. The catalyst is prepared by the anodic polarization of carbon paper electrodes in neutral phosphate buffer solutions containing IrCl3. The Ir-Pi film deposited on the substrate has significant amounts of phosphate and It centers in an oxidation state higher than +4. Phosphate plays a significant role in the deposition of the catalyst and also in its activity toward OER. The onset potential of OER on the Ir-Pi is about 150 mV lower in comparison with the Co-Pi under identical experimental conditions. Thus, Ir-Pi is a promising catalyst for electrochemical oxidation of water.

Energy-savvy solid-state and sonochemical synthesis of lithium sodium titanate as an anode active material for Li-ion batteries

Lithium sodium titanate insertion-type anode has been synthesized by classical solid-state (dry) and an alternate solution-assisted (wet) sonochemical synthesis routes. Successful synthesis of the target compound has been realized using simple Na- and Li-hydroxide salts along with titania. In contrast to the previous reports, these energy-savvy synthesis routes can yield the final product by calcination at 650 -750 degrees C for limited duration of 1-10 h. Owing to the restricted calcination duration (dry route for 1-2 h and wet route for 1-5 h), they yield homogeneous nanoscale lithium sodium titanate particles. Sono-chemical synthesis reduces the lithium sodium titanate particle size down to 80-100 nm vis-a-vis solid-state method delivering larger (200-500 nm) particles. Independent of the synthetic methods, the end products deliver reversible electrochemical performance with reversible capacity exceeding 80 mAh.g(-1) acting as a 1.3 V anode for Li-ion batteries. (C) 2015 Elsevier B.V. All rights reserved.

Modeling of Effect of Nucleation Rate and Electrodes' Resistance on Discharge Characteristics of Lead-Acid Batteries

Classical models are not successful in describing discharge characteristics of a lead-acid battery when the current density is varied over a wide range. A model is developed in this work to overcome this lacuna by introducing into the standard models two mechanisms that have not been used earlier. Lead sulfate particles nucleate and grow on active materials of electrodes during discharge, resulting in coverage of active area. Increasing rate of discharge builds supersaturation of lead sulfate rapidly, and causes increased extents of nucleation and coverage. Electrodes behave almost like an insulator due to deposition of lead sulfate when active materials are converted to a critical extent, and this can stop discharge process. Influence of this mechanism is also rate dependent. The new model developed is tested against data on polarization behavior, and capacity drawn as a function of current. The model successfully predicts both polarization curves and Peukert behavior. The model is used to predict charge that can be drawn at a current after partial discharge at a different current. Model suggests that altering nucleation behavior can be useful in enhancing capacity available for discharge. (C) 2015 The Electrochemical Society.

Interrelationship between Interphase Boundaries and Phase Contents near the Critical Compositions of Lead-Free Ferroelectric (Na0.5Bi0.5)TiO3-BaTiO3

Heterophase structures in lead-free perovskite-type ferroelectric solid solutions of (1 - z)(Na0.5Bi0.5)TiO3 - zBaTiO(3) are analysed for a few critical compositions near the morphotropic phase boundary (z = 0.05-0.07). Examples of the phase coexistence and elastic matching of the phases from different symmetry groups are considered to find optimum volume fractions of specific domain types and coexisting phases at the complete stress relief in two-phase samples. Some interrelations between these volume fractions are described using variants of the domain arrangement at changes in the composition and unit-cell parameters. The evaluated room-temperature volume fractions of the ferroelectric monoclinic (Cm symmetry) and tetragonal (P4mm symmetry) phases near the morphotropic phase boundary are in agreement with experimental data.

Effect of laser irradiation on optical properties of Ge12Sb25Se63 amorphous chalcogenide thin films

The change in photo-induced optical properties in thermally evaporated Ge12Sb25Se63 chalcogenide thin film under 532-nm laser illumination has been reported in this paper. The structure and composition of the film have been examined by X-ray diffraction and energy dispersive X-ray analysis, respectively. The optical properties such as refractive index, extinction coefficient and thickness of the films have been determined from the transmission spectra based on inverse synthesis method and the optical band gap has been derived from optical absorption spectra using the Tauc plot. It has been found that the mechanism of the optical absorption is due to allowed indirect transition. The optical band gap increases by 0.05 eV causing photo-bleaching mechanism, while refractive index decreases because of reduction in structural disordering. Deconvolution of Raman and X-ray photoelectron spectra into several peaks provides different structural units, which supports the optical photo-bleaching.