Electrochemical performance of mixed crystallographic phase nanotubes and nanosheets of titania and titania-carbon/silver composites for lithium-ion batteries

The role of homogeneity in ex situ grown conductive coatings and dimensionality in the lithium storage properties of TiO(2) is discussed here. TiO(2) nanotube and nanosheet comprising of mixed crystallographic phases of anatase and TiO(2) (B) have been synthesized by an optimized hydrothermal method. Surface modifications of TiO(2) nanotube are realized via coating the nanotube with Ag nanoparticles and amorphous carbon. The first discharge cycle capacity (at current rate = 10 mA g(-1)) for TiO(2) nanotube and nanosheet were 355 mAh g(-1) and 225 mAhg(-1), respectively. The conductive surface coating stabilized the titania crystallographic structure during lithium insertion-deinsertion processes via reduction in the accessibility of lithium ions to the trapping sites. The irreversible capacity is beneficially minimized from 110 mAh g(-1) for TiO(2) nanotubes to 96 mAh g(-1) and 57 mAhg(-1) respectively for Ag and carbon modified TiO(2) nanotubes. The homogeneously coated amorphous carbon over TiO(2) renders better lithium battery performance than randomly distributed Ag nanoparticles coated TiO(2) due to efficient hopping of electrons. (C) 2011 Elsevier B.V. All rights reserved.

Phase relations and activities in the Co Ni O system at 1373 K

The tie-lines delineating equilibria between CoO-NiO and Co-Ni solid solutions in the ternary Co-Ni-O system at 1373 K have been determined by electron microprobe andedax point count analysis of the oxide phase equilibrated with the alloy. The oxygen potentials corresponding to the tie-line compositions have been measured using a solid oxide galvanic cell with calcia-stabilized zirconia electrolyte and Ni + NiO reference electrode. Activities in the metallic and oxide solid solution have been derived using a new Gibbs-Duhem integration technique. Both phases exhibit small positive deviations from ideality; the values ofG E/X 1 X 2 are 2640 J mol−1 for the metallic phase and 2870 J mol−1 for the oxide solid solution.

Influence of Phase Connection and Terminal Conditions on Natural Frequencies of Three-Phase Transformer Windings

With the increasing use of extra high-voltage transmission in power system expansion, the manufacturers of power apparatus and the electric utilities are studying the nature of overvoltages in power systems due to lightning and, in particular, switching operations. For such analyses, knowledge of the natural frequencies of the windings of transformers under a wide variety of conditions is important. The work reported by the author in a previous paper is extended and equivalent circuits have been developed to represent several sets of terminal conditions. These equivalent circuits can be used to determine the natural frequencies and transient voltages in the windings. Comparison of the measured and the computed results obtained with a model transformer indicates that they are in good agreement. Hence, this method of analysis provides a satisfactory procedure for the estimation of natural frequencies and transient voltages in transformer windings.

Temperature gradient induced phase transitions and morphological changes in diamond thin film

The diamond films were deposited onto a wurtzite gallium nitride (GaN) thin film substrate using hot-filament chemical vapor deposition (HFCVD). During the film deposition a lateral temperature gradient was imposed across the substrate by inclining the substrate. As grown films predominantly showed the hexagonal phase, when no inclination was applied to the substrate. Tilting the substrate with respect to the heating filament by 6 degrees imposed a lateral temperature gradient across the substrate, which induced the formation of a cubic diamond phase. Diamond grains were predominantly oriented in the (100) direction. However, a further increase in the substrate tilt angle to 12 degrees, resulted in grains oriented in the (111) direction. The growth rate and hence the morphology of diamond grains varied along the inclined substrate. The present study focuses on the measurements of dominant phase formation and crystal orientation with varying substrate inclination using orientation-imaging microscopy (OIM). This technique enables direct examination of individual diamond grains and their crystallographic orientation. (C) 2012 Elsevier B.V. All rights reserved.

Relative effect of slope and equilibrium line altitude on the retreat of Himalayan glaciers

It has been observed that a majority of glaciers in the Himalayas have been retreating. In this paper, we show that there are two major factors which control the advance/retreat of the Himalayan glaciers. They are the slope of the glacier and changes in the equilibrium line altitude. While it is well known, that these factors are important, we propose a new way of combining them and use it to predict retreat. The functional form of this model has been derived from numerical simulations using an ice-flow code. The model has been successfully applied to the movement of eight Himalayan glaciers during the past 25 years. It explains why the Gangotri glacier is retreating while Zemu of nearly the same length is stationary, even if they are subject to similar environmental changes. The model has also been applied to a larger set of glaciers in the Parbati basin, for which retreat based on satellite data is available, though over a shorter time period.

Gibbs Energy of Formation of Ca3Ti8Al12O37 and Phase Relations and Chemical Potentials in the System Al2O3-TiO2-CaO

The quaternary oxide in the system Al2O3-CaO-TiO2 is found to have the composition Ca3Ti8Al12O37 rather than CaTi3Al8O19 as reported in the literature. The standard Gibbs energy of formation of Ca3Ti8Al12O37 from component binary oxides is measured in the temperature range from 900 to 1250 K using a solid-state electrochemical cell incorporating single crystal CaF2 as the solid electrolyte. The results can be represented by the equation: delta G(f(0x))(0) (+/- 70)/J mol(-1) = -248474 - 15.706(T/K). Combining this information with thermodynamic data on calcium aluminates and titanates available in the literature, subsolidus phase relations in the pseudo-ternary system Al2O3-CaO-TiO2 are computed and presented as isothermal sections. The evolution of phase relations with temperature is highlighted. Chemical potential diagrams are computed at 1200 K, showing the stability domains of the various phases in the chemical potential-composition space. In each chemical potential diagram, chemical potential of one component is plotted against the cationic fraction of the other two components. The diagrams are valid at relatively high oxygen potentials where Ti is present in its four-valent state in all the oxide phases.

Phase relationships and magnetic properties of TbxDy1-xFe1.95 alloys

The effect of Tb/Dy ratio on the structural and magnetic properties of (Tb,Dy)Fe-2 class of alloys has been investigated using nine alloys of TbxDy1-xFe1.95 (x = 0-1) covering the entire range. Our results indicate that the three phases viz. (Tb,Dy)Fe-2 (major phase), (Tb,Dy)Fe-3 and(Tb,Dy)-solid solution (minor phases) coexist in all the alloys. The volume fraction of pro-peritectic (Tb,Dy)Fe-3 phase however, has a minimum at x = 0.4 and a maximum at x = 0.6 compositions. The volume fraction of this phase decreases upon heat treatment at 850 degrees C and 1000 degrees C. A Widmanstatten type precipitate of (Tb,Dy)Fe-3 was observed for Dy-rich compositions (0 <= x <= 0.5). The microstructural investigations indicate that the ternary phase equilibria of Tb-Dy-Fe are sensitive to Tb/Dy ratio including the expansion of (Tb,Dy)Fe-2 phase field which is in contrast to the pseudo-binary assumption that is followed in available literature to date. The lattice parameter, Curie temperature and coercivity are found to increase with Tb addition. Split of (440) peak of (Tb,Dy)Fe-2 observed in x >= 0.3 alloys indicate, a spin reorientation transition from 100] to 111] occurs with Tb addition. (C) 2012 Elsevier B. V. All rights reserved.

Antenna Selection in Interference-Constrained Underlay Cognitive Radios: SEP-Optimal Rule and Performance Benchmarking

In the underlay mode of cognitive radio, secondary users are allowed to transmit when the primary is transmitting, but under tight interference constraints that protect the primary. However, these constraints limit the secondary system performance. Antenna selection (AS)-based multiple antenna techniques, which exploit spatial diversity with less hardware, help improve secondary system performance. We develop a novel and optimal transmit AS rule that minimizes the symbol error probability (SEP) of an average interference-constrained multiple-input-single-output secondary system that operates in the underlay mode. We show that the optimal rule is a non-linear function of the power gain of the channel from the secondary transmit antenna to the primary receiver and from the secondary transmit antenna to the secondary receive antenna. We also propose a simpler, tractable variant of the optimal rule that performs as well as the optimal rule. We then analyze its SEP with L transmit antennas, and extensively benchmark it with several heuristic selection rules proposed in the literature. We also enhance these rules in order to provide a fair comparison, and derive new expressions for their SEPs. The results bring out new inter-relationships between the various rules, and show that the optimal rule can significantly reduce the SEP.

Densification kinetics, phase assemblage and hardness of spark plasma sintered Cu-10 wt% TiB2 and Cu-10 wt% TiB2-10 wt% Pb composites

The present work demonstrates the synthesis of Cu-10 wt% TiB2 composites with a theoretical density of more than 90% by tailoring the spark plasma sintering (SPS) conditions in the temperature range of 400-700 degrees C. Interestingly, 10 wt% Pb addition to Cu-10 wt% TiB2 lowers the sinter density and the difference in the densification behavior of the investigated compositions was discussed in reference to the current profile recorded during a SPS cycle. The sintering kinetics and phase assemblage were also discussed in reference to surface melting of the constituents prior to bulk melting temperature, temperature dependent wettability of Pb on Cu, diffusion kinetics of Cu as well as the formation of various oxides. An important result is that a high hardness of around 2 GPa and relative density close to 92% qtheoretical was achieved for the Cu-10 wt% TiB2-10 wt% Pb composite, and such a combination has never been achieved before using any conventional processing route.

Spark plasma sintering may lead to phase instability and inferior mechanical properties: A case study with TiB2

In contrast to the widely reported beneficial aspects of spark plasma sintering in developing materials with better properties, we report here two interesting aspects recorded with difficult-to-sinter titanium diboride: (a) in situ formation of second phase (TiB) and (b) inferior hardness (by similar to 30%) and elastic modulus (by similar to 20%) for spark plasma sintered TiB2, with respect to hot pressed TiB2. The formation of TiB is discussed with reference to the enhanced reaction kinetics in the presence of pulsed electric field. (C) 2013 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Polymorphic phase boundaries and enhanced piezoelectric response in extended composition range in the lead free ferroelectric BaTi1-xZrxO3

Neutron powder diffraction study of Ba(Ti1-xZrx)O-3 at close composition intervals has revealed coexistence of ferroelectric phases: orthorhombic (Amm2) + tetragonal (P4mm) for 0.02 <= x <= 0.05 and rhombohedral (R3m) + orthorhombic (Amm2) for 0.07 <= x < 0.09. These compositions exhibit relatively enhanced piezoelectric properties as compared to their single phase counterparts outside this composition region, confirming the polymorphic phase boundary nature of the phase coexistence regions. (C) 2013 AIP Publishing LLC.

Estimation of Probabilistic Bounds on Phase CPI and Relevance in WCET Analysis

Estimating program worst case execution time(WCET) accurately and efficiently is a challenging task. Several programs exhibit phase behavior wherein cycles per instruction (CPI) varies in phases during execution. Recent work has suggested the use of phases in such programs to estimate WCET with minimal instrumentation. However the suggested model uses a function of mean CPI that has no probabilistic guarantees. We propose to use Chebyshev's inequality that can be applied to any arbitrary distribution of CPI samples, to probabilistically bound CPI of a phase. Applying Chebyshev's inequality to phases that exhibit high CPI variation leads to pessimistic upper bounds. We propose a mechanism that refines such phases into sub-phases based on program counter(PC) signatures collected using profiling and also allows the user to control variance of CPI within a sub-phase. We describe a WCET analyzer built on these lines and evaluate it with standard WCET and embedded benchmark suites on two different architectures for three chosen probabilities, p={0.9, 0.95 and 0.99}. For p= 0.99, refinement based on PC signatures alone, reduces average pessimism of WCET estimate by 36%(77%) on Arch1 (Arch2). Compared to Chronos, an open source static WCET analyzer, the average improvement in estimates obtained by refinement is 5%(125%) on Arch1 (Arch2). On limiting variance of CPI within a sub-phase to {50%, 10%, 5% and 1%} of its original value, average accuracy of WCET estimate improves further to {9%, 11%, 12% and 13%} respectively, on Arch1. On Arch2, average accuracy of WCET improves to 159% when CPI variance is limited to 50% of its original value and improvement is marginal beyond that point.

The Role of Weak Interactions in the Phase Transition and Distinct Mechanical Behavior of Two Structurally Similar Caffeine Co-crystal Polymorphs Studied by Nanoindentation

Although weak interactions, such as C-H center dot center dot center dot O and pi-stacking, are generally considered to be insignificant, it is their reorganization that holds the key for many a solid-state phenomenon, such as phase transitions, plastic deformation, elastic flexibility, and mechanochromic luminescence in solid-state fluorophores. Despite this, the role of weak interactions in these dynamic phenomena is poorly understood. In this study, we investigate two co-crystal polymorphs of caffeine:4-chloro-3-nitrobenzoic acid, which have close structural similarity (2D layered structures), but surprisingly show distinct mechanical behavior. Form I is brittle, but shows shear-induced phase instability and, upon grinding, converts to Form II, which is soft and plastically shearable. This observation is in contrast to those reported in earlier studies on aspirin, wherein the metastable drug forms are softer and convert to stable and harder forms upon stressing To establish a molecular level understanding, have investigated the two co-crystal polymorphs I and II by single crystal X-ray diffraction, nanoindentation to quantify mechanical properties, and theoretical calculations. The lower hardness (from nanoindentation) and smooth potential surfaces (from theoretical studies) for shearing of layers in Form II allowed us to rationalize the role of stronger intralayer (sp(2))C-H center dot center dot center dot O and nonspecific interlayer pi-stacking interactions in the structure of II. Although the Form I also possesses the same type of interactions, its strength is clearly opposite, that is, weaker intralayer (sp(3))C-H center dot center dot center dot O and specific interlayer pi-stacking interactions. Hence, Form I is harder than Form IL Theoretical calculations and indentation on (111) of Form I suggested the low resistance of this face to mechanical stress; thus, Form I converts to II upon mechanical action. Hence, our approach demonstrates the usefulness of multiple techniques for establishing the role of weak noncovalent interactions in solid-state dynamic phenomena, such as stress induced phase transformation, and hence is important in the context of solid-state pharmaceutical chemistry and crystal engineering.

Dielectric relaxation, phase transition and Rietveld studies of perovskite Pb0.94Sr0.06](Mn1/3Sb2/3)(0.05)(Zr0.52Ti0.48)(0.95)]O-3 ceramics

The frequency-dependent dielectric relaxation of Pb0.94Sr0.06](Mn1/3Sb2/3)(0.05)(Zr0.52Ti0.48)(0.95)]O-3 ceramics, synthesized in pure perovskite phase by a solid-state reaction technique is investigated in the temperature range from 303 to 773 K by alternating-current impedance spectroscopy. Using Cole-Cole model, an analysis of the imaginary part of the dielectric permittivity with frequency is performed assuming a distribution of relaxation times. The scaling behavior of the imaginary part of the electric modulus suggests that the relaxation describes the same mechanism at various temperatures. The variation of dielectric constant with temperature is explained considering the space-charge polarization. The SEM indicates that the sample has single phase with an average grain size similar to 14.2 mu m. The material exhibits tetragonal structure. A detailed temperature dependent dielectric study at various frequencies has also been performed. (C) 2013 Elsevier B.V. All rights reserved.