Fabrication and Phase Transformation in Crystalline Nanoparticles of PbZrO3 Derived By Sol-Gel

In this research fabrication of crystalline PbZrO3 (PZ) nanoparticles and their phase transformation behavior is investigated. A novel sol-gel method was used for the synthesis of air-stable and precipitate-free diol-based sol of PZ, which was dried at 150 degrees C and then calcined at 300-700 degrees C for 1 h. The morphology, crystallinity and phase formation of as synthesized nanoparticles were studied by the selected-area electron diffraction (SAED), X-ray diffraction (XRD), thermal gravimetric analysis/differential scanning calorimetry (TGA-DSC), and high resolution transmission electron microscope (HRTEM). The XRD, SAED, and TGA-DSC analyses confirmed the tetragonal lead rich zirconia phase (t-Z phase) and monoclinic zirconia phase (m-Z phase) as the intermediate phases during the calcinations process followed by crystallization of single orthorhombic PZ phase at about 700 degrees C. The average PZ particle size was observed about 20 nm as confirmed by TEM study. Energy-dispersive X-ray spectroscopy (EDX) analysis demonstrated that stoichiometric PbZrO3 was formed.

Topological close packed mu phase formation and the determination of diffusion parameters in the Co-Mo system

The study on the formation and growth of topological close packed (TCP) compounds is important to understand the performance of turbine blades in jet engine applications. These deleterious phases grow mainly by diffusion process in the superalloy substrate. Significant volume change was found because of growth of the p phase in Co-Mo system. Growth kinetics of this phase and different diffusion parameters, like interdiffusion, intrinsic and tracer diffusion coefficients are calculated. Further the activation energy, which provides an idea about the mechanism, is determined. Moreover, the interdiffusion coefficient in Co(Mo) solid solution and impurity diffusion coefficient of Mo in Co are determined.

A universal relation for the cohesive energy of nanoparticles

A universal relation between the cohesive energy and the particle size has been predicted based on the liquid-drop model. The universal relation is well supported by other theoretical models and the available experimental data. The universal relations for intermediate size range as well as for particles with very few atoms are discussed. A comparison of onset temperature of evaporation also establishes a universal relation.

Anomalous dynamical charges, phonons, and the origin of negative thermal expansion in Y2W3O12

We use a combination of classical model and first-principles density functional theory calculations to study lattice dynamics of Y2W3O12 and identify phonons responsible for its negative thermal expansion (NTE). Born dynamical charges of various atoms are found to deviate anomalously from their nominal values. We find that the phonons with energy from 4 to 10 meV are the primary contributors to its NTE. These phonons involve rotations of the YO6 octahedra and WO4 tetrahedra in mutually opposite sense and collective translational atomic displacements, reflecting a strong mixing between acoustic and optic modes.

Processing Response of Boron Modified Ti-6Al-4V Alloy In (alpha plus beta) Working Regime

Titanium alloys like Ti-6A-4V are the backbone materials for aerospace, energy and chemical industries. Hypoeutectic boron addition to Ti-6Al-4V alloy produces a reduction in as-cast grain size by roughly an order of magnitude resulting in the possibility of avoiding ingot breakdown step and thereby reducing the processing cost. In the present study, ISM processed as-cast boron added Ti-6Al-4V alloy is deformed in (alpha+beta)-phase field, where alpha-lath bending seemed to be the dominating deformation mechanism.

Gibbs Energy of Formation of MnO: Measurement and Assessment

Based on the measurements of Alcock and Zador, Grundy et al. estimated an uncertainty of the order of +/- 5 kJ mol(-1) for the standard Gibbs energy of formation of MnO in a recent assessment. Since the evaluation of thermodynamic data for the higher oxides Mn3O4, Mn2O3, and MnO2 depends on values for MnO, a redetermination of its Gibbs energy of formation was undertaken in the temperature range from 875 to 1300 K using a solid-state electrochemical cell incorporating yttria-doped thoria (YDT) as the solid electrolyte and Fe + Fe1-delta O as the reference electrode. The cell can be presented as Pt, Mn + MnO/YDT/Fe + Fe1+delta O, Pt Since the metals Fe and Mn undergo phase transitions in the temperature range of measurement, the reversible emf of the cell is represented by the three linear segments. Combining the emf with the oxygen potential for the reference electrode, the standard Gibbs energy of formation of MnO from alpha-Mn and gaseous diatomic oxygen in the temperature range from 875 to 980 K is obtained as: Delta G(f)(o)/Jmol(-1)(+/- 250) = -385624 + 73.071T From 980 to 1300 K the Gibbs energy of formation of MnO from beta-Mn and oxygen gas is given by: Delta G(f)(o)/Jmol(-1)(+/- 250) = -387850 + 75.36T The new data are in excellent agreement with the earlier measurements of Alcock and Zador. Grundy et al. incorrectly analyzed the data of Alcock and Zador showing relatively large difference (+/- 5 kJ mol(-1)) in Gibbs energies of MnO from their two cells with Fe + Fe1-delta O and Ni + NiO as reference electrodes. Thermodynamic data for MnO is reassessed in the light of the new measurements. A table of refined thermodynamic data for MnO from 298.15 to 2000 K is presented.

Influence of quantum confinement on the photoemission from superlattices of optoelectronic materials

We study the photoemission from quantum wire and quantum dot superlattices with graded interfaces of optoelectronic materials on the basis of newly formulated electron dispersion relations in the presence of external photo-excitation. Besides, the influence of a magnetic field on the photoemission from the aforementioned superlattices together with quantum well superlattices in the presence of a quantizing magnetic field has also been studied in this context. It has been observed taking into account HgTe/Hg1-xCdxTe and InxGa1-xAs/InP that the photoemission from these nanostructures increases with increasing photon energy in quantized steps and exhibits oscillatory dependences with the increase in carrier concentration. Besides, the photoemission decreases with increasing light intensity and wavelength, together with the fact that said emission decreases with increasing thickness exhibiting oscillatory spikes. The strong dependences of the photoemission on the light intensity reflects the direct signature of light waves on the carrier energy spectra. The content of this paper finds six applications in the fields of low dimensional systems in general. (C) 2010 Elsevier Ltd. All rights reserved.

Phase Diagram for the System RuO2-TiO2 in Air

There are conflicting reports in the literature regarding solid solubility in the system RuO2-TiO2. To resolve this issue a few experiments were conducted in air at 1673, 1723, and 1773 K. The results show limited terminal solid solubility. There is an extended solid-state miscibility gap that intersects the decomposition curve for the RuO2-rich solid solution generating a peritectoid reaction at 1698 K. The measured equilibrium compositions of the solid solutions are used to develop a thermodynamic description of the oxide solid solution with rutile structure. Using the subregular solution model, the enthalpy of mixing can be represented by the expression, Delta H-M/J center dot mol(-1) = XTiO2XRuO2 ( 34,100X(TiO2) + 30,750X(RuO2)). The binodal and spinodal curves and T-X phase diagram in air are computed using this datum and Gibbs energy of formation of RuO2 available in the literature. The computed results suggest that equilibrium was not attained during solubility measurements at lower temperatures reported in the literature.

Thermodynamic activities in the Pb(Zr1-XTiX)O-3 solid solution at 1373 K

Although Pb(Zr1-XTiX)O-3 solid solution is the cornerstone of the piezoelectric ceramics, there is no information in the literature on thermodynamic activities of the component phases in the solid solution. Using inter-crystalline ion exchange equilibria between Pb(Zr1-XTiX)O-3 solid solution with cubic perovskite structure and (Zr1-YTiY)O-2 solid solutions with monoclinic and tetragonal structures, activities of PbTiO3 and PbZrO3 in the perovskite solid solution have been derived at 1373 K using the modified Gibbs-Duhem integration technique of Jacob and Jeffes. Tie-lines from the cubic solid solution are skewed towards the ZrO2 corner. Activities in the zirconia-rich (Zr1-YTiY)02 solid solutions are taken from a recent emf study. The results for the perovskite solid solution at 1373 K can be represented by a sub-regular solution model: Delta G(E.M) (J mol(-1)) = X-PbTiO3 X-PbZrO3(5280X(PbTiO3) - 1980X(PbZrO3)) where Delta G(E.M) is the excess Gibbs energy of mixing of the cubic solid solution and Xi represents the mole fraction of component i. There is a significant positive deviation from ideality for PbTiO3-rich compositions and mild negative deviation near the PbZrO3 corner. The cubic solid solution is intrinsically stable against composition fluctuations at temperatures down to 840 K. The results contrast sharply with the recent calorimetric data on enthalpy of mixing which signal instability of the cubic perovskite solid solution. (C) 2007 Elsevier B.V. All rights reserved.

Energy harvesting using ionic electro-active polymer thin films with Ag-based electrodes

In this paper we employ the phenomenon of bending deformation induced transport of cations via the polymer chains in the thickness direction of an electro-active polymer (EAP)-metal composite thin film for mechanical energy harvesting. While EAPs have been applied in the past in actuators and artificial muscles, promising applications of such materials in hydrodynamic and vibratory energy harvesting are reported in this paper. For this, functionalization of EAPs with metal electrodes is the key factor in improving the energy harvesting efficiency. Unlike Pt-based electrodes, Ag-based electrodes have been deposited on an EAP membrane made of Nafion. The developed ionic metal polymer composite (IPMC) membrane is subjected to a dynamic bending load, hydrodynamically, and evaluated for the voltage generated against an external electrical load. An increase of a few orders of magnitude has been observed in the harvested energy density and power density in air, deionized water and in electrolyte solutions with varying concentrations of sodium chloride (NaCl) as compared to Pt-based IPMC performances reported in the published literature. This will have potential applications in hydrodynamic and residual environmental energy harvesting to power sensors and actuators based on micro-andn nano-electro-mechanical systems (MEMS and NEMS) for biomedical,maerospace and oceanic applications.

Interdiffusion in the Ni-Mo system

The interdiffusion coefficient in Ni(Mo) solid solution, impurity diffusion of Mo in Ni, average interdiffusion coefficient of the NiMo-sigma phase and activation energies for diffusion in solid solution and in the sigma phase of the Ni-Mo binary system are evaluated through the diffusion couple approach. These results are utilized to identify the possible diffusion mechanism. Low activation energy in the sigma phase indicates a grain-boundary-controlled diffusion process. (C) 2010 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Metal-spinel-corundum three phase equilibria in the system Ni-Cr-Al-O at 1373 K

The tie-lines representing the inter-crystalline ion exchange equilibria between the NiCr2O4-NiAl2O4 spinet solid solution and Cr2O3-Al2O3 corundum solid solution are determined by electron microprobe andEDAX pointcountanalysis of the oxide phases equilibrated with metallic Ni at 1373 K. The component activities in the spinet solid solution are derived from the tie-lines and thermodynamic data for Cr2O3-Al2O3 solid solution available in the literature. The Gibbs energy of mixing of the spinet solid solution calculated from the experimental data is discussed in relation to the values derived from the cation distribution models which assume random mixing of cations on both tetrahedral and octahedral sites. Positive deviation from the models is observed indicating significant positive enthalpy contribution arising form the size mismatch between Al+3 and Ni+2 ions on the tetrahedral site and Al+3, Ni+2 and Cr+3 on the octahedral site. Variation of the oxygen potential for threephase equilibrium involving metallic nickel, spinet solid solution and corundum solid solution is computed as a function of composition of the solid solutions at 1373 K. The oxygen potential exhibits a minimum at aluminum cationic fraction eta(Al)/(eta(Al) + eta(Cr)) = 0.524 in the oxide solid solutions.

Impedance studies on high energy Li3+ irradiated PZT thin films

The ferroelectric Pb(Zr0.48Ti0.52)O-3 (PZT) thin films prepared by the pulsed laser deposition technique were studied for their response to high energy lithium ion irradiation through impedance spectroscopy. The Debye peaks, observed in the impedance and modulus plots of irradiatedfilms, shifts towards higher frequencies compared to those of unirradiated films. This is equivalent to the trend observed with increase in temperature in the unirradiated films due to the dielectric relaxation. The irradiated films showed a decrease in the grain resistance compared to the unirradiated films. The activation energy of dielectric relaxation increases from 1.25 eV of unirradiated film to 1.62 eV of irradiated film. The observed modifications in the irradiated film were ascribed to the modifications in the grain structure due to the high value of electronic energy loss.

Pressure and thermally induced stages of wear in dry sliding of a steel ball against an aluminium-silicon alloy flat

Wear of etched near-eutectic aluminium silicon alloy slid against a steel ball under ambient is explored. The sliding velocity is kept low (0.01 m/s) and the nominal contact pressure is varied in a 15-40 MPa range. Four stages of wear are identified; ultra mild wear, mild wear, severe wear and post severe oxidative wear. The first transition is controlled by the protrusions of silicon particles, projecting out of the aluminium alloy matrix. Once these protrusions disappear under pressure and sliding, oxidation and bulk energy dissipation mechanisms take over to institute transitions to other stages of wear. The phenomenological characteristics of wear stages are explored using a variety of techniques including nanoindentation, focused ion beam milling, electron microscopy, X-ray photoelectron spectroscopy (XPS), energy dispersive X-ray spectroscopy (EDS) and optical interferometry. (c) 2010 Elsevier B.V. All rights reserved.

On the low temperature deformation mechanism in polycrystalline cadmium

The thermally activated plastic flow of polycrystalline cadmium was investigated by differentialstress creep tests at 86°K and tensile tests in the temperature range 86°–473°K. The activation energy (0.55 eV) at zero effective stress and the activation volume as a function of effective stress were obtained. It is concluded that intersection of glide and forest dislocations becomes rate controlling for low temperature deformation. The approximate stacking-fault width in cadmium is deduced to be “1.5b”.