Low oxygen potential boundary for the stability of YBA2Cu3O7−δ

On lowering the oxygen potential, the tetragonal phase of YBa2Cu3O7−δ was found to decompose into a mixture of Y2BaCuO5, BaCuO2 and BaCu2O2 in the temperature range 773–1173 K. The 123 compound was contained in a closed crucible of yttria-stabilized zirconia in the temperature range 773–1073 K. Oxygen was removed in small increments by coulometric titration through the solid electrolyte crucible at constant temperature. The oxygen potential was calculated from the open circuit e.m.f. of the solid state cell after successive titrations. Pure oxygen at a pressure of 1.01 × 105 Pa was used as the reference electrode. The decomposition of the 123 compound manifested as a plateau in oxygen potential. The decomposition products were identified by X-ray diffraction. At temperatures above 1073 K there was some evidence of reaction between the 123 compound, solid electrolyte crucible and platinum. For measurements above 1073 K, the 123 compound was contained in a magnesia crucible placed in a closed outer silica tube. The oxygen potential in the gas phase above the 123 compound was controlled and measured by a solid state cell based on yttria-stabilized zirconia which served both as a pump and sensor. The lower oxygen potential limit for the stability of the 123 compound is given by View the MathML source The oxygen non-stoichiometric parameter δ for the 123 compound has a value of 0.98 (View the MathML source) at dissociation.

Variation of the partial thermodynamic properties of oxygen with composition in YBa2Cu3O7−δ

The variation of equilibrium oxygen potential with oxygen concentration inYBa 2Cu3O7-δhas been measured in the temperature range of 773 to 1223 K. For temperatures up to 1073 K, the oxygen content of theYBa 2Cu3O7-δsample, held in a stabilized-zirconia crucible, was altered by coulometric titration. The compound was in contact with the electrolyte, permitting direct exchange of oxygen ions. For measurements above 1073 K, the oxide was contained in a magnesia crucible placed inside a closed silica tube. The oxygen potential in the gas phase above the 123 compound was controlled and measured by a solid-state cell based on yttria-stabilized zirconia, which served both as a pump and sensor. Pure oxygen at a pressure of 1.01 × 105 Pa was used as the reference electrode. The oxygen pressure over the sample was varied from 10-1 to 105 Pa. The oxygen concentrations of the sample equilibrated with pure oxygen at 1.01 × 105 Pa at different temperatures were determined after quenching in liquid nitrogen by hydrogen reduction at 1223 K. The plot of chemical potential of oxygen as a function of oxygen non-stoichiometry shows an inflexion at δ ∼ 0.375 at 873 K. Data at 773 K indicate tendency for phase separation at lower temperatures. The partial enthalpy and entropy of oxygen derived from the temperature dependence of electromotive force (emf ) exhibit variation with composition. The partial enthalpy for °= 0.3, 0.4, and 0.5 also appears to be temperature dependent. The results are discussed in comparison with the data reported in the literature. An expression for the integral free energy of formation of YBa2Cu3O6.5 is evaluated based on measurements reported in the literature. By integration of the partial Gibbs’ energy of oxygen obtained in this study, the variation of integral property with oxygen concentration is obtained at 873 K.

Tie lines and activities in the system CoO MgO SiO2 at 1373 K

The tie lines between (CoXMg1−X)O solid solution with rock salt structure and orthosilicate solid solution (CoYMg1−Y)-Si0.5O2, and between orthosilicate and metasilicate (CoZMg1-Z)SiO3 crystalline solutions, have been determined experimentally at 1373 K. The compositions of coexisting phases have been determined by electron probe microanalysis (EPMA) and lattice parameter measurement on equilibrated samples. The metasilicate solid solution exists only for 0 > Z > 0.213. The activity of CoO in the rock salt solid solution was determined as a function of composition and temperature in the range of 1023 to 1373 K using a solid-state galvanic cell: Pt, (CoXMg1−X)O+Co|(Y2O3)ZrO2|Co+CoO, Pt The free energy of mixing of (CoXMg1−X)O crystalline solution can be expressed by the equation ΔGE=X(1 −X)[(6048 − 2.146T)X+ (8745 − 3.09T)(1 −X)] J·mol−1 The thermodynamic data for the rock salt phase is combined with information on interphase partitioning of Co and Mg to generate the mixing properties for the ortho- and metasilicate solid solutions. For the orthosilicate solution (CoYMg1 −Y)Si0.5O2 at 1373 K, the excess Gibbs free energy of mixing is given by the relation ΔGE=Y(1 −Y)[2805Y+ 3261(1 −Y)] J·mol−1 For the metasilicate solution (CoZMg1 −Z)SiO3 at the same temperature, the excess free energy can be expressed by the relation ΔGE=Z(1 −Z)[2570Z+ 3627(1 −Z)] J·mol−1

Thermodynamics and phase equilibria involving the spinel solid solution FexMg1-xCr2O4

Activities of FeCr2O4 in the spinel solid solutions Fe X Mg1−X Cr2O4 (0parameter Ω s =−2260 (±200) J/mol. The lattice parameter of the spinel solid solutions quenched from 1200 K was found to obey Vegard’s law. The phase relations in the FeO-MgO-Cr2O3 system have been deduced from the results obtained in this study together with other relevant thermodynamic data from the literature. The tie-lines between the solid solutions with rock salt and spinel structures represent the influence of intercrystalline ion exchange. The tie-lines are skewed toward the FeCr2O4 corner, primarily because of the higher stability of FeCr2O4 compared to MgCr2O4, with respect to their component binary oxides. The oxygen partial pressure corresponding to the two three-phase regions, Fe + Fe X Mg1−X Cr2O4 + Cr2O3 and Fe + Fe Y Mg1−Y O + Fe X Mg1−X Cr2O4, have been evaluated as a function of composition at 1200 K.

Nanostructure of giant magnetoresistive oxide film Nd2/3Sr1/3MnO3 by scanning tunneling microscopy

Scanning tunneling microscopy was used to study the surface nanostructure of the epitaxial film Nd2/3Sr1/3MnO3 that shows giant magnetoresistance. The surface morphology of the film consists of a number of overlapping platelets of about 30–35 Å diameter that grow at an angle of 35°–45° to the surface normal. The peak to peak height of the platelets are multiples of the c‐axis lattice parameter of 7.85 Å showing that the growth of the platelets takes place by the layer by layer addition of one formula unit. The mean surface roughness is about 10 Å. In the range of a few microns the film exhibits no defects or dislocations. The film is unstable in ambient atmosphere and tends to get covered by an adsorbate layer. Tip‐surface interactions cause the adsorbate to be dislodged exposing the surface nanostructure. The degradation of the film in real time when imaged in air was recorded. The adsorbates increase the surface roughness of the film.

The generalized Onsager model for the secondary flow in a high-speed rotating cylinder

The generalizations of the Onsager model for the radial boundary layer and the Carrier-Maslen model for the end-cap axial boundary layer in a high-speed rotating cylinder are formulated for studying the secondary gas flow due to wall heating and due to insertion of mass, momentum and energy into the cylinder. The generalizations have wider applicability than the original Onsager and Carrier-Maslen models, because they are not restricted to the limit A >> 1, though they are restricted to the limit R e >> 1 and a high-aspect-ratio cylinder whose length/diameter ratio is large. Here, the stratification parameter A = root m Omega(2)R(2)/2k(B)T). This parameter A is the ratio of the peripheral speed, Omega R, to the most probable molecular speed, root 2k(B)T/m, the Reynolds number Re = rho w Omega R(2)/mu, where m is the molecular mass, Omega and R are the rotational speed and radius of the cylinder, k(B) is the Boltzmann constant, T is the gas temperature, rho(w) is the gas density at wall, and mu is the gas viscosity. In the case of wall forcing, analytical solutions are obtained for the sixth-order generalized Onsager equations for the master potential, and for the fourth-order generalized Carrier-Maslen equation for the velocity potential. For the case of mass/momentum/energy insertion into the flow, the separation-of-variables procedure is used, and the appropriate homogeneous boundary conditions are specified so that the linear operators in the axial and radial directions are self-adjoint. The discrete eigenvalues and eigenfunctions of the linear operators (sixth-order and second-order in the radial and axial directions for the Onsager equation, and fourth-order and second-order in the axial and radial directions for the Carrier-Maslen equation) are determined. These solutions are compared with direct simulation Monte Carlo (DSMC) simulations. The comparison reveals that the boundary conditions in the simulations and analysis have to be matched with care. The commonly used `diffuse reflection' boundary conditions at solid walls in DSMC simulations result in a non-zero slip velocity as well as a `temperature slip' (gas temperature at the wall is different from wall temperature). These have to be incorporated in the analysis in order to make quantitative predictions. In the case of mass/momentum/energy sources within the flow, it is necessary to ensure that the homogeneous boundary conditions are accurately satisfied in the simulations. When these precautions are taken, there is excellent agreement between analysis and simulations, to within 10 %, even when the stratification parameter is as low as 0.707, the Reynolds number is as low as 100 and the aspect ratio (length/diameter) of the cylinder is as low as 2, and the secondary flow velocity is as high as 0.2 times the maximum base flow velocity. The predictions of the generalized models are also significantly better than those of the original Onsager and Carrier-Maslen models, which are restricted to thin boundary layers in the limit of high stratification parameter.

Characteristics of j.f.e.t.s. taking the separation of gate electrode from the source and drain electrodes into account

The performance characteristics of a junction field-effect transistor (j.f.e.t.) are evaluated considering the presence of the gap between the gate electrode and the source and drain terminals. It is concluded that the effect of the gap is to demand a higher drain voltage to maintain the same drain current. So long as the device is operated at the same drain current, the presence of the gap does not change the performance of the device as an amplifier. The nature of the performance of the device as a variable resistor is not affected by the gap if it is less than or equal to the physical height of the channel. For gap lengths larger than the channel height, the effect of the gap is to add a series resistance in the drain.

Novel thiophene derivative hybrid composite solar cells

In this work composites of poly(3-hexylethiophene) (P3HT) and a thiophene derivative (7, 9-di (thiophen-2-yl)-8H-cyclopenta[a]acenaphthylen-8-one) (DTCPA) having donor acceptor architecture (DAD) were prepared. Photovoltaic properties of these hybrid composites were evaluated. DTCPA, which is a highly crystalline organic molecule with wide absorption range, was observed to improve the open circuit voltage of the solar cell. Furthermore, DTCPA crystals acts as a nucleating center and increases the molecular ordering of P3HT in the composite. Improved charge separation efficiency was observed by photoluminescence spectroscopy. Because of high built in potential in these devices, large open circuit voltage was observed. (C) 2011 Elsevier B.V. All rights reserved.

Dislocation mechanisms for plastic flow of nickel in the temperature range 4.2 – 1200 K

The temperature ranges of thermal and athermal deformation behaviour of nickel are identified by employing the temperature-dependence of flow-stress and strain-rate cycling data. The results are used to present a unified view of dislocation mechanisms of glide encompassing the two thermally activated and the intermediate athermal regimes of plastic flow.In the low-temperature thermally activated region (<250 K) the strain rate is found to be controlled by the repulsive intersection of glide and forest dislocations, in accordance with current ideas. The athermal stress in this region can be attributed mainly to the presence of strong attractive junctions which are overcome by means of Orowan bowing, a small contribution also coming from the elastic interactions between dislocations. The values of activation area and activation energy obtained in the high-temperature region (> 750 K) negate the operation of a diffusion-controlled mechanism. Instead, the data support a thermal activation model involving unzipping of the attractive junctions. The internal (long-range) stress contribution here results solely from the elastic interactions between dislocations. This view concerning the high-temperature plastic flow is further supported by the observation that the Cottrell–Stokes law is obeyed over large strains in the range 750–1200 K.

Polymer based photo detectors

Recent developments in our laboratory related to polymer-based light sensors are reviewed. The inherent processibility of the active polymer medium is utilized in the implementation of different designs for the opto-electronic applications. The utility of these devices as sensitive photodetectors, image sensors and position sensitive detectors is demonstrated. The schottky-type layer formation at interfaces of polymers such as polyalkylthiophenes and aluminum accompanied by the enhanced photo-induced charge separation due to high local electric field is tapped for some of these device structures. The sensitivity of polymer-based field effect transistors to light also provides a convenient lateral geometry for efficient optical-coupling and control of the transistor state. ne range of these polymer-detectors available with the option of operating in the diode and transistor modes should be an attractive feature for many potential applications.

Compositionally modulated Pb(Mg1/3Nb2/3)O-3-PbTiO3 relaxor thin films deposited by pulsed excimer laser ablation technique

Thin films of (1-x)Pb(Mg1/3Nb2/3)O-3 - xPbTiO(3) (x = 0.1 to 0.3)(PMN-PT) were deposited on the platinum coated silicon substrate by pulsed excimer laser ablation technique. A template layer of LaSr0.5Co0.5O3 (LSCO) was deposited on platinum substrate prior to the deposition of PMN-PT thin films. The composition and the structure of the films were modulated via proper variation of the deposition parameter such as substrate temperature, laser fluence and thickness of the template layers. We observed the impact of the thickness of LSCO template layer on the orientation of the films. A room temperature dielectric constant varying from 2000 to 4500 was noted for different composition of the films. The dielectric properties of the films were studied over the frequency range of 100 Hz - 100 kHz over a wide range of temperatures. The films exhibited the relaxor- type behavior that was characterized by the frequency dispersion of the temperature of dielectric constant maxima (T-m) and also diffuse phase transition. C1 Indian Inst Sci, Mat Res Ctr, Bangalore, Karnataka 560012 India.

Compositionally and structurally modulated Pb(Mg1/3Nb2/3)O3-PbTiO3 relaxor thin films for microactuator application

Thin films of (1-x)Pb(Mg1/3Nb2/3)O3-xPbTiO3(x = 0.1 to 0.3) (PMN-PT) were successfully grown on the platinum coated silicon substrate by pulsed excimer laser ablation technique. A thin template layer of LaSr0.5Co0.5O3 (LSCO) was deposited on platinum substrate prior to the deposition of PMN-PT thin films. The composition and the structure of the films were modulated via proper variation of the deposition parameter such as substrate temperature, laser fluence and thickness of the template layers. We observed the impact of the thickness of LSCO template layer on the orientation of the films. The crystallographic structure and compositional variation were confirmed with x-ray diffraction and energy diffraction x-ray (EDX) analysis. A room temperature dielectric constant varying from 2000 to 4500 was noted for different composition of the films. The dielectric properties of the films were studied over the frequency range of 100 Hz - 100 kHz over a wide range of temperatures. The films exhibited the relaxor-type behavior that was characterized by the frequency dispersion of the temperature of dielectric constant maxima (Tm) and also diffuse phase transition. This relaxor nature in PMN-PT thin films was attributed to freezing of the dipole moment, which takes place below a certain temperature. This phenomenon was found to be very similar to spin glass system, where spins are observed to freeze after certain temperature.

Scientific rationale toward cupola design

Numerous improvements in cupola design and operation have been made in the past to increase productivity, spout temperature and fuel efficiency. However, these improvements have been based on practice and experience. The present work establishes a scientific rationale for cupola design and operation using a mathematical model. The improved performance of a divided-blast cupola over the conventional one has been successfully explained by the model. Performance of a cupola, as influenced by the important design parameter--the distance of separation between the two rows of tuyeres and operational parameters, such as size of coke and metallic charge, blast rate and charge level--was analyzed. For a divided-blast cupola, an optimum distance of 800-900 mm separation between the two rows of tuyeres was found to be ideal, irrespective of the size of cupola.

Sensitivity of nucleation phenomena on range of interaction potential

Theoretical and computational investigations of nucleation have been plagued by the sensitivity of the phase diagram to the range of the interaction potential. As the surface tension depends strongly on the range of interaction potential and as the classical nucleation theory (CNT) predicts the free energy barrier to be directly proportional to the cube of the surface tension, one expects a strong sensitivity of nucleation barrier to the range of the potential; however, CNT leaves many aspects unexplored. We find for gas-liquid nucleation in Lennard-Jones system that on increasing the range of interaction the kinetic spinodal (KS) (where the mechanism of nucleation changes from activated to barrierless) shifts deeper into the metastable region. Therefore the system remains metastable for larger value of supersaturation and this allows one to explore the high metastable region without encountering the KS. On increasing the range of interaction, both the critical cluster size and pre-critical minima in the free energy surface of kth largest cluster, at respective kinetic spinodals, shift towards smaller cluster size. In order to separate surface tension contribution to the increase in the barrier from other non-trivial factors, we introduce a new scaling form for surface tension and use it to capture both the temperature and the interaction range dependence of surface tension. Surprisingly, we find only a weak non-trivial contribution from other factors to the free energy barrier of nucleation. (C) 2012 American Institute of Physics. [http://dx.doi.org/10.1063/1.3685835]

Exact entanglement studies of strongly correlated systems: role of long-range interactions and symmetries of the system

We study the bipartite entanglement of strongly correlated systems using exact diagonalization techniques. In particular, we examine how the entanglement changes in the presence of long-range interactions by studying the Pariser-Parr-Pople model with long-range interactions. We compare the results for this model with those obtained for the Hubbard and Heisenberg models with short-range interactions. This study helps us to understand why the density matrix renormalization group (DMRG) technique is so successful even in the presence of long-range interactions. To better understand the behavior of long-range interactions and why the DMRG works well with it, we study the entanglement spectrum of the ground state and a few excited states of finite chains. We also investigate if the symmetry properties of a state vector have any significance in relation to its entanglement. Finally, we make an interesting observation on the entanglement profiles of different states (across the energy spectrum) in comparison with the corresponding profile of the density of states. We use isotropic chains and a molecule with non-Abelian symmetry for these numerical investigations.