Structural investigation of combustion synthesized Cu/CeO2 catalysts by EXAFS and other physical techniques: Formation of a Ce1-xCuxO2-delta solid solution

The structure and chemical environment of Cu in Cu/CeO2 catalysts synthesized by the solution combustion method have been investigated by X-ray diffraction (XRD), transmission electron microscopy (TEM), electron paramagnetic resonance (EPR) spectroscopy, X-ray photoelectron spectroscopy (XPS), cyclic voltammetry (CV), and extended X-ray fine structure (EXAFS) spectroscopy. High-resolution XRD studies of 3 and 5 atom % Cu/CeO2 do not show CuO lines in their respective patterns. The structure could be refined for the composition Ce1-xCuxO2-delta (x = 0.03 and 0.05; delta similar to 0.13 and 0.16) in the fluorite structure with 5-8% oxide ion vacancy. High-resolution TEM did not show CuO particles in 5 atom % Cu/CeO2. EPR as well as XPS studies confirm the presence of Cu2+ species in the CeO2 matrix. Redox potentials of Cu species in the CeO2 matrix are lower than those in CuO. EXAFS investigations of these catalysts show an average coordination number of 3 around the Cu2+ ion in the first shell at a distance of 1.96 Angstrom, indicating the O2- ion vacancy around the Cu2+ ion. The Cu-O bond length also decreases compared to that in CuO. The second and third shell around the Cu2+ ion in the catalysts are attributed to -Cu2+-O2--Cu2+ - at 2.92 Angstrom and -Cu2+-O2--Ce4+- at the distance of 3.15 Angstrom, respectively. The present results provide direct evidence for the formation of a Ce1-xCuxO2-delta type of solid solution phase having -square-Cu2+-O-Ce4+- kind of linkages.

Study of formation of silicon carbide in the Acheson process

Formation of silicon carbide in the Acheson process was studied using a mass transfer model which has been developed in this study. The century old Acheson process is still used for the mass production of silicon carbide. A heat resistance furnace is used in the Acheson process which uses sand and petroleum coke as major raw materials.: It is a highly energy intensive process. No mass transfer model is available for this process. Therefore, a mass transfer model has been developed to study the mass transfer aspects of the process along with heat transfer. The reaction kinetics of silicon carbide formation has been taken from the literature. It has been shown that reaction kinetics has a reasonable influence on the process efficiency. The effect of various parameters on the process such as total gas pressure, presence of silicon carbide in the initial charge, etc. has been studied. A graphical user interface has also been developed for the Acheson process to make the computer code user friendly.

The influence of oxygen impurities on the formation of AlN-Al composites by infiltration of molten Al-Mg

The influence of residual oxygen in nitrogen on the formation of AlN-Al matrix by reactive infiltration has been investigated. Increasing the oxygen content from 10 ppm upwards decreased the nitride content in the matrix from 64 to 6%, Based on the analysis of the availability of oxygen at the Al-melt/gas interface, three distinct scenarios have been proposed (i) at lowest values, oxygen does not interfere with either infiltration or nitridation reaction; (ii) at intermediate values, nitridation is suppressed, however infiltration continues; and (iii) at a critical upper value, the melt passivates without any infiltration. This phenomenon offers control of the AlN/Al ratio in the matrix and the possibility of creation of microstructural gradierits by the appropriate choice of gas mixtures. (C) 2002 Elsevier Science B.V. All rights reserved.

Novel phase-transition behavior near liquid/liquid critical points of aqueous solutions: Formation of a third phase at the interface

We report a novel phase behavior in aqueous solutions of simple organic solutes near their liquid/liquid critical points, where a solid-like third phase appears at the liquid/liquid interface. The phenomenon has been found in three different laboratories. It appears in many aqueous systems of organic solutes and becomes enhanced upon the addition of salt to these solutions.

The extended Enskog operator for simple fluids with continuous potentials: single particle and collective properties

We generalized the Enskog theory originally developed for the hard-sphere fluid to fluids with continuous potentials, such as the Lennard–Jones. We derived the expression for the k and ω dependent transport coefficient matrix which enables us to calculate the transport coefficients for arbitrary length and time scales. Our results reduce to the conventional Chapman–Enskog expression in the low density limit and to the conventional k dependent Enskog theory in the hard-sphere limit. As examples, the self-diffusion of a single atom, the vibrational energy relaxation, and the activated barrier crossing dynamics problem are discussed.

Formation of amorphous xenon nanoclusters and microstructure evolution in pulsed laser deposited Ti(62.5)Si(37.5) thin films during Xe ion irradiation

As deposited amorphous and crystallized thin films of Ti 37.5% Si alloy deposited by pulsed laser ablation technique were irradiated with 100 keV Xe(+) ion beam to an ion fluence of about 10(16) ions-cm(-2). Transmission electron microscopy revealed that the implanted Xe formed amorphous nanosized clusters in both cases. The Xe ion-irradiation favors nucleation of a fcc-Ti(Si) phase in amorphous films. However, in crystalline films, irradiation leads to dissolution of the Ti(5)Si(3) intermetallic phase. In both cases, Xe irradiation leads to the evolution of similar microstructures. Our results point to the pivotal role of nucleation in the evolution of the microstructure under the condition of ion implantation.

Propensity of formation of zipper architecture vs. Lincoln log arrangement in solvated molecular complexes of melamine with hydroxybenzoic acids

Molecular complexes of melamine with hydroxy and dihydroxybenzoic acids have been analyzed to assess the collective role of the hydroxyl (OH) and carboxyl (COOH) functionalities in the recognition process. In most cases, solvents of crystallization do play a major role in self-assembly and structure stabilization. Hydrated compounds generate linear chains of melamine molecules with acid molecules pendant resulting in a zipper architecture. However, anhydrous and solvated compounds generate tetrameric units consisting of melamine dimers together with acid molecules. These tetramers in turn interweave to form a Lincoln log arrangement in the crystal. The salt/co-crystal formation in these complexes cannot be predicted apriori on the basis of Delta pK(a) values as there exists a salt-to-co-crystal continuum.

An improved Monte Carlo scheme for simulation of synthesis of nanoparticles in reverse micelles

An improved Monte Carlo technique is presented in this work to simulate nanoparticle formation through a micellar route. The technique builds on the simulation technique proposed by Bandyopadhyaya et al. (Langmuir 2000, 16, 7139) which is general and rigorous but at the same time very computation intensive, so much so that nanoparticle formation in low occupancy systems cannot be simulated in reasonable time. In view of this, several strategies, rationalized by simple mathematical analyses, are proposed to accelerate Monte Carlo simulations. These are elimination of infructuous events, removal of excess reactant postreaction, and use of smaller micelle population a large number of times. Infructuous events include collision of an empty micelle with another empty one or with another one containing only one molecule or only a solid particle. These strategies are incorporated in a new simulation technique which divides the entire micelle population in four classes and shifts micelles from one class to other as the simulation proceeds. The simulation results, throughly tested using chi-square and other tests, show that the predictions of the improved technique remain unchanged, but with more than an order of magnitude decrease in computational effort for some of the simulations reported in the literature. A post priori validation scheme for the correctness of the simulation results has been utilized to propose a new simulation strategy to arrive at converged simulation results with near minimum computational effort.

Calcium ruthenates: Determination of Gibbs energies of formation using electrochemical cells

Metallic Ru has been found to coexist separately with CaO, RuO2, and the interoxide phases, Ca2RuO4, Ca3Ru2O7, and CaRuO3, present along the pseudobinary system CaO-RuO2. The standard Gibbs energies of formation (Df((ox))G(o)) of the three calcium ruthenates from their component oxides have been measured in the temperature range 925-1350 K using solid-state cells with yttria-stabilized zirconia as the electrolyte and Ru+RuO2 as the reference electrode. The standard Gibbs energies of formation (Deltaf((ox))G(o)) of the compounds can be represented by Ca2RuO4:Deltaf((ox))G(o)/J mol(-1)=-38,340-6.611 T (+/-120), Ca3Ru2O7 : Df((ox))G(o)/J mol(-1)=-75,910-11.26 T (+/-180), and CaRuO3 : Deltaf((ox))G(o)/J mol(-1)=-35,480-3.844 T(+/-70). The data for Ca2RuO4 corresponds to the stoichiometric composition, which has an orthorhombic structure, space group Pbca, with short c axis ("S'' form). The structural features of the ternary oxides responsible for their mild entropy stabilization are discussed. A three-dimensional oxygen potential diagram for the system Ca-Ru-O is developed as a function of composition and temperature from the results obtained. Using the Neumann-Kopp rule to estimate the heat capacity of the ternary oxides relative to their constituent binary oxides, the standard enthalpies of formation of the three calcium ruthenates from the elements and their standard entropies at 298.15 K are evaluated. (C) 2003 The Electrochemical Society.

Carbothermal reduction and nitridation reaction of SiOx and preoxidized SiOx: Formation of α-Si3N4 fibers

The chemical composition of amorphous SiOx has been analyzed by oxidation studies and is found to be SiO1.7. SiO1.7 appears to be a monophasic amorphous material on the basis of 29Si nuclear magnetic resonance, high resolution electron microscopy, and comparative behavior of a physical mixture of Si and SiO2. Carbothermal reduction and nitridation reactions have been carried out on amorphous SiO1.7 and on amorphous SiO2 obtained from oxidation of SiO1.7. At 1623 K reactions of SiO1.7 lead exclusively to the formation of Si2N2O, while those of SiO2 lead exclusively to the formation of Si3N4. Formation of copious fibers of α-Si3N4 was observed in the latter reaction. It is suggested that the partial pressure of SiO in equilibrium with reduced SiO1.7 and SiO2 during the reaction is the crucial factor that determines the chemistry of the products. The differences in the structures of SiO2 and SiO1.7 have been considered to be the origin of the differences in the SiO partial pressures of the reduction products formed prior to nitridation. The effect of the ratios, C:SiO1.7 and C:SiO2, in the reaction mixture as well as the effect of the temperature on the course of the reactions have also been investigated.

Motion of a charged particle in superposed Heliotron and biconical cusp fields

We have studied the behaviour of a charged particle in an axially symmetric magnetic field having a neutral point, so as to find a possibility of confining a charged particle in a thermonuclear device. In order to study the motion we have reduced a three-dimensional motion to a two-dimensional one by introducing a fictitious potential. Following Schmidt we have classified the motion, as an ‘off-axis motion’ and ‘encircling motion’ depending on the behaviour of this potential. We see that the particle performs a hybrid type of motion in the negative z-axis, i.e. at some instant it is in ‘off-axis motion’ while at another instant it is in ‘encircling motion’. We have also solved the equation of motion numerically and the graphs of the particle trajectory verify our analysis. We find that in most of the cases the particle is contained. The magnetic moment is found to be moderately adiabatic.

Particle dynamics in a turbulent particle–gas suspension at high Stokes number. Part 2. The fluctuating-force model

A fluctuating-force model is developed for representing the effect of the turbulent fluid velocity fluctuations on the particle phase in a turbulent gas–solid suspension in the limit of high Stokes number, where the particle relaxation time is large compared with the correlation time for the fluid velocity fluctuations. In the model, a fluctuating force is incorporated in the equation of motion for the particles, and the force distribution is assumed to be an anisotropic Gaussian white noise. It is shown that this is equivalent to incorporating a diffusion term in the Boltzmann equation for the particle velocity distribution functions. The variance of the force distribution, or equivalently the diffusion coefficient in the Boltzmann equation, is related to the time correlation functions for the fluid velocity fluctuations. The fluctuating-force model is applied to the specific case of a Couette flow of a turbulent particle–gas suspension, for which both the fluid and particle velocity distributions were evaluated using direct numerical simulations by Goswami & Kumaran (2010). It is found that the fluctuating-force simulation is able to quantitatively predict the concentration, mean velocity profiles and the mean square velocities, both at relatively low volume fractions, where the viscous relaxation time is small compared with the time between collisions, and at higher volume fractions, where the time between collisions is small compared with the viscous relaxation time. The simulations are also able to predict the velocity distributions in the centre of the Couette, even in cases in which the velocity distribution is very different from a Gaussian distribution.

Crystallography of Hydride Formation in Zr-Nb Alloys

he crystallographic and morphological aspect associated with the formation of γ hydride phase (fct) from the β phase in β abilized Zr-20%Nb alloy has been reported. In this paper the βto γ transformation has been considered in the terms of the phenomenological theory of martensitic crystallography in order to predict the crystallographic features of the γ hydride in the β to γ transformation. The prediction made in the present analysis has been found to match very closely to the experimentally observed habit plane. The possibility of the α to γ transition through the formation of a transient β configuration has been examined.

The collective dynamics of self-propelled particles

We propose a method for the dynamic simulation of a collection of self-propelled particles in a viscous Newtonian fluid. We restrict attention to particles whose size and velocity are small enough that the fluid motion is in the creeping flow regime. We propose a simple model for a self-propelled particle, and extended the Stokesian Dynamics method to conduct dynamic simulations of a collection of such particles. In our description, each particle is treated as a sphere with an orientation vector p, whose locomotion is driven by the action of a force dipole Sp of constant magnitude S0 at a point slightly displaced from its centre. To simplify the calculation, we place the dipole at the centre of the particle, and introduce a virtual propulsion force Fp to effect propulsion. The magnitude F0 of this force is proportional to S0. The directions of Sp and Fp are determined by p. In isolation, a self-propelled particle moves at a constant velocity u0 p, with the speed u0 determined by S0. When it coexists with many such particles, its hydrodynamic interaction with the other particles alters its velocity and, more importantly, its orientation. As a result, the motion of the particle is chaotic. Our simulations are not restricted to low particle concentration, as we implement the full hydrodynamic interactions between the particles, but we restrict the motion of particles to two dimensions to reduce computation. We have studied the statistical properties of a suspension of self-propelled particles for a range of the particle concentration, quantified by the area fraction φa. We find several interesting features in the microstructure and statistics. We find that particles tend to swim in clusters wherein they are in close proximity. Consequently, incorporating the finite size of the particles and the near-field hydrodynamic interactions is of the essence. There is a continuous process of breakage and formation of the clusters. We find that the distributions of particle velocity at low and high φa are qualitatively different; it is close to the normal distribution at high φa, in agreement with experimental measurements. The motion of the particles is diffusive at long time, and the self-diffusivity decreases with increasing φa. The pair correlation function shows a large anisotropic build-up near contact, which decays rapidly with separation. There is also an anisotropic orientation correlation near contact, which decays more slowly with separation. Movies are available with the online version of the paper.

Particle dynamics in a turbulent particle–gas suspension at high Stokes number. Part 1. Velocity and acceleration distributions

The effect of fluid velocity fluctuations on the dynamics of the particles in a turbulent gas–solid suspension is analysed in the low-Reynolds-number and high Stokes number limits, where the particle relaxation time is long compared with the correlation time for the fluid velocity fluctuations, and the drag force on the particles due to the fluid can be expressed by the modified Stokes law. The direct numerical simulation procedure is used for solving the Navier–Stokes equations for the fluid, the particles are modelled as hard spheres which undergo elastic collisions and a one-way coupling algorithm is used where the force exerted by the fluid on the particles is incorporated, but not the reverse force exerted by the particles on the fluid. The particle mean and root-mean-square (RMS) fluctuating velocities, as well as the probability distribution function for the particle velocity fluctuations and the distribution of acceleration of the particles in the central region of the Couette (where the velocity profile is linear and the RMS velocities are nearly constant), are examined. It is found that the distribution of particle velocities is very different from a Gaussian, especially in the spanwise and wall-normal directions. However, the distribution of the acceleration fluctuation on the particles is found to be close to a Gaussian, though the distribution is highly anisotropic and there is a correlation between the fluctuations in the flow and gradient directions. The non-Gaussian nature of the particle velocity fluctuations is found to be due to inter-particle collisions induced by the large particle velocity fluctuations in the flow direction. It is also found that the acceleration distribution on the particles is in very good agreement with the distribution that is calculated from the velocity fluctuations in the fluid, using the Stokes drag law, indicating that there is very little correlation between the fluid velocity fluctuations and the particle velocity fluctuations in the presence of one-way coupling. All of these results indicate that the effect of the turbulent fluid velocity fluctuations can be accurately represented by an anisotropic Gaussian white noise.