Corrosion of 310 stainless steel in H2 H2O-H2S gas mixtures; studies at constant temperature and fixed oxygen potential

Corrosion of SAE 310 stainless steel in H2-H2O-H2S gas mixtures was studied at a constant temperature of 1150 K. Reactive gas mixtures were chosen to yield a constant oxygen potential of approximately 6 × 10-13 Nm-2 and sulfur potentials ranging from 0.19 × 10-2 Nm-2 to 33 × 10-2 Nm-2. The kinetics of corrosion were determined using a thermobalance, and the scales were analyzed using metallography, scanning electron microscopy, and energy dispersive X-ray analysis. Two corrosion regimes, which were dependent on sulfur potential, were identified. At high sulfur potentials (P S 2 ± 2.7 × 10-2 Nm-2) the corrosion rates were high, the kinetics obeyed a linear rate equation, and the scales consisted mainly of sulfide phases similar to those observed from pure sulfidation. At low sulfur potentials (P S 2 ± 0.19 × 10-2 Nm-2) the corrosion rates were low, the kinetics obeyed a parabolic rate equation, and scales consisted mainly of oxide phases. Thermochemical diagrams for the Fe-Cr-S-O, Fe-Ni-S-O, Cr-Ni-S-O, and Si-Cr-S-O systems were constructed, and the experimental results are discussed in relation to these diagrams. Based on this comparison, reasonable corrosion mechanisms were developed. At high sulfur potentials, oxide and sulfide phases initially nucleate as separate islands. Overgrowth of the oxide by the sulfide occurs and an exchange reaction governs the corrosion process. Preoxidation at low oxygen potentials and 1150 K is beneficial in suppressing sulfidation at high sulfur potentials.

A Sensor for Sulfur Gas Based on Silver β-Alumina

EMF measurements were made with an electrochemical cell of the type ~t/&(s)/&+-beta alumina/Ag~S(s)S. 2(g). S(s or 1)/R at temperatures between 95 and 241°C. Sflver $- alumina was prepared with the ion exchange technique. The patial pressure of diatomic gas obtained from cell voltages agreed with the literature data.

Application of composition gradient solid electrolytes in sensors and thermodynamic measurements

New compos~tiong radient solid electrolytes are developed which have application in high temperature solid state galvanic sensors and provide a new tool for thermodynamic measurements. The electrolyte consists oi a solid solution between two ionic conductors with a common mobile ion and spatial variation in composition of otber coxup nents. Incorporation of the composite electrolyte in sensors permits the use oi dissimilar gas electrodes. It is demonsuated, both experimentall y and theoretically, that the composition gradient of the relativeiy immobile species does not give rise to a diffusion potential.The emi of a cell is determined by the activity of the mobile species at the two eiectrodes. The thermodynamic properties of solid solutions can be measured using the gradient solid electrolyte. The experimental stuay is based on model systems A?(COj)x(S04)l-x (A=Na,K),where S \.aria across the electrolyte. The functionally gradient solid electrolytes used for activity measurements consist of pure carbonate at one ena and the solid solution under stuav at the other. The identical vaiues of activity, obtained h m t hree different modes of operation of the ceil. indicate unit transport number for the ddi metal ion in the graciient electrolyte. Tlle activities in the solid solutions exhibit moderate positive deviations from Raoult 's law.

Phase relations in the system Cu-Eu-O and thermodynamic properties of CuEu2O4 and CuEuO2

Phase relations in the system Cu-Eu-O have been determined by equilibrating samples of different average composition at 1200 K and by phase analysis after quenching using optical microscopy (OM), x-ray diffraction (XRD), scanning electron microscopy (SEM), and energy dispersive x-ray (EDX). The equilibration experiments were conducted in evacuated ampoules and under flowing inert gas and pure oxygen. The Cu-Eu alloys were found to be in equilibrium with EuO. The higher oxides of europium, Eu3O4 and Eu2O3, coexist with metallic copper. Two ternary oxides CuEu2O4 and CuEuO2 were found to be stable. The ternary oxide CuEuO2, with copper in the monovalent state, can coexist with Cu, Cu2O, Eu2O3 and CuEu2O4 in different phase fields. The compound CuEu2O4 can be in equilibrium with Cu2O, CuO, CuEuO2, Eu2O3, and O2 gas under different conditions at 1200 K. Thermodynamic properties of the ternary oxides were determined using three solid-state cells based on yttria-stabilized zirconia as the electrolyte in the temperature range from 875 to 1250 K. The cells essentially measure the oxygen chemical potential in the three-phase fields: Cu+Eu2O3+CuEuO2, Cu2O+CuEuO2+CuEu2O4, and Eu2O3+CuEuO2+CuEu2O4. The thermodynamic properties of the ternary oxides can be represented by the equations: $\begin{gathered} {\raise0.5ex\hbox{$Couldn't find \end for begin{gathered} Thermogravimetric analysis (TGA) studies in Ar+O2 mixtures confirmed the results from emf measurements. An oxygen potential diagram for the system Cu-Eu-O at 1200 K was evaluated from the results of this study and information available in the literature on the binary phases.

La-Doped Ba2In2O5 Electrolyte: Pechini Synthesis, Microstructure, Electrical Conductivity, and Application for CO Gas Sensing

Dense (Ba1―xLax)2In2O5+x (BLIO) electrolytes with different compositions (x = 0.4, 0.5, 0.6) were fabricated using powders obtained by the Pechini method. The formation of BLIO powders was investigated by using X-ray diffraction and scanning electron microscopy coupled with energy-dispersive X-ray spectroscopy. The calcination temperature and time were optimized. The sintered (Ba1―xLax)2In2O5+x electrolytes showed a relative density greater than ∼97%, and the major phase of three electrolyte compositions was indexed as a cubic perovskite. The electrical conductivity of BLIO ceramics at elevated temperatures in air was measured by ac-impedance spectroscopy. The activation energies for conduction in BLIO were 102 kJ mol―1 between 473 and 666 K and 118 kJ mol―1 between 769 and 873 K, which are comparable to that for 8 mol % yttria-stabilized cubic zirconia. Mixed-potential gas sensors utilizing BLIO-based electrolytes exhibited good sensitivity to different CO concentrations from ∼100 to ∼500 ppm and excellent selectivity to methane at around 873 K.

Nature and Properties of a Repulsive Fermi Gas in the Upper Branch of the Energy Spectrum

We generalize the Nozieres-Schmitt-Rink method to study the repulsive Fermi gas in the absence of molecule formation, i.e., in the so-called ``upper branch.'' We find that the system remains stable except close to resonance at sufficiently low temperatures. With increasing scattering length, the energy density of the system attains a maximum at a positive scattering length before resonance. This is shown to arise from Pauli blocking which causes the bound states of fermion pairs of different momenta to disappear at different scattering lengths. At the point of maximum energy, the compressibility of the system is substantially reduced, leading to a sizable uniform density core in a trapped gas. The change in spin susceptibility with increasing scattering length is moderate and does not indicate any magnetic instability. These features should also manifest in Fermi gases with unequal masses and/or spin populations.

Filling Characteristics for an Activated Carbon Based Adsorbed Natural Gas Storage System

The storage capacity of an activated carbon bed is studied using a 2D transport model with constant inlet flow conditions. The predicted filling times and variation in bed pressure and temperature are in good agreement with experimental observations obtained using a 1.82 L prototype ANG storage cylinder. Storage efficiencies based on the maximum achievable V/V (volume of gas/volume of container) and filling times are used to quantify the performance of the charging process. For the high permeability beds used in the experiments, storage efficiencies are controlled by the rate of heat removal. Filling times, defined as the time at which the bed pressure reaches 3.5 MPa, range from 120 to 3.4 min for inlet flow rates of 1.0 L min(-1) and 30.0 L min(-1), respectively. The corresponding storage efficiencies, eta(s), vary from 90% to 76%, respectively. Simulations with L/D ratios ranging from 0.35 to 7.8 indicate that the storage efficiencies can be improved with an increase in the LID ratios and/or with water cooled convection. Thus for an inlet flow rate of 30.0 L min(-1), an eta(s) value of 90% can be obtained with water cooling for an L/D ratio of 7.8 and a filling time of a few minutes. In the absence of water cooling the eta(s) value reduces to 83% at the same L/D ratio. Our study suggests that with an appropriate choice of cylinder dimensions, solutions based on convective cooling during adsorptive storage are possible with some compromise in the storage capacity.

Particle dynamics in the channel flow of a turbulent particle-gas suspension at high Stokes number. Part 1. DNS and fluctuating force model

The fluctuating force model is developed and applied to the turbulent flow of a gas-particle suspension in a channel in the limit of high Stokes number, where the particle relaxation time is large compared to the fluid correlation time, and low particle Reynolds number where the Stokes drag law can be used to describe the interaction between the particles and fluid. In contrast to the Couette flow, the fluid velocity variances in the different directions in the channel are highly non-homogeneous, and they exhibit significant variation across the channel. First, we analyse the fluctuating particle velocity and acceleration distributions at different locations across the channel. The distributions are found to be non-Gaussian near the centre of the channel, and they exhibit significant skewness and flatness. However, acceleration distributions are closer to Gaussian at locations away from the channel centre, especially in regions where the variances of the fluid velocity fluctuations are at a maximum. The time correlations for the fluid velocity fluctuations and particle acceleration fluctuations are evaluated, and it is found that the time correlation of the particle acceleration fluctuations is close to the time correlations of the fluid velocity in a `moving Eulerian' reference, moving with the mean fluid velocity. The variances of the fluctuating force distributions in the Langevin simulations are determined from the time correlations of the fluid velocity fluctuations and the results are compared with direct numerical simulations. Quantitative agreement between the two simulations are obtained provided the particle viscous relaxation time is at least five times larger than the fluid integral time.

Particle dynamics in the channel flow of a turbulent particle-gas suspension at high Stokes number. Part 2. Comparison of fluctuating force simulations and experiments

The particle and fluid velocity fluctuations in a turbulent gas-particle suspension are studied experimentally using two-dimensional particle image velocimetry with the objective of comparing the experiments with the predictions of fluctuating force simulations. Since the fluctuating force simulations employ force distributions which do not incorporate the modification of fluid turbulence due to the particles, it is of importance to quantify the turbulence modification in the experiments. For experiments carried out at a low volume fraction of 9.15 x 10(-5) (mass loading is 0.19), where the viscous relaxation time is small compared with the time between collisions, it is found that the gas-phase turbulence is not significantly modified by the presence of particles. Owing to this, quantitative agreement is obtained between the results of experiments and fluctuating force simulations for the mean velocity and the root mean square of the fluctuating velocity, provided that the polydispersity in the particle size is incorporated in the simulations. This is because the polydispersity results in a variation in the terminal velocity of the particles which could induce collisions and generate fluctuations; this mechanism is absent if all of the particles are of equal size. It is found that there is some variation in the particle mean velocity very close to the wall depending on the wall-collision model used in the simulations, and agreement with experiments is obtained only when the tangential wall-particle coefficient of restitution is 0.7. The mean particle velocity is in quantitative agreement for locations more than 10 wall units from the wall of the channel. However, there are systematic differences between the simulations and theory for the particle concentrations, possibly due to inadequate control over the particle feeding at the entrance. The particle velocity distributions are compared both at the centre of the channel and near the wall, and the shape of the distribution function near the wall obtained in experiments is accurately predicted by the simulations. At the centre, there is some discrepancy between simulations and experiment for the distribution of the fluctuating velocity in the flow direction, where the simulations predict a bi-modal distribution whereas only a single maximum is observed in the experiments, although both distributions are skewed towards negative fluctuating velocities. At a much higher particle mass loading of 1.7, where the time between collisions is smaller than the viscous relaxation time, there is a significant increase in the turbulent velocity fluctuations by similar to 1-2 orders of magnitude. Therefore, it becomes necessary to incorporate the modified fluid-phase intensity in the fluctuating force simulation; with this modification, the mean and mean-square fluctuating velocities are within 20-30% of the experimental values.

Variation of the gas and radiation content in the sub-Keplerian accretion disk around black holes and its impact to the solutions

We investigate the variation of the gas and the radiation pressure in accretion disks during the infall of matter to the black hole and its effect to the flow. While the flow far away from the black hole might be non-relativistic, in the vicinity of the black hole it is expected to be relativistic behaving more like radiation. Therefore, the ratio of gas pressure to total pressure (beta) and the underlying polytropic index (gamma) should not be constant throughout the flow. We obtain that accretion flows exhibit significant variation of beta and then gamma, which affects solutions described in the standard literature based on constant beta. Certain solutions for a particular set of initial parameters with a constant beta do not exist when the variation of beta is incorporated appropriately. We model the viscous sub-Keplerian accretion disk with a nonzero component of advection and pressure gradient around black holes by preserving the conservations of mass, momentum, energy, supplemented by the evolution of beta. By solving the set of five coupled differential equations, we obtain the thermo-hydrodynamical properties of the flow. We show that during infall, beta of the flow could vary up to similar to 300%, while gamma up to similar to 20%. This might have a significant impact to the disk solutions in explaining observed data, e.g. super-luminal jets from disks, luminosity, and then extracting fundamental properties from them. Hence any conclusion based on constant gamma and beta should be taken with caution and corrected. (C) 2011 Elsevier B.V. All rights reserved.

A Review of Photo-Induced Inter-Diffusion in Nano-Layered Chalcogenide Films

Abstract | A growing interest in the research of chalcogenide glasses can be currently witnessed, which to a large extent is caused by newly opened fields of applications for these materials. Applications in the field of micro- and opto-electronics, xerography and lithography, acousto-optic and memory switching devices and detectors for medical imaging seem to be most remarkable. Accordingly, photo induced phenomena in chalcogenide glasses are attracting much interest. These phenomena can be found both in uniform thin films as well as multilayered films. Among amorphous multilayers, chalcogenide multilayers are attractive because of the potential it has for tailoring the optical properties. I will be presenting some basic idea of photoinduced effects followed by the diffusion mechanisms of Se, Sb and Bi in to As2S3 films.

Growth and consumption rates of the phase layers during interdiffusion in a diffusion couple with finite end member

The relations for the growth and consumption rates of a layer with finite thickness as an end member and the product phases in the interdiffusion zone are developed. We have used two different methodologies, the diffusion based and the physico-chemical approach to develop the same relations. We have shown that the diffusion based approach is rather straightforward; however, the physico-chemical approach is much more versatile than the other method. It was found that the position of the marker plane becomes vague in the second stage of the interdiffusion process in pure A thin layer/B couple, where two phases grow simultaneously.

Gas-phase synthesis of size-classified polyhedral In(2)O(3) nanoparticles

Monodisperse polyhedral In(2)O(3) nanoparticles were synthesized by differential mobility classification of a polydisperse aerosol formed by evaporation of indium at atmospheric pressure. When free molten indium particles oxidize, oxygen is absorbed preferentially on certain planes leading to the formation of polyhedral In(2)O(3) nanoparticles. It is shown that the position of oxygen addition, its concentration, the annealing temperature and the type of carrier gas are crucial for the resulting particle shape and crystalline quality. Semiconducting nanopolyhedrals, especially nanocubes used for sensors, are expected to offer enhanced sensitivity and improved response time due to the higher surface area as compared to spherical particles.