A thermodynamic criterion for selection of gas compositions for diamond deposition

Isoactivity lines for carbon with respect to diamond as the standard state have been calculated in the ternary system C-H-O at 1223 K to identify the diamond deposition domain. The gas composition is calculated by suppressing the formation of all condensed forms of carbon using the SOLGASMIX free-energy minimization program. Thirty six gas species were included in the calculation. From the gas composition, isoactivity lines are computed using recent data on the Gibbs energy of diamond. Except for activities less than 0.1, the isoactivity lines are almost linear on the C-H-O ternary diagram. Gas compositions which generate activity of diamond ranging from 1 to 100 at 1223 K fall inside a narrow wedge originating from the point representing CO. This wedge is very similar to the revised lens-shaped diamond growth domain identified by Bachman et al., using inputs from experiment. The small difference between the calculated and observed domains may be attributed to variation in the supersaturation required for diamond deposition with gas composition. The diamond solubility in the gas phase along the isoactivity line for a(di)=100 and P=6.7 kPa exhibits a minimum at 1280 K, which is close to the optimum temperature found experimentally. At higher supersaturations, non-diamond forms of carbon, including amorphous varieties, are expected. The results suggest that thermodynamic calculations can be useful for locating diamond growth domains in more complex CVD systems containing halogens, for which very little experimental data is available.

Theory of Gas Hydrates: Effect of the Approximation of Rigid Water Lattice

One of the assumptions of the van der Waals and Platteeuw theory for gas hydrates is that the host water lattice is rigid and not distorted by the presence of guest molecules. In this work, we study the effect of this approximation on the triple-point lines of the gas hydrates. We calculate the triple-point lines of methane and ethane hydrates via Monte Carlo molecular simulations and compare the simulation results with the predictions of van der Waals and Platteeuw theory. Our study shows that even if the exact intermolecular potential between the guest molecules and water is known, the dissociation temperatures predicted by the theory are significantly higher. This has serious implications to the modeling of gas hydrate thermodynamics, and in spite of the several impressive efforts made toward obtaining an accurate description of intermolecular interactions in gas hydrates, the theory will suffer from the problem of robustness if the issue of movement of water molecules is not adequately addressed.

Diffraction Of Elastic Waves By Two Parallel Rigid Strips Embedded In An Infinite Orthotropic Medium

The elastodynamic response of a pair of parallel rigid strips embedded in an infinite orthotropic medium due to elastic waves incident normally on the strips has been investigated. The mixed boundary value problem has been solved by the Integral Equation method. The normal stress and the vertical displacement have been derived in closed form. Numerical values of stress intensity factors at inner and outer edges of the strips and vertical displacement at points in the plane of the strips for several orthotropic materials have been calculated and plotted graphically to show the effect of material orthotropy.

Internal nitride formation during gas-phase thermal nitridation of titanium

Titanium nitride surface layers were prepared by gas-phase thermal nitridation of pure titanium in an ammonia atmosphere at 1373 K for different times. In addition to the surface nitride layer, nitride/hydride formation was observed in the bulk of the specimen. The cross-section of the specimen was characterized by various techniques such as optical microscopy, scanning electron microscopy, energy dispersive X-ray spectroscopy, secondary ion mass spectrometry and nanomechanical testing, and the mechanism of formation of these phases is discussed.

Experimental investigation of catalytic and non-catalytic surface reactions on SiO2 thin films with shock heated oxygen gas

The present study is to investigate the interaction of strong shock heated oxygen on the surface of SiO2 thin film. The thermally excited oxygen undergoes a three-body recombination reaction on the surface of silicon dioxide film. The different oxidation states of silicon species on the surface of the shock-exposed SiO2 film are discussed based on X-ray Photoelectron Spectroscopy (XPS) results. The surface morphology of the shock wave induced damage at the cross section of SiO2 film and structure modification of these materials are analyzed using scanning electron microscopy and ion microscopy. Whether the surface reaction of oxygen on SiO2 film is catalytic or non-catalytic is discussed in this paper.

Seismic behaviour of rigid-faced reinforced soil retaining wall models:reinforcement effect

This paper presents the results of shaking table tests on models of rigid-faced reinforced soil retaining walls in which reinforcement materials of different tensile strength were used. The construction of the model retaining walls in a laminar box mounted on a shaking table, the instrumentation and the results from the shaking table tests are described in detail and the effects of the reinforcement parameters on the acceleration response at different elevations of the retaining wall, horizontal soil pressures and face deformations are presented. It was observed from these tests that the horizontal face displacement response of the rigid-faced retaining walls was significantly affected by the inclusion of reinforcement and even low-strength polymer reinforcement was found to be efficient in significantly reducing the deformation of the face. The acceleration amplifications were, however, observed to be less influenced by the reinforcement parameters. The results obtained from this study are helpful in understanding the relative performance of reinforced soil retaining walls under the different test conditions used in the experiments.

Study of gas cavity size hysteresis in a packed bed using DEM

When a high velocity gas jet is introduced into a packed bed a cavity is formed. The size of the cavity shows hysteresis on increasing and decreasing gas flow rates. This hysteresis leads to different cavity sizes at same gas flow rate depending on the bed history. The size of cavity affects the gas flow profiles in the packed bed. In this study the cavity size hysteresis phenomenon has been modeled using discrete element method along with turbulent gas flow. A reasonable agreement has been found between computed and experimental results on cavity size ysteresis. The effect of various parameters, such as nozzle height from the bed bottom and packing height, on the cavity size hysteresis has been studied. It is found that inter-particle interaction forces along with gas drag and bed porosity play an important role in describing the cavity size hysteresis. The injection of gas flow allows the particles to go to an unconstrained state than they were previously in, and their ability to remain in that state, even under decreased gas drag force, leads to the phenomenon of cavity size hysteresis. (c) 2007 Elsevier Ltd. All rights reserved.

On the theory of the indentation test for the measurement of tensile strength of brittle materials

A theoretical solution has been obtained for the state of stress in a rectangular plate under a pair of symmetrically placed rigid indenters. The stress distributions along the two central axes have been calculated for a square plate assuming the pressure distribution under the indenters as uniform, parabolic and one resulting from 'constant displacement' on a semiinfinite boundary, for different ratios of indenter-width to side of square. The results are compared with those of photoelastic analysis of Berenbaum and Brodie and the validity of the solution is discussed. The solution has been extended to orthotropic materials and numerical results for one type of coal are given.

A simple classical approach for the melting temperature of inert-gas nanoparticles

Like the metal and semiconductor nanoparticles, the melting temperature of free inert-gas nanoparticles decreases with decreasing size. The variation is linear with the inverse of the particle size for large nanoparticles and deviates from the linearity for small nanoparticles. The decrease in the melting temperature is slower for free nanoparticles with non-wetting surfaces, while the decrease is faster for nanoparticles with wetting surfaces. Though the depression of the melting temperature has been reported for inert-gas nanoparticles in porous glasses, superheating has also been observed when the nanoparticles are embedded in some matrices. By using a simple classical approach, the influence of size, geometry and the matrix on the melting temperature of nanoparticles is understood quantitatively and shown to be applicable for other materials. It is also shown that the classical approach can be applied to understand the size-dependent freezing temperature of nanoparticles.

Ce0.78Sn0.2Pt0.02O2-delta: A new non-deactivating catalyst for hydrogen production via water-gas shift reaction

We demonstrate the activity of Ce0.78Sn0.2Pt0.02O2-delta, a new catalyst, towards water-gas shift (WGS) reaction. Over 99.5% CO conversion to H-2 is observed at 300 +/- 25 degrees C. Based on different characterization techniques we found that the present catalyst is resistant to deactivation due to carbonate formation and sintering of Pt on the surface when subjected to longer duration of reaction conditions. The catalyst does not require any pre-treatment or activation between start-up/shut-down reaction operations. Formation of side products such as methane, methanol, formaldehyde, coke etc. was not observed under the WGS reaction conditions indicating the high selectivity of the catalyst for H-2. Temperature programmed reduction of the catalyst in hydrogen (H-2-TPR) shows reversible reduction of Ce4+ to Ce3+, Sn4+ to Sn2+ and Pt4+ to Pt-0 oxidation state with oxygen storage capacity (OSC) of 3500 mu mol g(-1) at 80 degrees C. Such high value of OSC indicates the presence of highly activated lattice oxygen. CO oxidation in presence of stoichiometric O-2 shows 100% conversion to CO2 at room temperature. The catalyst also exhibits 100% selectivity for CO2 at room temperature towards preferential oxidation (PROX) of residual CO in presence of excess hydrogen in the feed. (C) 2010 Elsevier B.V. All rights reserved.

Synthesis of FeCu Nanopowder by Levitational Gas Condensation Process

Condensation from the vapor state is an important technique for the preparation of nanopowders. Levitational gas condensation is one such technique that has a unique ability of attaining steady state. Here, we present the results of applying this technique to an iron-copper alloy (96Fe-4Cu). A qualitative model of the process is proposed to understand the process and the characteristics of resultant powder. A phase diagram of the alloy system in the liquid-vapor region was calculated to help understand the course of condensation, especially partitioning and coring during processing. The phase diagram could not explain coring in view of the simultaneous occurrence of solidification and the fast homogenization through diffusion in the nanoparticles; however, it could predict the very low levels of copper observed in the levitated drop. The enrichment of copper observed near the surface of the powder was considered to be a manifestation of the lower surface energy of copper compared with that of iron. Heat transfer calculations indicated that most condensed particles can undergo solidification even when they are still in the proximity of the levitated drop. It helped us to predict the temperature and the cooling rate of the powder particles as they move away from the levitated drop. The particles formed by the process seem to be single domain, single crystals that are magnetic in nature. They, thus, can agglomerate by forming a chain-like structure, which manifests as a three-dimensional network enclosing a large unoccupied space, as noticed in scanning electron microscopy and transmission electron microscopy studies. This also explains the observed low packing density of the nanopowders.

Gas Sensing Characteristics of Superconducting Cuprates

Gas sensing characteristics of YBa2Cu3O7−δ, La2−x SrxCuO4, and Bi2Y1−xCaxSr2Cu2O8 have been examined. La2−x SrxCuO4 (x = 0.075), and Bi2YSr2Cu2O8 are found to show good sensitivity (≈10 ppm) to ethyl alcohol and such vapours.

Room-temperature gas sensors based on gallium nitride nanoparticles

Room-temperature sensing characteristics for H-2, ethanol, NH3, H2S and water have been investigated with thick-film sensors based on GaN nanoparticles, prepared by a simple chemical route. In general, GaN nanoparticles exhibit satisfactory sensor properties for these gases and vapors even at room temperature. The sensitivity for ethanol is found to be highest, the sensitivity and recovery times being smallest. Gas sensor properties of GaN seem to be related to intrinsic defects, which act as sorption sites for the gas molecules. (c) 2010 Elsevier Ltd. All rights reserved.

Gradient solid-electrolyte for use with dissimilar gas electrodes

The EMF of a solid-state cell, incorporating a composite solid-electrolyte with gradual variation in composition, and dissimilar gas electrodes, has been studied as a function of temperature and partial pressures at the electrodes. The cell with the configuration: Pt, CO2' + O2' parallel-to Na2CO3\Na(SO4)x(CO3)1-x\Na2SO4 parallel-to SO3'' + SO2'' + O2'', Pt x=0 x=1 was investigated in the temperature range 973 to 1079 K. The solid-electrolyte surface exposed to SO3 + SO2 + O2 gas mixture was doped-Na2SO4, whereas the CO2 + O2 gas mixture was in contact with pure Na2CO3. The composition of the solid solution between the carbonate and sulfate, with hexagonal structure, was varied gradually between the boundary values. It has been found that the EMF of the cell is close to that calculated from thermodynamic data, assuming unit transport number for Na+ ions. The gradient in the concentration of sulfate and carbonate ions in the electrolyte does not give rise to a significant diffusion potential.

Gas-liquid nucleation at large metastability: unusual features and a new formalism

Nucleation at large metastability is still largely an unsolved problem, even though it is a problem of tremendous current interest, with wide-ranging practical value, from atmospheric research to materials science. It is now well accepted that the classical nucleation theory (CNT) fails to provide a qualitative picture and gives incorrect quantitative values for such quantities as activation-free energy barrier and supersaturation dependence of nucleation rate, especially at large metastability. In this paper, we present an alternative formalism to treat nucleation at large supersaturation by introducing an extended set of order parameters in terms of the kth largest liquid-like clusters, where k = 1 is the largest cluster in the system, k = 2 is the second largest cluster and so on. At low supersaturation, the size of the largest liquid-like cluster acts as a suitable order parameter. At large supersaturation, the free energy barrier for the largest liquid-like cluster disappears. We identify this supersaturation as the one at the onset of kinetic spinodal. The kinetic spinodal is system-size-dependent. Beyond kinetic spinodal many clusters grow simultaneously and competitively and hence the nucleation and growth become collective. In order to describe collective growth, we need to consider the full set of order parameters. We derive an analytic expression for the free energy of formation of the kth largest cluster. The expression predicts that, at large metastability (beyond kinetic spinodal), the barrier of growth for several largest liquid-like clusters disappears, and all these clusters grow simultaneously. The approach to the critical size occurs by barrierless diffusion in the cluster size space. The expression for the rate of barrier crossing predicts weaker supersaturation dependence than what is predicted by CNT at large metastability. Such a crossover behavior has indeed been observed in recent experiments (but eluded an explanation till now). In order to understand the large numerical discrepancy between simulation predictions and experimental results, we carried out a study of the dependence on the range of intermolecular interactions of both the surface tension of an equilibrium planar gas-liquid interface and the free energy barrier of nucleation. Both are found to depend significantly on the range of interaction for the Lennard-Jones potential, both in two and three dimensions. The value of surface tension and also the free energy difference between the gas and the liquid phase increase significantly and converge only when the range of interaction is extended beyond 6-7 molecular diameters. We find, with the full range of interaction potential, that the surface tension shows only a weak dependence on supersaturation, so the reason for the breakdown of CNT (with simulated values of surface tension and free energy gap) cannot be attributed to the supersaturation dependence of surface tension. This remains an unsettled issue at present because of the use of the value of surface tension obtained at coexistence.