Diffusion and chemical reaction in the porous structures of solid oxide fuel cells

The Rolls-Royce Integrated-Planar Solid Oxide Fuel Cell (IP-SOFC) consists of ceramic modules which have electrochemical cells printed on the outer surfaces. The cathodes are the outermost layer of each cell and are supplied with oxygen from air flowing over the outside of the module. The anodes are in direct contact with the ceramic structure and are supplied with fuel from internal gas channels. Natural gas is reformed into hydrogen for use by the fuel cells in a separate reformer module of similar design except that the fuel cells are replaced by a reforming catalyst layer. The performance of the modules is intrinsically linked to the behaviour of the gas flows within their porous structures. Because the porous layers are very thin, a one-dimensional flow model provides a good representation of the flow property variations between fuel channel and fuel cell or reforming catalyst. The multi-component convective-diffusive flows are simulated using a new theory of flow in porous material, the Cylindrical Pore Interpolation Model. The effects of the catalysed methane reforming and water-gas shift chemical reactions are also considered using appropriate kinetic models. It is found that the shift reaction, which is catalysed by the anode material, has certain beneficial effects on the fuel cell module performance. In the reformer module it was found that the flow resistance of the porous support structure makes it difficult to sustain a high methane conversion rate. Although the analysis is based on IP-SOFC geometry, the modelling approach and general conclusions are applicable to other types of SOFC.

SiO2 coating of silver nanoparticles by photoinduced chemical vapor deposition.

Gas-phase silver nanoparticles were coated with silicon dioxide (SiO2) by photoinduced chemical vapor deposition (photo-CVD). Silver nanoparticles, produced by inert gas condensation, and a SiO2 precursor, tetraethylorthosilicate (TEOS), were exposed to vacuum ultraviolet (VUV) radiation at atmospheric pressure and varying temperatures. The VUV photons dissociate the TEOS precursor, initiating a chemical reaction that forms SiO2 coatings on the particle surfaces. Coating thicknesses were measured for a variety of operation parameters using tandem differential mobility analysis and transmission electron microscopy. The chemical composition of the particle coatings was analyzed using energy dispersive x-ray spectrometry and Fourier transform infrared spectroscopy. The highest purity films were produced at 300-400 degrees C with low flow rates of additional oxygen. The photo-CVD coating technique was shown to effectively coat nanoparticles and limit core particle agglomeration at concentrations up to 10(7) particles cm(-3).

Spark plasma sintering of TiNi nano-powders for biological application

Nano-sized TiNi powder with an average size of 50nm was consolidated using spark plasma sintering (SPS) at 800 °C for 5min. A layer of anatase TiO 2 coating was formed on the sintered TiNi by chemical reaction with a hydrogen peroxide (H2O2) solution at 60 °C followed by heat treatment at 400 °C to enhance the bioactivity of the metal surface. Cell culture using osteoblast cells and a biomimetic test in simulated body fluid proved the biocompatibility of the chemically treated SPS TiNi. © IOP Publishing Ltd.

Microbial carbonate precipitation: Correlation of S-wave velocity with calcite precipitation

The use of microbial induced precipitation as a soil improvement technique has been growing in geotechnical domains where ureolytic bacteria that raise the pH of the system and induce calcium carbonate (CaCO3) precipitation are used. For many applications, it is useful to assess the degree of CaCO 3 precipitation by non-destructive testing. This study investigates the feasibility of S-wave velocity measurements to evaluate the amount of calcite precipitation by laboratory testing. Two sets of cemented specimen were tested. The first were samples terminated at different stages of cementation. The second were samples that went through different chemical treatments. These variations were made to find out if these factors would affect the S-wave velocity- cementation relationship. If chemical reaction efficiency was assumed to be constant throughout each test, the relationship between S-wave velocity (Vs) and the amount of CaCO3 precipitation was found to be approximately linear. This correlation between S-wave velocity and calcium carbonate precipitation validates its use as an indicator of the amount of calcite precipitation © 2011 ASCE.

Effects of Lewis number on scalar variance transport in premixed flames

The influences of differential diffusion rates of heat and mass on the transport of the variances of Favre fluctuations of reaction progress variable and non-dimensional temperature have been studied using three-dimensional simplified chemistry based Direct Numerical Simulation (DNS) data of statistically planar turbulent premixed flames with global Lewis number ranging from Le = 0.34 to 1.2. The Lewis number effects on the statistical behaviours of the various terms of the transport equations of variances of Favre fluctuations of reaction progress variable and non-dimensional temperature have been analysed in the context of Reynolds Averaged Navier Stokes (RANS) simulations. It has been found that the turbulent fluxes of the progress variable and temperature variances exhibit counter-gradient transport for the flames with Lewis number significantly smaller than unity whereas the extent of this counter-gradient transport is found to decrease with increasing Lewis number. The Lewis number is also shown to have significant influences on the magnitudes of the chemical reaction and scalar dissipation rate contributions to the scalar variance transport. The modelling of the unclosed terms in the scalar variance equations for the non-unity Lewis number flames have been discussed in detail. The performances of the existing models for the unclosed terms are assessed based on a-priori analysis of DNS data. Based on the present analysis, new models for the unclosed terms of the active scalar variance transport equations are proposed, whenever necessary, which are shown to satisfactorily capture the behaviours of unclosed terms for all the flames considered in this study. © 2010 Springer Science+Business Media B.V.

Analysis of high pressure premixed flames using Equivalent Reactor Networks for predicting NOx emissions

This paper describes a computational study of lean premixed high pressure methane-air flames, using Computational Fluid Dynamics (CFD) together with a reactor network approach. A detailed chemical reaction mechanism is employed to predict pollutant concentrations, placing emphasis on nitrogen oxide emissions. The reacting flow field is divided into separate zones in which homogeneity of the physical and chemical conditions prevails. The defined zones are interconnected forming an Equivalent Reactor Network (ERN). Three flames are examined for which experimental data is available. Flame A is characterised by an equivalence ratio of 0.43 while Flames B and C are richer with equivalence ratios of 0.5 and 0.56 respectively. Computations are performed for a range of operating conditions, quantifying the effect in the emitted NOx levels. Model predictions are compared against the available experimental data. Sensitivity analysis is performed to investigate the effect of the network size, in order to define the optimum number of reactors for accurate predictions of the species mass fractions. © 2012 Elsevier Ltd. All rights reserved.

Permeability of aged grout around tunnels in London

Prediction of the long-term settlement of clay soils over tunnels requires a knowledge of the permeability of the soil and of the tunnel lining; however, determination of the lining permeability in the field is difficult. An important contributor to this problem is the lack of knowledge concerning the permeability of the grout between the lining and the soil. This paper presents the results of tests to characterise the properties of grout samples from London Underground tunnels, investigating permeability, porosity, micro structure and composition. The tests revealed that the newer grout was impermeable relative to the surrounding clay. However, the older samples showed much greater permeabilities and an altered grout composition, suggesting that degradation had taken place. Exposure to groundwater appeared to have caused carbonation and sulfate reaction. The combination of chemical reaction and leaching of cementitious and degradation products appears to have made these grouts more permeable, so that the grout could act as a drainage path rather than a barrier. This challenges the typical assumption that the grout acts as an impermeable barrier.

Differentiated adipose-derived stem cells act synergistically with RGD-modified surfaces to improve neurite outgrowth in a co-culture model.

Peripheral nerve damage is a problem encountered after trauma and during surgery and the development of synthetic polymer conduits may offer a promising alternative to autografts. In order to improve the performance of the polymer to be used for nerve conduits, poly-ε-caprolactone (PCL) films were chemically functionalized with RGD moieties, using a chemical reaction previously developed. In vitro cultures of dissociated dorsal root ganglion (DRG) neurons provide a valid model to study different factors affecting axonal growth. In this work, DRG neurons were cultured on RGD-functionalized PCL films. Adult adipose-derived stem cells differentiated to Schwann cells (dASCs) were initially cultured on the functionalized PCL films, resulting in improved attachment and proliferation. dASCs were also co-cultured with DRG neurons on treated and untreated PCL to assess stimulation by dASCs on neurite outgrowth. Neuron response was generally poor on untreated PCL films, but long neurites were observed in the presence of dASCs or RGD moieties. A combination of the two factors enhanced even further neurite outgrowth, acting synergistically. Finally, in order to better understand the extracellular matrix (ECM)-cell interaction, a β1 integrin blocking experiment was carried out. Neurite outgrowth was not affected by the specific antibody blocking, showing that β1 integrin function can be compensated by other molecules present on the cell membrane. Copyright © 2013 John Wiley & Sons, Ltd.

Reversible CO2 absorption by the 6H perovskite Ba 4Sb2O9

A novel compound for carbon capture and storage (CCS) applications, the 6H perovskite Ba4Sb2O9, was found to be able to absorb CO2 through a chemical reaction at 873 K to form barium carbonate and BaSb2O6. This absorption was shown to be reversible through the regeneration of the original Ba4Sb 2O9 material upon heating above 1223 K accompanied by the release of CO2. A combined synchrotron X-ray diffraction, thermogravimetric, and microscopy study was carried out to characterize first the physical absorption properties and then to analyze the structural evolution and formation of phases in situ. Importantly, through subsequent carbonation and regeneration of the material over 100 times, it was shown that the combined absorption and regeneration reactions proceed without any significant reduction in the CO2 absorption capacity of the material. After 100 cycles the capacity of Ba4Sb2O9 was ∼0.1 g (CO 2)/g (sorbent), representing 73% of the total molar capacity. This is the first report of a perovskite-type material showing such good properties, opening the way for studies of new classes of inorganic oxide materials with stable and flexible chemical compositions and structures for applications in carbon capture. © 2013 American Chemical Society.

Topologically invariant reaction coordinates for simulating multistate chemical reactions.

Evaluating free energy profiles of chemical reactions in complex environments such as solvents and enzymes requires extensive sampling, which is usually performed by potential of mean force (PMF) techniques. The reliability of the sampling depends not only on the applied PMF method but also the reaction coordinate space within the dynamics is biased. In contrast to simple geometrical collective variables that depend only on the positions of the atomic coordinates of the reactants, the E(gap) reaction coordinate (the energy difference obtained by evaluating a suitable force field using reactant and product state topologies) has the unique property that it is able to take environmental effects into account leading to better convergence, a more faithful description of the transition state ensemble and therefore more accurate free energy profiles. However, E(gap) requires predefined topologies and is therefore inapplicable for multistate reactions, in which the barrier between the chemically equivalent topologies is comparable to the reaction activation barrier, because undesired "side reactions" occur. In this article, we introduce a new energy-based collective variable by generalizing the E(gap) reaction coordinate such that it becomes invariant to equivalent topologies and show that it yields more well behaved free energy profiles than simpler geometrical reaction coordinates.

Kinetics of the chemical looping oxidation of H2 by a co-precipitated mixture of CuO and Al2O3

Chemical-looping combustion (CLC) has the inherent property of separating CO2 from flue gases. Instead of air, it uses an oxygen-carrier, usually in the form of a metal oxide, to provide oxygen for combustion. When used for the combustion of gaseous fuels, such as natural gas, or synthesis gas from the gasification of coal, the technique gives a stream of CO2 which, on an industrial scale, would be sufficiently pure for geological sequestration. An important issue is the form of the metal oxide, since it must retain its reactivity through many cycles of complete reduction and oxidation. Here, we report on the rates of oxidation of one constituent of synthesis gas, H2, by co-precipitated mixtures of CuO+Al2O3 using a laboratory-scale fluidised bed. To minimise the influence of external mass transfer, and also of errors in the measurement of [H2], particles sized to 355-500μm were used at low [H2], with the temperature ranging from 450 to 900°C. Under such conditions, the reaction was slow enough for meaningful measurements of the intrinsic kinetics to be made. The reaction was found to be first order with respect to H2. Above ∼800°C, the reaction of CuO was fast and conformed to the shrinking core mechanism, proceeding via the intermediate, Cu2O, in: 2CuO+H2→Cu2O+H2O, ΔH1073 K0=- 116.8 kJ/mol; Cu2O+H2→2Cu+H2O, ΔH1073 K0-80.9 kJ/mol. After oxidation of the products Cu and Cu2O back to CuO, the kinetics in subsequent cycles of chemical looping oxidation of H2 could be approximated by those in the first. Interestingly, the carrier was found to react at temperatures as low as 300°C. The influence of the number of cycles of reduction and oxidation is explored. Comparisons are drawn with previous work using reduction by CO. Finally, these results indicate that the kinetics of reaction of the oxygen carrier with gasifier synthesis gases is very much faster than rates of gasification of the original fuel. © 2010 The Institution of Chemical Engineers.

Deposition of diamond-like carbon films by photon-enhanced chemical vapour deposition of methane using a windowless hydrogen lamp

Thin films of diamond-like carbon (DLC) have been deposited using a novel photon-enhanced chemical vapour deposition (photo-CVD) method. This low energy method may be a way to produce better interfaces in electronic devices by reducing damage due to ion bombardment. Methane requires high energy photons for photolysis to take place and these are not transmitted in most photo-CVD methods owing to the presence of a window between the lamp and the deposition environment. In our photo-CVD system there is no window and all the high energy photons are transmitted into the reaction gas. Initial work has proved promising and this paper presents recent results. Films have been characterized by measuring electron energy loss spectra, by ellipsometry and by fabricating and testing diode structures. Results indicate that the films are of a largely amorphous nature and are semiconducting. Diode structures have on/off current ratios of up to 106.