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.

Failure mechanisms and toughness of Al2O3 ductile-particle toughened ceramics and SiC fibre-ceramic composites

The development of high performance ceramics and ceramic composites often relies on assumptions about their behaviour during loading and at failure. A crucial influence on the mechanical properties of these materials is the degree of sub-critical cracking, which post mortem investigations cannot adequately reveal. Hence a clear picture of the dynamic micromechanisms of cracking is required if applications of fracture and damage mechanics to theoretical models is to be meaningful.

Homogeneous pinhole free 1 nm Al2O3 tunnel barriers on graphene

We report on the topographical and electrical characterisations of 1 nm thick Al2O3 dielectric films on graphene. The Al 2O3 is grown by sputtering a 0.6 nm Al layer on graphene and subsequentially oxidizing it in an O2 atmosphere. The Al 2O3 layer presents no pinholes and is homogeneous enough to act as a tunnel barrier. A resistance-area product in the mega-ohm micrometer-square range is found. Comparatively, the growth of Al 2O3 by evaporation does not lead to well-wetted films on graphene. Application of this high quality sputtered tunnel barrier to efficient spin injection in graphene is discussed. © 2012 American Institute of Physics.