In situ X-ray studies of crotyl alcohol selective oxidation over Au/Pd(1 1 1) surface alloys

The selective oxidation of crotyl alcohol to crotonaldehyde over ultrathin Au overlayers on Pd(1 1 1) and Au/Pd(1 1 1) surface alloys has been investigated by time-resolved X-ray photoelectron spectroscopy (XPS) and mass spectrometry. Pure gold is catalytically inert towards crotyl alcohol which undergoes reversible adsorption. In contrast, thermal processing of a 3.9 monolayer (ML) gold overlayer allows access to a range of AuPd surface alloy compositions, which are extremely selective towards crotonaldehyde production, and greatly reduce the extent of hydrocarbon decomposition and eventual carbon laydown compared with base Pd(1 1 1). XPS and CO titrations suggest that palladium-rich surface alloys offer the optimal balance between alcohol oxidative dehydrogenation activity while minimising competitive decomposition pathways, and that Pd monomers are not the active surface ensemble for such selox chemistry over AuPd alloys. Crown Copyright © 2008.

Heterogeneous catalysis in an oscillatory baffled flow reactor

The first demonstration of heterogeneous catalysis within an oscillatory baffled flow reactor (OBR) is reported, exemplified by the solid acid catalysed esterification of organic acids, an important prototypical reaction for fine chemicals and biofuel synthesis. Suspension of a PrSOH-SBA-15 catalyst powder is readily achieved within the OBR under an oscillatory flow, facilitating the continuous esterification of hexanoic acid. Excellent semi-quantitative agreement is obtained between OBR and conventional stirred batch reaction kinetics, demonstrating efficient mixing, and highlighting the potential of OBRs for continuous, heterogeneously catalysed liquid phase transformations. Kinetic analysis highlights acid chain length (i.e. steric factors) as a key predictor of activity. Continuous esterification offers improved ester yields compared with batch operation, due to the removal of water by-product from the catalyst, evidencing the versatility of the OBR for heterogeneous flow chemistry and potential role as a new clean catalytic technology. © The Royal Society of Chemistry 2013.

The effect of frequency and microstructure on corrosion fatigue crack propagation in high strength aluminium alloys

Fatigue crack growth in high strength aluminium alloy 7150 commercial plate material has been studied in both laboratory air and acidified aqueous salt solution. The aggressive aqueous environment enhanced fatigue crack growth rates by up to an order in magnitude compared to laboratory air. The enhancement in fatigue crack growth rate was accompanied by evidence of embrittlement in the crack path, involving both brittle intergranular and transgranular failure modes. Both the enhancement of fatigue crack growth rates and the extent of intergranular growth modes are dependent on cyclic frequency which, along with the absence of a similar frequency effect in a spray-formed version of the material with a significantly different grain structure, supports a mechanism of grain boundary hydrogen diffusion for intergranular corrosion fatigue crack growth. The convergence of corrosion fatigue crack growth rates at high ΔK in both spray-formed and conventional plate materials coincides with the operation of identical transgranular corrosion fatigue modes dependent on strain-controlled hydrogen diffusion ahead of the crack tip. © 1997 Acta Metallurgica Inc.

Fatigue crack growth behaviour in molten-metal processed SiC particle-reinforced aluminium alloys

Fatigue crack initiation and subsequent short crack growth behaviour of 2014-5wt%SiC aluminium alloy composites has been examined in 4-point bend loading using smooth bar specimens. The growth rates of long fatigue cracks have also been measured at different stress ratios using pre-cracked specimens. The distributions of SiC particles and of coarse constituent particles in the matrix (which arise as a result of the molten-metal processing and relatively slow cooling rate) have been investigated. Preferential crack initiation sites were found to be SiC-matrix interfaces, SiC particles associated with constituent particles and the coarse constituent particles themselves. For microstructurally short cracks the dispersed SiC particles also act as temporary crack arresters. In the long crack growth tests, higher fatigue crack growth rates were obtained than for monolithic alloys. This effect is attributed to the contribution of void formation, due to the decohesion of SiC particles, to the fatigue crack growth process in the composite. Above crack depths of about 200 μm 'short' crack growth rates were in good agreement with the long crack data, showing a Pris exponent, m = 4 in both cases. For the long crack and short crack growth tests little effect of specimen orientation and grain size was observed on fatigue crack growth rates, but, specimen orientation affected the toughness. No effect of stress ratio in the range R = 0.2-0.5 was seen for long crack data in the Paris region.

Effects of microstructure, temperature and R-ratio on fatigue crack propagation and threshold behaviour in two Ni-base alloys

Fatigue crack propagation and threshold data for two Ni-base alloys, Astroloy and Nimonic 901, are reported. At room temperature the effect which altering the load ratio (R-ratio) has on fatigue behaviour is strongly dependent on grain size. In the coarse grained microstructures crack growth rates increase and threshold values decrease markedly as R rises from 0. 1 to 0. 8, whereas only small changes in behaviour occur in fine grained material. In Astroloy, when strength level and gamma grain size are kept constant, there is very little effect of processing route and gamma prime distribution on room temperature threshold and crack propagation results. The dominant microstructural effect on this type of fatigue behaviour is the matrix ( gamma ) grain size itself.

Coupling of Heck and hydrogenation reactions in a continuous compact reactor

A continuous multi-step synthesis of 1,2-diphenylethane was performed sequentially in a structured compact reactor. This process involved a Heck C-C coupling reaction followed by the addition of hydrogen to perform reduction of the intermediate obtained in the first step. Both of the reactions were catalysed by microspherical carbon-supported Pd catalysts. Due to the integration of the micro-heat exchanger, the static mixer and the mesoscale packed-bed reaction channel, the compact reactor was proven to be an intensified tool for promoting the reactions. In comparison with the batch reactor, this flow process in the compact reactor was more efficient as: (i) the reaction time was significantly reduced (ca. 7 min versus several hours), (ii) no additional ligands were used and (iii) the reaction was run at lower operational pressure and temperature. Pd leached in the Heck reaction step was shown to be effectively recovered in the following hydrogenation reaction section and the catalytic activity of the system can be mostly retained by reverse flow operation. © 2009 Elsevier Inc. All rights reserved.

Hydrogen production by steam reforming of DME in a large scale CFB reactor. Part I:computational model and predictions

This study presents a computational fluid dynamic (CFD) study of Dimethyl Ether steam reforming (DME-SR) in a large scale Circulating Fluidized Bed (CFB) reactor. The CFD model is based on Eulerian-Eulerian dispersed flow and solved using commercial software (ANSYS FLUENT). The DME-SR reactions scheme and kinetics in the presence of a bifunctional catalyst of CuO/ZnO/Al2O3+ZSM-5 were incorporated in the model using in-house developed user-defined function. The model was validated by comparing the predictions with experimental data from the literature. The results revealed for the first time detailed CFB reactor hydrodynamics, gas residence time, temperature distribution and product gas composition at a selected operating condition of 300 °C and steam to DME mass ratio of 3 (molar ratio of 7.62). The spatial variation in the gas species concentrations suggests the existence of three distinct reaction zones but limited temperature variations. The DME conversion and hydrogen yield were found to be 87% and 59% respectively, resulting in a product gas consisting of 72 mol% hydrogen. In part II of this study, the model presented here will be used to optimize the reactor design and study the effect of operating conditions on the reactor performance and products.

A CFD study of biomass pyrolysis in a downer reactor equipped with a novel gas-solid separator-II thermochemical performance and products

A Eulerian-Eulerian CFD model was used to investigate the fast pyrolysis of biomass in a downer reactor equipped with a novel gas-solid separation mechanism. The highly endothermic pyrolysis reaction was assumed to be entirely driven by an inert solid heat carrier (sand). A one-step global pyrolysis reaction, along with the equations describing the biomass drying and heat transfer, was implemented in the hydrodynamic model presented in part I of this study (Fuel Processing Technology, V126, 366-382). The predictions of the gas-solid separation efficiency, temperature distribution, residence time and the pyrolysis product yield are presented and discussed. For the operating conditions considered, the devolatilisation efficiency was found to be above 60% and the yield composition in mass fraction was 56.85% bio-oil, 37.87% bio-char and 5.28% non-condensable gas (NCG). This has been found to agree reasonably well with recent relevant published experimental data. The novel gas-solid separation mechanism allowed achieving greater than 99.9% separation efficiency and < 2 s pyrolysis gas residence time. The model has been found to be robust and fast in terms of computational time, thus has the great potential to aid in future design and optimisation of the biomass fast pyrolysis process.

Pyrolysis of Napier grass in a fixed bed reactor:effect of operating conditions on product yields and characteristic

This study presents a report on pyrolysis of Napier grass stem in a fixed bed reactor. The effects of nitrogen flow (20 to 60 mL/min), and reaction temperature (450 to 650 degrees C) were investigated. Increasing the nitrogen flow from 20 to 30 mL/min increased the bio-oil yield and decreased both bio-char and non-condensable gas. 30 mL/min nitrogen flow resulted in optimum bio-oil yield and was used in the subsequent experiments. Reaction temperatures between 450 and 600 degrees C increased the bio-oil yield, with maximum yield of 32.26 wt% at 600 degrees C and a decrease in the corresponding bio-char and non-condensable gas. At 650 degrees C, reductions in the bio-oil and bio-char yields were recorded while the non-condensable gas increased. Water content of the bio-oil decreased with increasing reaction temperature, while density and viscosity increased. The observed pH and higher heating values were between 2.43 to 2.97, and 25.25 to 28.88 MJ/kg, respectively. GC-MS analysis revealed that the oil was made up of highly oxygenated compounds and requires upgrading. The bio-char and non-condensable gas were characterized, and the effect of reaction temperature on the properties was evaluated. Napier grass represents a good source of renewable energy when all pyrolysis products are efficiently utilized.

Giant piezoresistance in silicon-germanium alloys

We use first-principles electronic structure methods to show that the piezoresistive strain gauge factor of single-crystalline bulk n-type silicon-germanium alloys at carefully controlled composition can reach values of G = 500, three times larger than that of silicon, the most sensitive such material used in industry today. At cryogenic temperatures of 4 K we find gauge factors of G = 135 000, 13 times larger than that observed in Si whiskers. The improved piezoresistance is achieved by tuning the scattering of carriers between different (Delta and L) conduction band valleys by controlling the alloy composition and strain configuration.

First-principles calculation of carrier-phonon scattering in n-type Si1−xGex alloys

First-principles electronic structure methods are used to find the rates of inelastic intravalley and intervalley n-type carrier scattering in Si1-xGex alloys. Scattering parameters for all relevant Delta and L intra- and intervalley scattering are calculated. The short-wavelength acoustic and the optical phonon modes in the alloy are computed using the random mass approximation, with interatomic forces calculated in the virtual crystal approximation using density functional perturbation theory. Optical phonon and intervalley scattering matrix elements are calculated from these modes of the disordered alloy. It is found that alloy disorder has only a small effect on the overall inelastic intervalley scattering rate at room temperature. Intravalley acoustic scattering rates are calculated within the deformation potential approximation. The acoustic deformation potentials are found directly and the range of validity of the deformation potential approximation verified in long-wavelength frozen phonon calculations. Details of the calculation of elastic alloy scattering rates presented in an earlier paper are also given. Elastic alloy disorder scattering is found to dominate over inelastic scattering, except for almost pure silicon (x approximate to 0) or almost pure germanium (x approximate to 1), where acoustic phonon scattering is predominant. The n-type carrier mobility, calculated from the total (elastic plus inelastic) scattering rate, using the Boltzmann transport equation in the relaxation time approximation, is in excellent agreement with experiments on bulk, unstrained alloys..

Study of DNA damage with a new system for irradiation of samples in a nuclear reactor

FAPESP:97/5550

New mechanical samples positioning system for irradiations on a radial channel at nuclear research reactor in a full-power continuous operation

FAPESP:97/5550