An analytic solution to the transient diffusion-reaction problem in particles dispersed in a slurry reactor

In this work, we present the solution of the equations that govern the reactant transport in a well mixed system that contains particles where diffusion and first-order reaction occur. The transport equations are coupled by an interfacial boundary condition that includes mass transfer resistance. The statement of the problem allows arbitrary time depending feed functions. The evaluation of the solution obtained by the Laplace method requires the solution of an eigenvalue problem. We discuss the evaluation of the solution, and typical results for three different feed functions: step, pulse and oscillatory functions are presented. The resulting equations are able to show the effect of internal and external mass transfer limitations on the particle and fluid concentrations and on kinetic experimental results.     

A description of phase inversion behaviour in agitated liquid-liquid dispersions under the influence of the Marangoni effect

The influence of the Marangoni effect on phase inversion behaviour is examined by integrating a microscopic study of the drop coalescence process, in which thin film drainage in the presence of insoluble surfactant occurs, into a macroscopic phase inversion model which has been developed previously using a Monte Carlo technique. This is achieved via an immobility factor, obtained from a comparison of the film drainage times for surfactant-laden systems and surfactant-free systems as a function of the drop approach velocity, surface Péclet number, initial surfactant concentration and the Hamaker constant, which is then used to modify the coalescence probability in the phase inversion model. On the one hand, the results indicate that the Marangoni effect removes any influence that the viscosity ratio has on phase inversion due to immobilisation of the interface, thus shielding the flow in the film from the effects of the flow in the dispersed phase; the point at which phase inversion occurs therefore tends towards equivolume holdups with the addition of surfactant. On the other hand, when comparisons are made with pure systems in which surfactant is absent, the system is seen to be either stabilised or de-stabilised from inversion depending on the viscosity ratio of the system. This is attributed to the influence of surfactant on the dispersion morphologies on either side of the inversion (i.e. water-in-oil dispersions and oil-in-water dispersions) and depends on the dispersed phase holdup; the Marangoni effect is felt stronger when the dispersed phase holdup is low.     

Investigation of the chromate conversion coating on Alclad 2024 aluminium alloy: effect of the pH of the chromate bath

The parameters of the chromate bath, like temperature, pH, and fluoride content, strongly affect the morphology and chemical composition of the chromate conversion coating and as a consequence have a large influence on its corrosion performance. In this paper, electrochemical impedance spectroscopy (EIS) was used in combination with other techniques to investigate the role played by the pH of the chromate bath on the properties of the chromate film formed on Alclad 2024 aluminium alloy. Scanning electron microscopy (SEM), atomic force microscopy (AFM) and spectroscopic ellipsometry (SE) have shown the formation of a thicker and less dense chromate layer when the pH of the chromate bath is changed from 2.4 to 1.2. The analysis of the EIS spectra have highlighted that this change in pH leads to the formation of more protective and more resistant chromate corrosion products (CCP) inside the defects of the chromate film. When a thin, dense and protective layer of CCP is formed in the defects, the corrosion behaviour of the chromate conversion coating improves for two main reason: (a) further attack of the defects is avoided or delayed; (b) the change in volume caused by the formation of the CCP is limited resulting in a low level of stress in the film, which as a consequence is not detached from the aluminium substrate.     

Semiconductor nanostructures in an alumina template matrix: micro- versus macro-scale photoelectrochemical behavior

We show herein that the photoelectrochemical behavior of a given semiconductor nanodot (p-CuSCN or n-TiO₂) in an alumina template matrix, is remarkably different than that of its macro-sized counterpart. Three separate examples of this distinct difference in behavior are presented. It is shown how the photoresponse (e.g. photocurrent) may be amplified (from a low level typical of the signal emanating from a ∼10⁻¹¹ cm² region corresponding to a semiconductor nanodot) by using a large number of electrically inter-connected Au nanowires to support the overlying semiconductor nanodots. The anomalous photoresponse of p-CuSCN nanodots in the template matrix was also numerically simulated by a simple parallel equivalent circuit consisting of a semiconductor and a photocapacitor. Possible practical application scenarios are finally presented for these nanostructures.     

Diffusion in porous silicon: effects on the reactivity of alkenes and electrochemistry of alkylated porous silicon

Alkenes are known to react with hydrogen-terminated silicon surfaces to produce robust organic monolayers that are attached to the surface via covalent SiC bonds. In this report we investigate the dependence of the rate of alkylation of porous silicon samples on the reaction time using photochemical initiation. The kinetics of the photochemical alkylation of hydrogen-terminated porous silicon by undec-1-ene in toluene were observed to be pseudo first order, however the apparent rate constant decreased as the concentration of undec-1-ene increased. This behaviour is opposite to what would be expected if the rate-limiting process was an elementary chemical reaction step involving the alkene. Instead, it suggests that transport of the alkene to reactive sites and in the correct orientation is the rate-limiting step. Comparison of the rates of alkylation of porous silicon by undec-1-ene and dimethoxytrityl (DMT)-undecenol is consistent with such an interpretation as the bulky DMT headgroup gives a lower rate of alkylation. The diffusion of some simple redox-active probe molecules in porous silicon was investigated using a scanning electrochemical microscope (SECM). The probe molecules are converted at diffusion-controlled rate at an inlaid disk ultramicroelectrode (UME) consisting of the cross-section of a microwire sealed in glass. If the microelectrode is placed a short distance above the porous silicon, the microelectrode current depends on kinetics of the electrochemical reactions at the porous silicon and the mass transport properties within the open thin layer cell formed by the microelectrode and the alkylated porous silicon. In order to differentiate the effects of finite heterogeneous kinetics at silicon from diffusion limitations, current-distance curves were fitted over a wide range of applied potentials (on the Si) and it was observed that the diffusion coefficient in the porous layer was strongly anisotropic. The measured diffusion rates are comparable to those in bulk water along the pores, but with negligible diffusion between pores. This indicates that few pore-pore interconnections exist in the porous silicon.     

Molecular sieve properties obtained by cracking of methane on activated carbon fibers

Molecular sieve properties of activated carbon fibers modified by cracking treatment with methane are studied herein. The effect of methane treatment on the porous texture of the samples has been studied while varying temperature and time. These materials have been evaluated for their selectivity during CO₂ and CH₄ separation; their uptakes have been compared with non-treated activated carbon fibers (studied previously), which were considered suitable to be used as molecular sieves. Kinetics of CO₂ and CH₄ uptake have also been investigated in this research. The treatment produced materials exhibiting fast kinetics and high selectivity during CO₂ and CH₄ separation; at the same time however, the CO₂ uptake capacity was diminished.     

Magnetic resonance imaging of H, Na, and Cl penetration in Portland cement mortar

The first magnetic resonance imaging profiles of chloride content in low- and high-permeability Portland cement mortar have been obtained using a novel material science imaging technique. The penetration of water as well as chloride and sodium ions, into mortar specimens was monitored for a period of 72 h. Marked differences in penetration depth were observed in low- and high-permeability mortar. These preliminary experiments show significant differences between the extent and nature in the penetration of chlorides compared to water and sodium.     

Mixture-proportioning of high-performance concrete

The paper presents a new approach to design concrete mixtures. It is based upon a set of models relating composition and engineering properties of concrete, to be implemented into software, linked with a material database. The principles underlying the various models are summarized, most of which focus on the granular structure of fresh/hardened concrete. A global approach to concrete is promoted, where performance specifications can be formulated in terms of fresh concrete (yield stress, plastic viscosity, slump and air content), hardening concrete (adiabatic temperature rise and autogenous shrinkage) and hardened concrete (compressive strength at any age, tensile strength, elastic modulus, creep and shrinkage). This approach is illustrated through the design of a special high-shrinkage high-performance concrete (HPC) for road application. To date, durability is lacking in the model and requires further research.     

A Refinement on the Notion of Type I and II (Co)MoS Phases in Hydrotreating Catalysts

Hydrotalcite-like compounds with boron anions in the interlayer were obtained using a coprecipitation method. The effect of different pH values during the preparation was investigated and the effect on crystallinity and phase distribution studied. The influence of different methods of acidity regulation was also analyzed. The efficiency of synthesis of boron-containing anionic clays was evaluated, and the good thermal stability of the materials was noted. Surface characteristics were determined by X-ray photoelectron spectroscopy and correlated to the bulk properties obtained by X-ray diffraction and ²⁷Al and ¹¹B MAS NMR. The samples tested in gas-phase Beckmann rearrangement showed caprolactam formation, and the results were related to the surface features.