Methanol oxidation on Au/TiO2 catalysts

We have investigated the adsorption and reaction of methanol with Au/TiO₂ catalysts using a pulsed flow reactor, DRIFTS and TPD. The TiO₂ (P25) surface adsorbed a full monolayer of methanol, much of it in a dissociative manner, forming methoxy groups associated with the cationic sites, and hydroxyl groups at the anions. The methoxy is relatively stable until 250 °C, at which point decomposition occurs, producing mainly dimethyl ether by a bimolecular surface reaction. As the concentration of methoxy on the surface diminishes, so the mechanism reverts to a de-oxygenation pathway, producing mainly methane and water (at ~330 °C in TPD), but also with some coincident CO and hydrogen. Au catalysts were prepared by the deposition-precipitation method to give Au loadings between 0.5–3 wt %. The effect of low levels of Au on the reactivity is marked. The pathway which gives methane, which is characteristic of titania, remains, but a new feature of the reaction is the evolution of CO₂ and H₂ at lower temperature (a peak is seen in TPD at 220 °C), and the elimination of the DME-producing state. Clearly this is associated with the presence of Au and appears to be due to the production of a formate species on the surface of the Au component. This formate species is mainly involved in the reaction of methanol with the Au/TiO₂ catalysts which results in a combustion pathway being followed, with complete conversion occurring by ~130 °C.     

Ultrasonic Dispersion of Ceramic Powders

Ultrasonication is very effective in dispersing alumina and barium titanate slurries. When optimum conditions are used, very short durations (2 to 3 min) are enough to achieve well-dispersed, stable suspensions.     

Dynamic behaviour of viologen-activated nanostructured TiO2: correlation between kinetics of charging and coloration

The dynamic response of viologen-activated nanostructured titanium dioxide has been studied by means of electrical and electro-optical measurements. We show that the state of charge of the semiconductor network is the key factor mediating between the electrode potential and colouration of viologen. Theoretically, we relate the electrode potential to the statistics of occupancy of both TiO₂ nanoparticles and oxidized viologen molecules attached to the surface, on the assumption of quasi-equilibrium of Fermi levels in these contacting phases. Experimentally, we determine the statistical function from steady-state measurements (electrochemical impedance spectroscopy) of the capacitance of the semiconductor film. From this understanding we explain the main features that correlate the simultaneous voltammetry and transmittance responses. Finally, the redox process of viologen is resolved separately from the TiO₂ response by means of transmittance data.     

HEAT TRANSFER IN A THIN LIQUID FILM IN THE PRESENCE OF AN ELECTRIC FIELD

Heat transfer enhancement in an evaporating thin liquid film utilizing a electric field under isothermal interfacial condition is presented. A new mathematical model subjected to van der Waals attractive forces, capillary pressure, and an electric field is developed to describe the heat transfer enhancement in the evaporating thin liquid film. The effect of the electrostatic field on the curvature of the thin film, evaporative flux, pressure gradient distribution, heat flux, and heat transfer coefficient in the thin film is presented. The results show that applying an electric field can enhance heat transfer in a thin liquid film significantly. In addition, utilizing electric fields on the evaporating film will be a way to expand the extended meniscus region to attain high heat transfer coefficients and high rates of heat flux.     

CRUDi framework proposal: financial industry application

The alignment of information systems with the business goals of an organisation, although a topic of great importance, is not always properly valued or taken into consideration. In general, managers have different opinions to chief information officers (CIOs) in relation to IS, especially with regard to their importance and value to the business and also in terms of investment needs. Here, we discuss and study new approaches to methods and tools for assessing the relative importance of each information system to business, focusing on the financial sector including banks and insurance companies. We suggest the introduction of new key indicators for better decision support and to identify investment priorities, and present results regarding the relative importance of each process to support the business strategy. The primary goal for the inherent research project is to analyse the main problems and difficulties encountered by IS and IT managers, featuring different players and how they relate. The main contributions of this work are the CRUDi framework as a tool to improve alignment between business and IS strategies and the CRUDi survey and its results qualifying the financial sector's opinion regarding the relative importance of processes and investments.     

Effect of advanced chilling methods on lipid damage during sardine (Sardina pilchardus) storage

Slurry ice is a biphasic system consisting of small spherical ice crystals surrounded by seawater at subzero temperature. Its effect on lipid damage (hydrolysis and oxidation) was evaluated during the chilled storage of a fatty fish species, sardine (Sardina pilchardus). Slurry ice treatment was checked alone and in combination with ozone and compared to traditional flake icing during a 22‐day storage. Different lipid damage indices (free fatty acids, FFA; peroxide value, PV; thiobarbituric acid index, TBA‐i; fluorescent compounds, FR) were checked and compared to sensory assessment and nucleotide degradation (K value). According to lipid hydrolysis (FFA) and oxidation (PV and FR) developments, slurry ice showed an inhibitory effect (p <0.05) on lipid damage during storage, as well as an inhibition of nucleotide autolytic degradation. Ozonised slurry ice did not provide differences (p >0.05) from slurry ice alone when considering lipid hydrolysis, nucleotide degradation and some lipid oxidation indices (PV and FR), although a higher (p <0.05) TBA‐i was observed at day 22 of storage when compared to flake ice and slurry ice treatments. However, a lower (p <0.05) fluorescence development was observed for fish treated under ozonised slurry ice when compared to traditionally iced fish. Sensory assessment showed a higher shelf life for fish samples treated under ozonised slurry ice than for their counterparts under slurry ice (15 d versus 12 d), while flake icing led to a far shorter shelf life (5 d). According to sensory and biochemical (lipid matter and nucleotide) analysis, slurry ice has proved to be a promising technology for damage inhibition and quality retention in a fatty fish species such as sardine. Ozonised slurry ice was also shown to be useful, since a longer shelf life was obtained in the present experiment and a pro‐oxidant effect of ozone on sardine lipids was not proved.     

The role of temperature in copper electrocrystallization in ammonia-chloride solutions

This paper presents the analysis of temperature effect on the copper electrocrystallization process from the stainless steel/Cu(II)-Cu(I)-NH₄Cl-NH₃-H₂O system. Electrochemical techniques and scanning electron microscopy with energy dispersion spectroscopy were employed. An increment in temperature had a favorable effect in increasing the kinetic and nucleation parameters, favoring the copper reduction on the stainless steel substrate. From the chronoamperometric study, it was possible to find the transfer coefficient (α), which does not have a significant variation with temperature, and the exchange current density (i₀) for different temperatures, where a 50.63 kJ/mol value was estimated for the activation energy. The potentiostatic study suggested the presence of two processes involved: an electron transfer reaction and a 3D nucleation—growth process, under combined charge transfer and diffusion limitations. In addition, an important current contribution could be accounted for on the basis of the existence of a capacitive component in the system. This capacitive behavior was associated to the oxide layer (Cr₂O₃)-chloride interactions on the stainless steel surface. Current transients analyses at different potentials, based on the models of: Milchev (low overpotential), Scharifker-Mostany (SM) and Heermann-Tarallo (HT) (high overpotential) allowed to obtain the values of nucleation parameters, such as: the nucleation rate constant (A), the active nucleation sites number (N₀), the stationary nucleation rate (I_st = A × N₀) and the nuclei saturation number (N_s). Finally, the deposits obtained were analyzed by SEM, showing an acceptable correlation between the nucleation parameters and morphology of the deposits obtained. An increment in temperature favored the growth of the cluster before the coalescence occurred.     

Removal of fulvic acid from aqueous media by adsorption onto modified vermiculite

Clay minerals are low cost materials that can be structurally modified and exploited for removal of natural organic matter from freshwaters. The present study shows that vermiculites modified by ion exchange with hexadecyltrimethylammonium or intercalation with poly(hydroxy iron) cations are potential adsorbents for removal of fulvic acid, whereas the adsorption on the raw clay mineral is negligible. The efficiency of the modified vermiculite was evaluated by measuring adsorption isotherms by the batch technique using initial fulvic acid concentrations between 2.5 and 50.0 mg L^− 1, with one hour of contact time. At least 94% of the fulvic acid initially present in a 20 mg L^− 1 solution was sorbed onto either the intercalated poly(hydroxy iron) cations or the organically modified vermiculite. Up to an initial concentration of 5.0 mg L^− 1 the adsorption is irreversible, and no quantifiable fulvic acid was measured in the desorption experiments. For initial fulvic acid concentrations between 10.0 and 50.0 mg L^− 1, desorption was between 2.3% and 4.9% for Fe(III) intercalated vermiculite, and between 1.4% and 9.2% for the organoclay. The adsorption percentages on intercalated poly(hydroxy iron) cations increased upon lowering pH and increasing the ionic strength, indicating the occurrence of strong binding mechanisms such as ligand exchange. Adsorption percentage of fulvic acid onto the organoclay also increased with lowering of pH, but in this case the adsorption percentages showed a small decrease at high ionic strength, suggesting that electrostatic attraction plays an important role in the adsorption process.     

A quantitative feedback solution to the multivariable tracking error problem

This paper introduces a novel solution for the multi‐input multi‐output (MIMO) quantitative feedback theory control design problem with tracking error specifications. Looking for a minimum controller overdesign, the technique finds new controller quantitative feedback theory bounds based on necessary and sufficient conditions for the existence of suitable associated prefilter matrix elements. It improves previous approaches to the subject and includes (i) the possibility of a free selection of the nominal plant, (ii) a less conservative application of the Schwartz inequality to decisively reduce the potential controller overdesign, (iii) a methodology to design independently the elements of the prefilter matrix, and (iv) a scope of application to both sequential and nonsequential MIMO controller design methods. The benefits of the new control design technique are illustrated by means of two examples. The first one, a standard 2 × 2 MIMO problem, is provided for comparison purposes with previous approaches. The second example, included as a major control challenge, deals with a well‐known demanding distillation column benchmark problem. Copyright © 2013 John Wiley & Sons, Ltd.     

Soap-based detergent formulations: X. Nature of detergent deposits

The cumulative deposition of detergent residue on unsoiled cotton and polyester-cotton permanent press finish cloth was determined for a variety of detergent formulations after washing 25 consecutive times in 300 ppm hard water in a laboratory Tergotometer. Included in this study were: a phosphate-built laundry detergent, two carbonate-built detergents, tallow soap and various tallow soap formulations with anionic and amphoteric lime soap dispersing agents, and a glassy sodium silicate. Sample swatches washed with each formulation were analyzed for calcium, magnesium, and organic acid content. Fabric washed with the carbonate detergents showed the highest calcium and magnesium content, while those washed with the phosphate detergent and the soap-lime soap dispersant-builder formulations had the lowest. Fabric washed with soap alone had a much higher fatty acid residue than those washed with the other detergent formulations. However, the amount of organic acids left on the fabric after washing with a soap-lime soap dispersing agent formulation was no greater than that produced by phosphate- and carbonate-built detergents. The presence or absence of deposits also was verified visually with a scanning electron microscope. Each formulation also was tested for detergency by measuring the soil buildup in a multiwash procedure. Generally, the buildup of soil paralleled the deposit of detergent residue on the unsoiled cloths.