Combustion of methane in catalytic honeycomb monolith burners

The heat transfer efficiency, stability, and pollutant emissions characteristics of ultra‐lean methane–air combustion in some precious metal‐based honeycomb monoliths were investigated. The interpretation of the experimental results was assisted using numerical modelling of the gas‐phase combustion process. The thermal radiation output of the monoliths varied between 27 and 30 per cent of the thermal input, and this compared favourably with equivalent porous inert media burners. The minimum fuel concentrations for very‐low emission stable combustion were found to be significantly lower than for conventional gas‐phase combustion and were shown to vary with the nature and loading of the catalyst, as well as with flow rates. The palladium catalyst was found to have a larger window of mixture strengths and flow rates for stable operation than the platinum one. During all the runs under stable combustion conditions, only extremely small amounts of CO, NO_x and unburnt hydrocarbons were detected. Thus, the operating conditions verified ‘near‐zero’ pollutant emissions that only a catalytic combustion process can achieve at present. Temperature profiles inside the monoliths channels proved that the catalyst's role was not only to enable the ignition of fuel mixtures below flammability limits, but also to ensure the complete oxidation of the fuel to CO₂ via surface reactions in the steady state. The reaction zone inside the catalysts was found to end at about 10 mm from the monolith's entrance. The effect of monolith length was investigated and a reduction of 70 per cent in the original length was found possible. Copyright © 2000 John Wiley & Sons, Ltd.     

Catalytic and inhibitory effects of Pt surfaces on the oxidation of CH4/O2/N2 mixtures

The catalytic oxidation of lean CH₄/O₂/N₂ mixtures was studied by injecting a stream of the mixture onto a polycrystalline platinum foil whose temperatures could be varied by resistance heating between 300 and 1800 K. Experiments were performed in the stagnation point flow configuration under steady‐state conditions in order to derive the fuel conversion efficiencies and the product selectivities to CO and CO₂. These were compared with a numerical model. With increasing foil temperature, the first appearance of CO in the products signalled the onset of homogeneous oxidation. The surface temperatures of the transition from catalytic to homogeneous oxidations were higher than those of the ‘reversed’ transition from homogeneous to catalytic, causing hysteresis in the fuel conversion and product selectivities curves. For the conditions investigated, the number of thermal cycles applied to the foils were found not to affect the fuel conversion with surface temperature in the catalytic regime. In contrast, they increased the peak of CO selectivity by a factor of two and enhanced the hysteresis behaviour by lowering the temperature of the transition from homogeneous to catalytic oxidation. Decreasing fuel concentrations in the fuel‐lean mixture feed did not change appreciably the catalytic oxidation conversion curve, but reduced the temperature of the transition from catalytic to homogeneous oxidation, and eliminated the hysteresis. The peak of CO selectivity was found not to vary significantly in the range of fuel mixture strengths studied. The fuel conversion efficiency curves with surface temperature were successfully modelled over the whole catalytic oxidation regime using one global chemical reaction of methane oxidation. A combination of existing detailed heterogeneous and homogeneous chemical mechanisms of methane oxidation offered the advantage of predicting the CO and CO₂ products selectivities, but was found to predict larger conversions in the kinetically controlled catalytic oxidation regime. The agreement with the experimental conversions was restored in the mass transport rate limited regime and permitted a discussion of the inhibitory role of the Pt surface in the transitions between catalytic and homogeneous oxidation regimes. Both the global and detailed chemical mechanisms yielded higher fuel conversions than those measured once the homogeneous oxidation regime was established, showing the need for further validation in this regime, in particular with respect to the formation of CO. Copyright © 2000 John Wiley & Sons, Ltd.     

Dynamic simulation and experimental evaluation of EPDM terpolymerization with vanadium-based catalyst

The development of a simplified kinetic model describing some effects observed in catalyzed olefin terpolymerization is presented. Based on the method of moments, the model describes the influence of Al/V ratio and diene concentration on reaction yield and on polymer characteristics such as molecular weight, ethylene incorporation, and polydispersity. In order to verify the model validity, the terpolymerization reactions were performed using VOCl₃–Al₂Et₃Cl₃ systems and 2-ethylidenebi-cyclo[2.2.1]hept-5-ene (ENB) as diene. The results of dynamic simulation fit well the experimental data for Al/V up to 15, but the model fails under high diene concentration, where branching reactions, neglected by reason of simplification, become significant. © 1998 John Wiley & Sons, Inc. J. Appl. Polym. Sci. 70: 1173–1189, 1998     

Nano-polymer-dispersed liquid crystal as phase modulator for a tunable vertical-cavity surface-emitting laser at 1.55 mum

We demonstrate what we believe is the first nonmechanical tunable vertical-cavity surface-emitting laser operating in the C band. This was achieved as a result of the combination of an InGaAs quantum well structure with a 6lambda thickness tunable index nano-polymer-dispersed liquid-crystal material. Experimental results exhibited a potential tunable range close to 10 nm, in the preliminary version, and excellent single mode locking due to the side-mode suppression ratio (more than 20 dB) over the whole spectral range. Another decisive advantage, compared to mechanical solutions, was the tuning response time of a few tens of microseconds (>30 micros) to scan the full spectral range (10 nm), making this device appropriate for some access network functions, as well as being robust and low cost. The voltage values are the main limitation to wavelength range extension. We present a first version of the device optically pumped. The next version will be electrically pumped as required for the access network applications targeted here.     

Risk and protection factors in fatal accidents

This paper aims at addressing the interest and appropriateness of performing accident severity analyses that are limited to fatal accident data. Two methodological issues are specifically discussed, namely the accident-size factors (the number of vehicles in the accident and their level of occupancy) and the comparability of the baseline risk. It is argued that - although these two issues are generally at play in accident severity analyses - their effects on, e.g., the estimation of survival probability, are exacerbated if the analysis is limited to fatal accident data. As a solution, it is recommended to control for these effects by (1) including accident-size indicators in the model, (2) focusing on different sub-groups of road-users while specifying the type of opponent in the model, so as to ensure that comparable baseline risks are worked with. These recommendations are applied in order to investigate risk and protection factors of car occupants involved in fatal accidents using data from a recently set up European Fatal Accident Investigation database (Reed and Morris, 2009). The results confirm that the estimated survival probability is affected by accident-size factors and by type of opponent. The car occupants’ survival chances are negatively associated with their own age and that of their vehicle. The survival chances are also lower when seatbelt is not used. Front damage, as compared to other damaged car areas, appears to be associated with increased survival probability, but mostly in the case in which the accident opponent was another car. The interest of further investigating accident-size factors and opponent effects in fatal accidents is discussed.     

Semi-industrial production of a minimally processed infant formula powder using membrane filtration

Infant formula (IF) is submitted to several heat treatments during production, which can lead to denaturation or aggregation of proteins and promote Maillard reaction. The objective of this study was to investigate innovative minimal processing routes for the production of first-age IF powder, thus ensuring microbial safety with minimal level of protein denaturation. Three nutritionally complete IF powders were produced at a semi-industrial scale based on ingredients obtained by fresh bovine milk microfiltration (0.8 and 0.1-µm pore size membranes). Low-temperature vacuum evaporation (50°C) and spray-drying (inlet and outlet temperatures of 160 and 70°C, respectively) were conducted to produce the T? formula with no additional heat treatment. The T+ formula was produced with a moderate heat treatment (75°C for 2 min) applied before spray-drying, whereas the T+++ formula received successive heat treatments (72°C for 30 s on the milk; 90°C for 2–3 s before evaporation; 85°C for 2 min before spray-drying), thus mimicking commercial powdered IF. Protein denaturation and Maillard reaction products were followed throughout the production steps and the physicochemical properties of the powders were characterized. The 3 IF powders presented satisfactory physical properties in terms of a_w, free fat content, glass transition temperature, and solubility index, as well as satisfactory bacteriological quality with a total flora <10³ cfu/g and an absence of pathogens when a high level of bacteriological quality of the ingredients was ensured. Protein denaturation occurred mostly during the heat treatments of T+ and T+++ and was limited during the spray-drying process. The IF powder produced without heat treatment (T-) presented a protein denaturation extent (6 ± 4%) significantly lower than that in T+++ (58 ± 0%), but not significantly different from that in T+ (10 ± 4%). Although T? tended to contain less Maillard reaction products than T+ and T+++, the Maillard reaction products did not significantly discriminate the infant formulas in the frame of this work. The present study demonstrated the feasibility of producing at a semi-industrial scale an infant formula being bacteriologically safe and containing a high content of native proteins. Application of a moderate heat treatment before spray-drying could further guarantee the microbiological quality of the IF powders while maintaining a low protein denaturation extent. This study opens up new avenues for the production of minimally processed IF powders.     

Self-organized TiO2 nanotube arrays: synthesis by anodization in an ionic liquid and assessment of photocatalytic properties

Self-organized TiO(2) nanotube (NT) arrays were produced by anodization in ethylene glycol (EG) electrolytes containing 1-n-butyl-3-methyl-imidazolium tetrafluoroborate (BMI.BF(4)) ionic liquid and water. The morphology of the as-formed NTs was considerably affected by changing the anodization time, voltage, and water and ionic liquid electrolyte concentrations. In general, a nanoporous layer was formed on the top surface of the TiO(2) NTs, except for anodization at 100 V with 1 vol % of BMI.BF(4), where the NT's mouth was revealed. The length and bottom diameter of the NTs as well as the pore diameter of the top layer showed a linear relationship with increased anodization voltage. These TiO(2) NTs were tested as photocatalysts for methyl orange photodegradation and hydrogen evolution from water/methanol solutions by UV light irradiation. The results show that the TiO(2) NTs obtained by anodization in EG/H(2)O/BMI.BF(4) electrolytes are active and efficient for both applications.     

Disposable indicators for monitoring lighting conditions in museums

Photoinduced alterations of light-sensitive artifacts represent one of the main problems that conservators and curators have to face for environmental control in museums and galleries. Therefore, increasing attention has been recently devoted to developing strategies of indoor light monitoring, especially aimed at minimizing the cumulated light exposure for the objects on exhibit. In this work a prototype of a light dosimeter, constituted by a photosensitive dyes/polymer mixture applied on a paper substrate, is presented. This indicator, specially designed for a preventive assessment of the risk of damage for highly light-sensitive objects, undergoes a progressive color variation as its exposure to the light increases. Different, easily distinguishable color steps are exhibited depending on the light dose received, so that the dosimeter can be used straightforwardly to have a first, instrumentation-free estimation of the total light exposure. A reflectance spectroscopy study in the 350-860 nm range was carried out on prototype dosimeters exposed to light emitted from a tungsten-halogen lamp to investigate the response of the dosimeter to the light and to study the fading mechanism. Two different approaches were evaluated for the calibration of the prototype: colorimetry and principal component analysis of the reflectance spectra. The usefulness of the two methods in providing a quantitative indication of the light dose received was evaluated.     

Proton exchange membrane water electrolysis with short-side-chain Aquivion membrane and IrO2 anode catalyst

A series of three membrane types has been screened for medium temperature solid polymer electrolyte water electrolysis in membrane electrode assemblies coated with 2 mg cm⁻² of iridium oxide as a catalyst for the oxygen evolution reaction, synthesised via a hydrolysis method from the hexachloroiridic acid precursor, and deposited on the membrane either directly by spray deposition or by decal transfer. The short-side-chain perfluorosulfonic acid Aquivion^® ionomer of equivalent weight 870 meq g⁻¹, in membranes of thickness 120 μm, gives higher water electrolysis performance at 120 °C than a composite membrane of Aquivion^® with zirconium phosphate, while a sulfonated ether-linked polybenzimidazole, sulfonated poly-[(1-(4,4′-diphenylether)-5-oxybenzimidazole)-benzimidazole], shows promising performance and no transport limitations up to 2 A cm⁻². The lowest cell voltage was observed at 120 °C for an MEA prepared using spray-coating directly on the Aquivion^® membrane, 1.57 V at 1 A cm⁻².