Identification of the adverse effect of nitrate on the phosphate release rate and improvement of EBPR process models.

The adverse effect of nitrate on the phosphate release rate in the anaerobic phase was observed and was hardly explainable with conventional EBPR process models. Four possible mechanisms were proposed including substrate competition, reduced fermentation, parallel reaction and sequential reaction. Batch experiments were designed and conducted to identify the dominant mechanism. Results showed that the sequential reaction was the only possible mechanism where only denitrification occurred if any nitrate existed in the anaerobic phase. Then the phosphate release following after the nitrate was completely removed. Nitrate inhibition effect was added into the PHA storage rate to incorporate the sequential reaction in the conventional ASM3 plus EAWAG bio-P module (ASM3 + P). Nitrate inhibition coefficient, K(I,NO,PAO) was found to be as low as 0.05 mg/L. This correlated well with experimental observation where no also meant that the anaerobic compartment of a continuous flow reactor could be seriously affected by the residual nitrate contained in the sludge recycle flow. This phenomenon caused overestimation of the phosphate uptake rate and consequently underestimation of PO4(3-) -P concentration. This problem was resolved by incorporation of a nitrate inhibition term in the ASM3 + P for more accurate simulation of the EBPR process.     

Design of a retention tank: comparison of stormwater quality models with various levels of complexity.

Stormwater quality simulation models are useful tools for the design and management of sewer systems. Modelling results are highly sensitive to experimental data used for calibration. This sensitivity is examined for three modelling approaches of various complexities (site mean concentration approach, event mean concentration approach and build-up, washoff and transport modelling approach) applied to a typical case study (design of a dry detention tank), accounting for the variability of calibration data and their effect on simulation results. Calibrated models with different calibration data sets were used to simulate 3 years of rainfall with different retention tank specific volumes. Annual pollutant load interception efficiencies were determined. Simulations results revealed (i) that there is no advantage in using the EMC model compared to the SMC model and (ii) that the BWT model resulted in higher design ratios than those given by the SMC/hydraulic approach. For both EMC and BWT models, using an increasing number n of events for calibration leads to narrower confidence intervals for the design ratios. It is crucial for design ratios to account for successive storm events in chronological order and to account for the maximum allowable flow to be transferred to the downstream WWTP.     

Catalytic epoxidation of olefins in the presence of a vanadyl porphyrin complex

It was found that vanadyl porphyrin complexes synthesized from petroleum metal porphyrin concentrates stimulated epoxidation during the olefin oxygenation process. The yields of obtained oxiranes turned out to be 38–75%, depending on the olefin structure. An epoxidation mechanism that suggests the formation of a protonated dioxygen adduct as an intermediate during oxygenation of olefins in the presence of vanadyl porphyrin complexes was proposed. An analogy is drawn between the epoxide formation reaction upon the catalytic oxygenation of olefins and the Prilezhaev reaction.     

Understanding silica-supported metal catalysts: Pd/silica as a case study

Supported metal catalysts, particularly noble metals supported on SiO₂, have attracted considerable attention due to the importance of the silica–metal interface in heterogeneous catalysis and in electronic device fabrication. Several important issues, e.g., the stability of the metal–oxide interface at working temperatures and pressures, are not well-understood. In this review, the present status of our understanding of the metal–silica interface is reviewed. Recent results of model studies in our laboratories on Pd/SiO₂/Mo(1 1 2) using LEED, AES and STM are reported. In this work, epitaxial, ultrathin, well-ordered SiO₂ films were grown on a Mo(1 1 2) substrate to circumvent complications that frequently arise from the silica–silicon interface present in silica thin films grown on silicon.     

Inhibition of microbial growth in ready‐to‐eat food stored at ambient temperature by modified atmosphere packaging

This study was undertaken to develop a modified atmosphere package to control microbial growth in ready‐to‐eat (RTE) products stored at ambient temperature. Ethanol and/or limonene associated with modified atmosphere (CO₂ : O₂ : N₂ = 30% : 5% : 65%) was used to inhibit the growth of total air‐borne microorganisms and Escherichia coli in RTE products stored at 25°C. The results indicated that 0.05% ethanol vapour in the headspace was effective to inhibit the growth of air‐borne microorganisms and E. coli at 25°C for 72 h in a model study, and the effectiveness was related to ethanol content. Both 73 ppm limonene and 0.05% ethanol vapour enhanced the bacteriostatic effect of modified atmosphere in RTE sushi roll products, and no off‐flavour was detected using this formulated gas; however, no significant inhibitory effect was observed for RTE cold noodle products. This study concludes that combinations of carbon dioxide, ethanol or limonene vapours are effective to inhibit microbial growth in RTE food at ambient temperature, and the outcome may be due to the hurdle effect. Copyright © 2003 John Wiley & Sons, Ltd.     

Verhalten von Magnesiumlegierungen für Anwendungen im Fahrzeugbau bei mechanisch‐elektrochemischer Komplexbeanspruchung: Einfluss passivierender Deckschichten und Mechanismen der lokalen Schädigung

Behavior of Magnesium‐Alloys for Automotive Applications under Mechanical and Environmental Loading: Influence of Passivating Films and Mechanisms of Local Breakdown To assure an efficient design of components under cyclic loading, all available data concerning fatigue have to be observed. Therefore the influences of manufacturing on the material condition, the mechanical loads and environmental effects have to be analysed. Magnesium‐alloys are of special interest for lightweight applications because of their excellent strength‐density ratio. The corrosion resistance of magnesium‐alloys depends on the same factors that are critical to other metals. The alloys have a good stability to atmospheric exposure and a good resistance to attack by alkali, chromic and hydrofluoric acids. However, because of the electrochemical activity of magnesium, the relative importance of some factors is greatly amplified. The nature and composition of passive films formed on magnesium‐alloys depend on the prevailing conditions, viz. alloy‐composition, passivation potential, pH, electrolyte composition and temperature. Passive films may be damaged by local breakdown. Because of this, magnesium‐alloys suffer a degradation of their properties when exposed to an aqueous environment. The main topic of the present investigations is the verification of mechanisms of the local breakdown of the protecting film. At least two mechanisms are possible for this localization: mechanical breakdown by slip steps and electrochemical breakdown (for e.g. by the effects of chloride ions). Corrosion and passivation of different high purity alloys have been studied in different solutions (neutral, alkaline with specific anions and cations) using electrochemical techniques. The diecasted alloys were tested as produced and machined. The results clarified that depending on alloy/material and surface condition/corrosion environment different mechanisms for electrochemical breakdown of the protecting films are possible. Hence fatigue life under environmental loading is influenced by surface and testing conditions.     

State of polarization changes: Classification and measurement

We propose a standardization procedure that provides a convenient, quantitative and reproducible laboratory-based method for measuring the state of polarization (SOP) fluctuations produced by polarization varying devices. This method is based on the SOP distributions generated by commercial polarization scramblers. We show that these devices generate distributions of the maximum change of the SOP (in a given sample time) that follow Rayleigh statistics, which scale linearly with scrambling frequency and the sample time. We use this procedure to measure the SOP fluctuations in a short length of coiled fiber subject to mechanical perturbations.     

Study of the effect of BDMA catalyst in the epoxy novolac curing process by isothermal DSC

Epoxy novolac/anhydride cure kinetics has been studied by differential scanning calorimetry under isothermal conditions. The system used in this study was an epoxy novolac resin (DEN431), with nadic methyl anhydride as hardener and benzyldimethylamine as accelerator. Kinetic parameters including the reaction order, activation energy and kinetic rate constants, were investigated. The cure reaction was described with the catalyst concentration, and a normalized kinetic model developed for it. It is shown that the cure reaction is dependent on the cure temperature and catalyst concentration, and that it proceeds through an autocatalytic kinetic mechanism. The curing kinetic constants and the cure activation energies were obtained using the Arrhenius kinetic model. A suggested kinetic model with a diffusion term was successfully used to describe and predict the cure kinetics of epoxy novolac resin compositions as a function of the catalyst content and temperature. Copyright © 2003 Society of Chemical Industry     

Oligo(ethylene oxide) side‐chain steric screening effects on conductimetric properties of grafted poly(4‐vinylpyridinium) salts in aqueous solutions

A set of poly[N‐oligo(ethylene oxide)yl 4‐vinylpyridinium tosylate] (P4VOEOOTs) has been prepared by spontaneous polymerization of 4‐vinylpyridine. This method gives a grafted polyelectrolyte having a positive charge on every backbone pyridinic moiety. The P4VP15Ts, P4VP164Ts, P4VP350Ts and P4VP750Ts aqueous solution conductivities were determined in the concentration range from 6 × 10^?4 to 10^?2 M at 25 °C. The variation of the conductivity versus concentration of the investigated system exhibits typical polyelectrolyte behaviour. The polyelectrolyte mobility was found to be dependent on the oligo(ethylene oxide) (OEO) side‐chain length. Manning's rod‐like model fails to describe these results. A simple steric effect is proposed to explain the influence of the OEO length. Copyright © 2003 Society of Chemical Industry     

Flow Reaction Forces upon Blowdown of Safety Valves

The activation of safety valves causes the development of flow reaction forces that have to be transferred in an adequate way via the piping to the steel structure or via the connected vessel into the foundation. If the safety valve outlet piping is connected to a blowdown system or, in case of blowing off into the atmosphere, are equipped with a T‐piece at the outlet, the stationary reaction forces are compensated completely. The transient opening process, however, develops flow reaction forces which culminate in peaks of short duration. In this article, a simple method will be proposed for the estimation of the resulting reaction forces as a function of the length of the pipe at the safety valve outlet. CFD calculations and blowdown tests executed with a full‐lift safety valve have confirmed this method on principle. Special importance is attributed to the short duration of the effect of the reaction forces which seems to have only a negligible impact on the supporting steel structure.