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.     

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.     

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.     

Effects of surface charge, micro-bubble size and particle size on removal efficiency of electro-flotation.

Flotation is a water treatment alternative to sedimentation, and uses small bubbles to remove low-density particles from potable water and wastewater. The effect of zeta potential, bubble size and particle size on removal efficiency of the electro-flotation process was investigated because previous model-simulations indicated that these attributes are critical for high collision efficiency between micro-bubbles and particles. Solutions containing Al3+ as the metal ion were subjected to various conditions. The zeta potentials of bubbles and particles were similar under identical conditions, and their charges were influenced by metal ion concentration and pH. Maximum removal efficiency was 98 and 12% in the presence and absence of flocculation, respectively. Removal efficiency was higher when particle size was similar to bubble size. These results agree with modelling simulations and indicate that collision efficiency is greater when the zeta potential of one is negative and that of the other is positive and when their sizes are similar.     

On the issue of trend and noise in the estimation of extreme rainfall properties.

Up until today extreme rainfall properties are frequently applied in sewer design guidelines. Uncertainty in the estimation of such properties will hence directly influence the dimensions of sewers, structures and pumps. In this paper the issue of potential trend and noise in the estimation is investigated for 6 rain series ranging from 19 to 55 years in duration. Different to recent research that predicts a climate induced-increase in heavy precipitation no clear indication for such trend was found in the investigated historical rain series. Another important aspect is the length of the rain series that is required for the estimation of extreme rainfall properties and the associated uncertainty. The analysis indicates that at least a period of 10 years should be used for the estimation. But even so the possible deviation expressed in terms of the 90 percentile is in the order of 5 to 10% of the 'true value', defined as the value derived when the whole given series is used for the estimation.     

Robust vector control of induction motors using full-order observer in consideration of core loss

This paper proposes a method for designing a robust full-order observer for vector-controlled induction motors taking core loss into account. Although conventional research focuses on parameter identification, global stability of the identification remains questionable. Therefore, robustness against some parameters is required. This paper describes the design of a robust full-order observer which takes core loss into account, using both the gain-scheduled H/sub /spl infin// control and the linear matrix inequality technique. This design always results in a stable controller. The robustness of the proposed method against variations of resistances is evaluated by experiments.     

Knowledge-based control and case-based diagnosis based upon empirical knowledge and fuzzy logic for the SBR plant.

Because biological wastewater treatment plants (WWTPs) involve a long time-delay and various disturbances, in general, skilled operators manually control the plant based on empirical knowledge. And operators usually diagnose the plant using similar cases experienced in the past. For the effective management of the plant, system automation has to be accomplished based upon operating recipes. This paper introduces automatic control and diagnosis based upon the operator's knowledge. Fuzzy logic was employed to design this knowledge-based controller because fuzzy logic can convert the linguistic information to rules. The controller can manage the influent and external carbon in considering the loading rate. The input of the controller is not the loading rate but the dissolved oxygen (DO) lag-time, which has a strong relation to the loading rate. This approach can replace an expensive sensor, which measures the loading rate and ammonia concentration in the reactor, with a cheaper DO sensor. The proposed controller can assure optimal operation and prevent the over-feeding problem. Case-based diagnosis was achieved by the analysis of profile patterns collected from the past. A new test profile was diagnosed by comparing it with template patterns containing normal and abnormal cases. The proposed control and diagnostic system will guarantee the effective and stable operation of WWTPs.     

Photocatalytic oxidation of low concentration 2,4-D solution with new TiO2 fiber catalyst in a continuous flow reactor.

Environmental pollution by low concentrations of 2,4-Dichlorophenoxyacetic acid (2,4-D) is a concern these days due to ever increasingly stringent regulations. Photocatalysis with immobilized TiO2 fiber is a promising oxidation method. Laboratory experiments on photocatalytic degradation of 0.045 mmol l(-1) 2,4-D with the world's first high-strength TiO2 fiber catalyst were carried out in a continuous flow reactor in which the degradations were, in general, similar to those with high 2,4-D concentrations investigated elsewhere. Degradation and mineralization of 2,4-D were significantly enhanced with no initial pH adjustments. The rate constants for total organic carbon (TOC) without pH adjustment were about two-fold bigger than the pH adjustment cases. CO2 gas measurement and carbon mass-balance were carried out for the first time, where about 34% organic carbon converted into CO2 gas during four-hour oxidation. 2,4-Dichlorophenol (2,4-DCP), phenol, benzyl alcohol and two unknowns (RT = 2.65 and 3.78 min.) were detected as aromatic intermediates while Phenol was the new aromatic in HPLC analysis. Dechlorination efficiencies were high (> 70%) in all the cases, and more than 90% efficiencies were observed in chloride mass balance. Bigger flow rates and solution temperature fixed at 20 degrees C without pH adjustment greatly enhanced 2,4-D mineralization. These results can be an important basis in applying the treatment method for dioxin-contaminated water and wastewater.