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.     

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.     

Co-digestion of manure and biowaste according to the EC animal by-products regulation and Finnish national regulations.

The objective of this study was to compare methane production and characteristics of digested material in anaerobic digestion concepts according to the Animal By-Products Regulation (ABP-Regulation) of the EC (hygienisation of biowaste for 1 hour at 70 degrees C, particle size < 12 mm) and Finnish national regulations (treatment temperature 55 degrees C, feeding interval 24 h, hydraulic retention time (HRT) 20 d, particle size < 40 mm) and with small variations in treatment methods for treating manure and biowaste. Moreover, the survival of three different salmonella bacteria in these processes was studied. Hygienisation of biowaste prior to digestion at 35 degrees C enhanced methane production by 14-18% compared to similar treatment without hygienisation. The differences in treatment temperature, HRT and hygienisation of biowaste prior to digestion did not significantly affect the characteristics of digested material. The concepts according to the ABP-Regulation and Finnish national regulations were effective in destroying salmonella bacteria to an undetectable level.     

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.     

Mass Transfer in a Flat Gas/Liquid Interface using non‐Newtonian Media

Gas/liquid mass transfer has been investigated using a stirred vessel gas/liquid contactor using non‐Newtonian media and carbon dioxide as absorbent and gas phase, respectively. The volumetric mass transfer coefficients at different operational variables have been determined. Non‐Newtonian media (liquid phase) were prepared as aqueous solutions of sodium carboxymethyl cellulose salt. The influence of the rheological properties, polymer concentration, stirring rate, and gas flow rate on mass transfer was studied for these liquid phases. Kinematic viscosity and density experimental data were used to calculate the average molecular weight corresponding to the polymer employed. The Ostwald model has been used to fit the rheological behavior of aqueous solutions of the polymer employed as absorbent phase. Reasonably good agreement was found between the predictions of the proposed models and the experimental data of mass transfer coefficients.