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.     

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     

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.     

Catalytic aminolysis of epoxide by alumina prepared from amine-protected Al precursor

The catalytic activities of alumina prepared from an Al alkoxide-amine adduct monomer for the reaction of cyclopentene oxide with piperidine was determined after various pretreatments, including calcination and exposure to moisture. They were compared with the activity of alumina prepared by the conventional hydrolysis method. It was found that the as-prepared sample from the alkoxide-amine monomer preparation was five times more active than a conventional preparation, suggesting that it has a higher density of surface Lewis acid sites. However, its activity was much more severely suppressed by exposure to moisture.     

TEM Studies of High Temperature Corrosion Behaviour of TiAl Intermetallics with Surface Modifications

The oxidation/sulphidation behaviour of a Ti‐46.7Al‐1.9W‐0.5Si alloy with a TiAl₃ diffusion coating was studied in an environment of H₂/H₂S/H₂O at 850^oC. The kinetic results demonstrate that the TiAl₃ coating significantly increased the high temperature corrosion resistance of Ti‐46.7Al‐1.9W‐0.5Si. The SEM, EDX, XRD and TEM analysis reveals that the formation of an Al₂O₃ scale on the surface of the TiAl₃‐coated sample was responsible for the enhancement of the corroison resistance. The Ti‐46.7Al‐1.9W‐0.5Si alloy was also modified by Nb ion implantation. The Nb ion implanted and as received sampels were subjected to cyclic oxidation in an open air at 800^oC. The Nb ion implantation not only increased the oxidation resistance but also substantially improved the adhesion of scale to the substrate.     

Kinetic Characteristics of Amino Acid Salt Crystallization in Methanol‐Water System

Nucleation and growth mechanisms and kinetics of crystals of an amino acid salt were investigated in a methanol‐water system by measuring and evaluating the induction time as a function of the supersaturation ratio and temperature in batch salting out crystallization experiments. Discrimination between the possible crystallization mechanisms, and estimation of the kinetic parameters were carried out using nonlinear parameter identification. The results concerning the growth mechanism obtained were checked additionally by measuring the induction time as a function of number density of seed crystals.