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.     

Synthesis of heterocyclic metal complexes and their evaluation as marine antifoulants

4-Amino-3-thio-1,24-triazolidine (L₁) and 4-amino-5-thio-1,3,4-thiadiazole (L_II) as well as their metal complexes of the general formulae ML_I·2H₂O and ML_IICl (M; Pb(II), Cd(II) and Zn(II)) were prepared. With Sn(II), we obtained Sn(L_I)₂·2H₂O and SnL_IICl, respectively. The structures of the compounds were identified through elemental analysis, and IR and UV spectra measurements, in addition to thermal analysis in case of the metal complexes. The antifouling properties of the compounds were tested by their incorporation into paint formulations which were applied to PVC substrates and tested in water from Alexandria western harbour. When the compounds were added at 17·5% by volume, the coated panels were fouled after 3 months of immersion. The addition of 6·7% by volume of tributyltin oxide to 15·8% of the prepared compounds in one formulation elevated the paint efficiency and prevented fouling for 11 months. Paint containing solely tributyltin oxide at the same concentration was inactive against algae.     

A method of identifying latent human errors in work systems

Work system improvements are implemented in various manufacturing processes to prevent problems caused by human errors. However, they are almost always applied to problems which have already occurred. This paper examines a method of identifying latent human errors existing within the work systems beforehand. A procedure for applying failure mode and effect analysis to this identification problem was defined based on over 1000 empirical errors: a work system decomposition criterion and fundamental error modes for listing latent human errors, and then applied to three practical manufacturing processes in order to evaluate its effectiveness.     

Modeling of Diffusion in Capillary Porous Materials During the Drying Process

This paper presents a model of heterogenous diffusion in capillary porous materials during the process of drying. The governing heat and mass transfer equations have been established using the liquid as well as vapor flow. Two models have been presented. Model 1 does not consider the heat conduction while the model 2 has been established by considering the conduction. The developed models and the numerical solutions of the resulting differential equations can take into account the moisture and temperature dependent thermophysical properties of the product. All equations have been established in spherical coordinates but the programme written for the purpose of calculations can be used for other geometries also. Numerical calculations have been performed for gas concrete and tiles using model 1, while model 2 has been used for gas concrete only because of the lack of data for thermophysical properties of the tile. For gas concrete it was seen that conduction has only marginal effect on the drying process and the numerical predictions of the drying process were reasonably accurate.     

Polymer networks based on α,ω-methacrylate-terminated poly(1,3-dioxolane)

α,ω-Methacrylate-terminated poly(1,3-dioxolane)s (polyDXL) were synthesized by cationic ring-opening polymerization of DXL in the presence of methylene-bis(oxyethylmethacrylate) as transfer agent. If the initiator concentration is small compared with the transfer agent concentration, the molecular weights of the polymers are governed by the ratio of the reacted monomer to the reacted transfer agent. The α,ω-methacrylate-terminated polyDXLs obtained undergo free radical polymerization with formation of polyacetal networks. The properties of the networks as function of the molecular weight of the corresponding prepolymers are reported.     

A new monitoring system for piping systems in fossil fired power plants

A CEC-funded project has been performed to tackle the problem of producing an advanced Life Monitoring System (LMS) which would calculate the creep and fatigue damage experienced by high temperature pipework components. Four areas were identified where existing Life Monitoring System technology could be improved:

1. 1. the inclusion of creep relaxation

2. 2. the inclusion of external loads on components

3. 3. a more accurate method of calculating thermal stresses due to temperature transients

4. 4. the inclusion of high cycle fatigue terms.

The creep relaxation problem was solved using stress reduction factors in an analytical in-elastic stress calculation. The stress reduction factors were produced for a number of common geometries and materials by means of non-linear finite element analysis. External loads were catered for by producing influence coefficients from in-elastic analysis of the particular piping system and using them to calculate bending moments at critical positions on the pipework from load and displacement measurements made at the convenient points at the pipework. The thermal stress problem was solved by producing a completely new solution based on Green's Function and Fast Fourier transforms. This allowed the thermal stress in a complex component to be calculated from simple non-intrusive thermocouple measurements made on the outside of the component. The high-cycle fatigue problem was dealt with precalculating the fatigue damage associated with standard transients and adding this damage to cumulative total when a transient occurred.

The site testing provided good practical experience and showed up problems which would not otherwise have been detected.     

Effects of hydrolysis on the physical properties of short glass-fibre reinforced poly(ethylene terephthalate)

The mechanical fracture strength and toughness of short-fibre composites, injection moulded from compounds of poly(ethylene terephthalate) (PET) containing 10 and 30% (by weight) (w/o) glass, have been investigated and the dependence upon matrix hydrolytic stability determined. Mouldings have been characterised by several physical techniques to evaluate molecular weight, degradation rates, crystallinity and morphology, whilst time-dependent gravimetric data were derived to quantify sorption kinetics and allow comparisons with theoretical reaction rates to be made. During melt processing, PET is hydrolysed extremely rapidly by traces of moisture (<0.02w/o). yet the inherent strength of moulded composites declines significantly only below an apparently critical molecular weight. However, on long-term humid ageing in hot water, impact behaviour especially is rendered more complex by simultaneous crystallisation, molecular reorder and losses of interfacial bond strength.