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.     

Optimal Control of the Primary Drying Stage of Freeze Drying of Solutions in Vials Using Variational Calculus

The problem of operating freeze drying of pharmaceutical products in vials placed in trays of a freeze dryer to remove free water (in frozen state) at a minimum time was formulated as an optimal control problem. Two different types of freeze dryer designs were considered. In type I freeze dryer design, upper and lower plate temperatures were controlled together, while in type II freeze dryer design, upper and lower plate temperatures were controlled independently. The heat input to the material being dried and the drying chamber pressure were considered as control variables. Constraints were placed on the system state variables by the melting and scorch temperatures during primary drying stage. Necessary conditions of optimality for the primary drying stage of freeze drying process in vials are derived and presented. Furthermore, an approach for constructing the optimal control policies that would minimize the drying time for the primary drying stage was given. In order to analyze optimal control policy for the primary drying stage of the freeze-drying process in vials, a rigorous multi-dimensional unsteady state mathematical model was used. The theoretical approach presented in this work was applied in the freeze drying of skim milk. Significant reductions in the drying times of primary drying stage of freeze drying process in vials were obtained, as compared to the drying times obtained from conventional operational policies.     

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.     

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.     

Network topology and the theory of rubber elasticity

The earliest investigations on rubber elasticity, commencing in the 19th century, were necessarily limited to phenomenological interpretations. The realisation that polymers consist of very long molecular chains. commencing c. 1930, gave impetus to the molecular theory of rubber elasticity (1932-). according to which the high deformability of an elastomer, and the elastic force generated by deformation, stem from the configurations accessible to long molecular chains. Theories of rubber elasticity put forward from 1934-1946 relied on the assumption that the junctions of the rubber network undergo displacements that are affine in macroscopic strain. The theory of James and Guth (1947) dispensed with this premise, and demonstrated instead that the mean positions of the junctions of a ‘phantom’ network consisting of Gaussian chains devoid of material properties are affine in the strain. The vital significance of the distinction between the actual distribution of chain vectors in a network and their distribution if the junctions would be fixed at their mean positions went unnoticed for nearly 30 years. Experimental investigations, commencing with the incisive work of Gee in 1946. revealed large departures from the relationship of stress to strain predicted by the theories cited. This discrepancy prompted extensive studies, theoretical and experimental, during succeeding years. Inquiry into the fundamentals of polymer networks, formed for example by interlinking very long polymer molecules, exposed the need to take account of network imperfections, typically consisting of chains attached at only one end to a network junction. Various means were advocated to make corrections for these imperfections. The cycle rank ζ of the network has been shown (1976) to be the fundamental measure of its connectivity, regardless of the junction functionality and pattern of imperfections. Often overlooked is the copious interpenetration of the chains comprising typical elastomeric networks. Theories that attempt to represent such networks on a lattice are incompatible with this universal feature. Moreover, the dense interpenetration of chains may limit the ability of junctions in real networks to accommodate the fluctuations envisaged in the theory of phantom networks. It was suggested in 1975 that departures from the form predicted for the elastic equation of state are due to constraints on the fluctuations of junctions whose effect diminishes with deformation and with dilation. Formulation of a self-consistent theory based on this suggestion required recognition of the non-affine connection between the chain vector distribution function and the macroscopic strain in a real network, which may partake of characteristics of a phantom network in some degree. Implementation of the idea was achieved through postulation of domains of constraint affecting the equilibrium distribution of fluctuations of network junctions from their mean positions. This led in due course to a theory that accounts for the relationship of stress to strain virtually throughout the ranges of strain accessible to measurement. The theory establishes connections between structure and elastic properties. This is achieved with utmost frugality in arbitrary parameters.     

Breakdown characteristics of oil and paper insulation for a very fast transient voltage

This paper describes the dielectric breakdown characteristics of oil and oil‐impregnated paper for very fast transient (VFT) voltages. Blumlein circuits generate VFT voltages of 60 and 300 ns in a pulse width that simulates disconnecting switching surges in gas‐insulated switch gears. We measured the breakdown voltages of needle‐to‐plane, plane‐to‐plane oil gaps and several pieces of paper between plane electrodes for VFT and lightning impulse voltages. The measured data were formulated in V‐t characteristics and Weibull probability distributions. The inclination n of V‐t characteristics of insulating paper is 150, which is less than n = 13.7 of the plane‐to‐plane oil gap in the VFT time range. The shape parameters of Weibull distribution obtained in this study show that the scattering of breakdown voltages of paper is much less than that of oil. © 2002 Wiley Periodicals, Inc. Electr Eng Jpn, 141(4): 16–24, 2002; Published online in Wiley InterScience ( www.interscience.wiley.com ). DOI 10.1002/eej.10043     

Specification methods for material-handling control algorithms in flexible manufacturing systems

Good methods are needed to specify, test, and debug material-handling control logic. This article surveys a number of representative methods for defining and describing control algorithms for programmable material-handling equipment used in flexible manufacturing systems. The methods are evaluated with regard to their suitability for communication between people and as bases for interfaces to automatic program generators. It is concluded that no single method is entirely satisfactory. Three methods (position diagrams, function block diagrams, and operation networks) have potential to be combined into an effective hybrid approach that minimizes the need for the user to switch between various conceptual models.     

Facile modifications of polyimide via chloromethylation: II. Synthesis and characterization of thermocurable transparent polyimide having methylene acrylate side groups

From chloromethylated polyimide, a useful starting material for modification of aromatic polyimides, a thermocurable transparent polyimide having acrylate side groups was prepared. In the presence of 1,8‐diazabicyclo[5,4,0]undec‐7‐ene, chloromethylated polyimide was esterified with acrylic acid to synthesize poly(imide methylene acrylate). The polymer was soluble in organic solvent, which makes it possible to prepare a planar film by spin coating. The polymer film became insoluble after thermal treatment at 230 °C for 30 min. Optical transparency of the film at 400 nm (for 1 µm thickness) was higher than 98 % and not affected by further heating at 230 °C for 250 min. Adhesion properties measured by the ASTM D3359‐B method ranged from 4B to 5B. Preliminary results of planarization testing showed a high degree of planarization (DOP) value (>0.53). These properties demonstrate that poly(imide methylene acrylate) could be utilized as a thermocurable transparent material in fabricating display devices such as TFT‐LCD. Copyright © 2004 Society of Chemical Industry