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.     

Studies on miscibility of blends of ethylene methyl acrylate and polydimethyl siloxane rubber

Blends of ethylene methyl acrylate (EMA) and poly(dimethylsiloxane) rubber (PDMS) are demonstrated to be miscible. The miscibility results in a single and composition-dependent glass transition temperature. IR spectra of the blends provide direct evidence of chemical reaction between EMA and PDMS rubber.     

Ammonia Decomposition on Ir(100): From Ultrahigh Vacuum to Elevated Pressures

Ammonia decomposition on Ir(100) has been studied over the pressure range from ultrahigh vacuum to 1.5 Torr and at temperatures ranging from 200 to 800 K. The kinetics of the ammonia decomposition reaction was monitored by total pressure change. The apparent activation energy obtained in this study (84 kJ/mol) is in excellent agreement with our previous studies using supported Ir catalysts (Ir/Al₂O₃ 82 kJ/mol). Partial pressure dependence studies of the reaction rate yielded a positive order (0.9±0.1) with respect to ammonia and negative order (–0.7 ±0.1) with respect to hydrogen. Temperature-programmed desorption data from clean and hydrogen co-adsorbed Ir(100) surfaces indicate that ammonia undergoes facile decomposition on both these surfaces. Recombinative desorption of N₂ is the rate-determining step with a desorption activation energy of 63 kJ/mol. Co-adsorption data also indicate that the observed negative order with respect to hydrogen pressure is due to enhancement of the reverse reaction (NH _x + H NH _x+1, x=0–2) in the presence of excess H atoms on the surface.     

Propagation of correlations in local random quantum circuits

We derive a dynamical bound on the propagation of correlations in local random quantum circuits—lattice spin systems where piecewise quantum operations—in space and time—occur with classical probabilities. Correlations are quantified by the Frobenius norm of the commutator of two positive operators acting on disjoint regions of a one-dimensional circular chain of length L. For a time \(t=O(L)\), correlations spread ballistically to spatial distances \(\mathcal {D}=t\), growing at best, diffusively with time for any distance within that radius with extensively suppressed distance- dependent corrections. For \(t=\varOmega (L^2)\), all parts of the system get almost equally correlated with exponentially suppressed distance- dependent corrections and approach the maximum amount of correlations that may be established asymptotically.     

Interdiffusion in the Fe-Pt System

Diffusion-couple experiments are conducted in the Fe-Pt system. The phase boundary compositions of the phases measured in this study are found to be different than the compositions published previously. In the γ-FePt solid solution, the interdiffusion coefficient increases with the Pt content up to 25 at. pct Pt. Fe is the faster diffusing species in this phase. The trend in the interdiffusion coefficient is explained with the help of calculated driving force for diffusion. To reduce errors, the average interdiffusion coefficients are calculated in the FePt and FePt₃ compounds.     

Development of topical gel containing aceclofenac-crospovidone solid dispersion by “Quality by Design (QbD)” approach

This article describes the development, optimization, and evaluation of Carbopol 940 topical gel containing aceclofenac-crospovidone (1:4) solid dispersion using “Quality by Design (QbD)” approach based on 2³ factorial design. The effect of crospovidone, tri-ethanolamine, and ethyl alcohol amount on the drug permeation profile of the topical gel containing aceclofenac-crospovidone solid dispersion was optimized by 2³ factorial design. The optimized gel showed improved permeation profile with cumulative drug permeation of 26.262 ± 2.157%, and permeation flux of 0.059 ± 0.011 μg/cm²/h. These gels were characterized by pH, viscosity, gel strength and FTIR study. The in vivo anti-inflammatory activity of the optimized gel was evaluated in rats using carrageenan-induced rat-paw oedema model and found excellent anti-inflammatory comparable with a marketed gel without producing any skin irritation.     

Ultra‐selective epoxidation of styrene on pure Cu{111} and the effects of Cs promotion

Styrene undergoes efficient epoxidation to styrene epoxide on the Cu{111} surface. At the optimum condition (Θ_o = 0.03 ML) ∼20% of the styrene is converted to the epoxide with almost 100% selectivity. Comparison with Ag{111} shows that the epoxidation activity and selectivity of Cu greatly exceed those of Ag. Incipient oxidation of the Cu{111} surface does not suppress the adsorption of styrene, but the oxidised metal is catalytically inert. Submonolayer amounts of Cs enhance styrene uptake and increase conversion to the epoxide without adversely affecting epoxidation selectivity. This effect is due to inhibition of Cu oxidation by Cs. Our findings are discussed in the light of current understanding of Ag‐catalysed alkene epoxidation. This revised version was published online in July 2006 with corrections to the Cover Date.     

Ultra-high temperature (>300 °C) suspended thermodiode in SOI CMOS technology

This paper reports for the first time on the performance and long-term stability of a silicon on insulator (SOI) thermodiode with tungsten metallization, suspended on a dielectric membrane, at temperatures beyond 300 °C. The thermodiode has been designed and fabricated with minute saturation currents (due to both small size and the use of SOI technology) to allow an ultra-high temperature range and minimal non-linearity. It was found that the thermodiode forward voltage drop versus temperature plot remains linear up to 500 °C, with a non-linearity error of less than 7%. Extensive experimental results on performance of the thermodiode that was fabricated using a Complementary Metal Oxide Semiconductor (CMOS) SOI process are presented. These results are backed up by infrared measurements and a range of 2-D (dimension) and 3-D simulations using ISE and ANSYS software. The on-chip drive electronics for the thermodiode and the micro-heater, as well as the sensor transducing circuit were placed adjacent to the membrane. We demonstrate that the thermodiode is considerably more reliable in long-term direct current operation at high temperatures when compared to the more classical resistive temperature detectors (RTDs) using CMOS metallization layers (tungsten or aluminum). We also compare a membrane thermodiode with a reference thermodiode placed on the silicon substrate and assess their relative performance at elevated temperatures. The experimental results from this comparison confirm that the thermodiode suffers minimal piezo-junction/piezo-resistive effects.     

Fault estimation and tolerant control for discrete‐time switched systems with sojourn probabilities

This paper addresses the issue of fault estimation and accommodation for a discrete‐time switched system with actuator faults. Here, we assume that the sojourn probabilities are known a priori. By using the reduced‐order observer method, the sojourn probability approach, and the Lyapunov technique, a fault estimation algorithm is obtained for the considered system. The main objective of this work is to design a dynamic output feedback fault‐tolerant controller based on the obtained fault estimation information such that the closed‐loop discrete‐time switched system with available sojourn probabilities is robustly mean‐square stable and satisfies a prescribed mixed and passivity disturbance attenuation level in the presence of actuator faults. More precisely, a dynamic output feedback fault‐tolerant controller is established in terms of linear matrix inequalities. Finally, numerical examples are provided to illustrate the usefulness and effectiveness of the proposed design technique.