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.     

Optically preamplified receiver performance due to VSB filtering for 40-Gb/s optical signals modulated with various formats

Optically preamplified receiver performance according to the vestigial sideband (VSB) filtering has been numerically investigated for 40-Gb/s optical signals modulated with nonreturn-to-zero, duobinary nonreturn-to-zero (NRZ), return-to-zero (RZ), carrier-suppressed RZ, and duobinary carrier-suppressed RZ formats. The VSB filtering enables the spectral widths of NRZ, duobinary NRZ, and RZ signals to be reduced without severe power penalties at the receiver. On the other hand, carrier-suppressed RZ and duobinary carrier-suppressed RZ signals have no large advantages over VSB filtering because of the characteristics of their signals. Our results suggest that RZ signals are the most suitable modulation format for VSB filtering, without considering the filter loss, because of the tolerance of the intersymbol interference and a large spectral width. However, duobinary NRZ signals are the most suitable modulation format for VSB filtering, considering the filter loss, because of their narrow spectral width.     

NO emission characteristics in counterflow diffusion flame of blended fuel of H2/CO2/Ar

Flame structure and NO emission characteristics in counterflow diffusion flame of blended fuel of H₂/CO₂/Ar have been numerically simulated with detailed chemistry. The combination of H₂, CO₂ and Ar as fuel is selected to clearly display the contribution of hydrocarbon products to flame structure and NO emission characteristics due to the breakdown of CO₂. A radiative heat loss term is involved to correctly describe the flame dynamics especially at low strain rates. The detailed chemistry adopts the reaction mechanism of GRI 2.11, which consists of 49 species and 279 elementary reactions. All mechanisms including thermal, NO₂, N₂O and Fenimore are taken into account to separately evaluate the effects of CO₂ addition on NO emission characteristics. The increase of added CO₂ quantity causes flame temperature to fall since at high strain rates a diluent effect is prevailing and at low strain rates the breakdown of CO₂ produces relatively populous hydrocarbon products and thus the existence of hydrocarbon products inhibits chain branching. It is also found that the contribution of NO production by N₂O and NO₂ mechanisms are negligible and that thermal mechanism is concentrated on only the reaction zone. As strain rate and CO₂ quantity increase, NO production is remarkably augmented. Copyright © 2002 John Wiley & Sons, Ltd.     

An EM‐based adaptive multiple target tracking filter

Tracking targets of interest is one of the major research areas in radar surveillance systems. We formulate the problem as incomplete data estimation and apply EM to the MAP estimate. The resulting filter has a recursive structure analogous to the Kalman filter. The advantage is that the measurement‐update deals with multiple measurements in parallel and the parameter‐update estimates the system parameters on the fly. Experiments tracking separate targets in parallel show that tracking maintenance ratio of the proposed system is better than that of NNF and RMS position error is smaller than that of PDAF. Also, the system parameters are correctly obtained even from incorrect initial values. Copyright © 2001 John Wiley & Sons, Ltd.     

A 0.9 V 92 dB Double-Sampled Switched-RC Delta-Sigma Audio ADC

A 0.9 V third-order double-sampled delta-sigma audio ADC is presented. A new method using a combination of a switched-RC technique and a floating switched-capacitor double-sampling configuration enabled low-voltage operation without clock boosting or bootstrapping. A three-level quantizer with simple dynamic element matching was used to improve linearity. The prototype IC implemented in a 0.13 CMOS process achieves 92 dB DR, 91 dB SNR and 89 dB SNDR in a 24 kHz audio signal bandwidth, while consuming 1.5 mW from a 0.9 V supply. The prototype operates from 0.65 V to 1.5 V supply with minimal performance degradation.     

Properties of nanoporous organosilicate hybrid thin films with a bimodal pore size distribution

Low dielectric poly[methylsilsesquioxane‐ran‐trifluoropropylsilsesquioxane‐ran‐(2,4,6,8‐tetramethyl‐2,4,6,8‐tetraethylenecyclotetrasiloxane)silsesquioxane]s {P[M‐ran‐TFP‐ran‐(TCS)]SSQs} having various compositions were synthesized using trifluoropropyl trimethoxysilane, methyl trimethoxysilane and 2,4,6,8‐tetramethyl‐2,4,6,8‐tetra(trimethoxysilylethyl)cyclotetrasiloxane. The chemical composition of the polymers and the content of SiOH end‐groups were controlled by adjusting the reaction conditions, and they were characterized by ¹H‐NMR. The thermally decomposable trifluoropropyl groups on the P[M‐ran‐TFP‐ran‐(TCS)]SSQ backbone and heptakis(2,3,6‐tri‐O‐methyl)‐β‐cyclodextrin (CD) were employed as pore generators. The dielectric constants of the porous CD/P[M‐ran‐TFP‐ran‐(TCS)]SSQ films were in the range 2.0–2.7 (at 100 kHz) depending on the concentration of the porogens, and showed no change over 4 days under aqueous conditions. The pore size of the films showed a bimodal distribution, with diameters of ca 0.5–1.0 nm for those originating from the trifluoropropyl groups and 1.7 nm from the CD. The elastic modulus and hardness of the 30 vol% CD‐blended film with a dielectric constant of 2.26 were 2.40 and 0.38 GPa, respectively, as determined by a nanoindenter. Copyright © 2005 Society of Chemical Industry     

Slow eroding biodegradable multiblock poloxamer copolymers

Biodegradable multiblock poloxamers (BMPs) with gel duration of 8 h to several weeks were prepared by varying their molecular weights from 4000 to 40 000 g mol^?1. The molecular weight of the BMP was controlled by changing the poloxamer to coupling agent ratio. Assuming a micelle packing model of the BMP gel, as in the case of a poloxamer gel, the micelle properties and critical gel concentration of BMPs were investigated on the basis of the scaling concept. The findings suggest that the control of molecular weight by hydrolyzable groups can be a facile approach to optimize the gel properties for biomedical applications. Copyright © 2005 Society of Chemical Industry     

Synthesis and characterization of an interpenetrating polymer network composed of poly(methacrylic acid) and poly(vinyl alcohol)

Temperature and pH‐responsive interpenetrating polymer network (IPN) hydrogels, constructed with poly(methacrylic acid) (PMAA) and poly(vinyl alcohol) (PVA), by a sequential IPN method, were studied. The characterization of IPN hydrogels was investigated by Fourier‐transform infrared spectroscopy, differential scanning calorimetry (DSC) and swelling under various conditions. The IPN hydrogels exhibited relatively high swelling ratios, in the range 230–380 %, at 25 °C. The swelling ratios of the PMAA/PVA IPN hydrogels were pH and temperature dependent. DSC was used for the quantitative determination of the amounts of freezing and non‐freezing water. The amount of free water increased with increasing PMAA content in the IPN hydrogels. Copyright © 2004 Society of Chemical Industry     

High performance biofilm process for treating wastewater discharged from coal refining plants containing nitrogen, cyanide and thiocyanate.

Wastewater discharge from coal refining plants contains a number of biologically toxic compounds; 2000-2500 mg/l of COD of which 40% is composed of phenol, 100-400 mg/l of thiocyanate, 10-40 mg/l of cyanide, 100-250 mg/l of NH4+-N and 150-300 mg/l of total nitrogen. In order to treat this kind of high strength wastewater, we have developed a high performance biofilm process using fluidizing bio-carriers of the tube chip type. The fluidizing biofilm carriers are made of a composite of polyethylene and several inorganic materials, whose density is controlled at 0.97-0.98 g/ml. The fluidizing biofilm carriers show sound fluidization characteristics inside bioreactors. The wastewater is treated using three consecutive series reactors in oxic-anoxic-oxic arrangement. Each reactor is charged with the fluidizing biofilm carriers of 50 vol%. Furthermore, newly cultured active microorganisms for the thiocyanate biodegradation are added in the biofilm process. At total hydraulic retention time of 2.2 days, this process can achieve steady state removal efficiencies: COD, 99%; thiocyanate, 99%; NH4+-N, 99% and total nitrogen, 90%.     

Production and structural features of a water-soluble polysaccharide from a mutant strain of Agrobacterium sp.

We have developed a mutant strain derived from Agrobacterium sp. ATCC 31750, which produces a water-soluble polysaccharide having potential utility to the food, feed, pharmaceutical and cosmetic industries. A high concentration of product (15 g/L) is obtained by 48 h cultivation of the mutant strain under optimized fermentation conditions. The water-soluble polysaccharide obtained from cultures of the mutant strain beta82 has Glc:Man:Gal in approximate molar ratios of 5.8:6.7:1.0. The molecular weight of the polysaccharide was determined to be approximately 1000 kDa by HPSEC analysis. Linkage analysis contained 3-Glcp, 3-Manp, terminal Glcp and terminal Manp, as well as a small proportion of 3- and 3,4-Galp, and 4,6-Manp residues. Based on analyses using FT-IR and ¹³C NMR spectrometers, most glycosidic bonds joining these sugar residues are of the α-type, and acetyl groups are apparently attached to the polymer chain at random.