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     

Steric requirements for coal swelling by amine bases

A set of six coals ranging in rank from lignite to hvA bituminous was swollen with a series of alkyl-substituted pyridines and a smaller set of 4-alkylanilines. The size and branching of the alkyl groups was varied and the effect of this variation on the dissolution of the amines in the coal and the resulting coal swelling was measured volumetrically. In a few cases, substituents which hindered the amine nitrogen were studied. The lignite and subbituminous coal have a much higher tolerance to branched, bulky groups than do the bituminous coals. The presence of tertiary groups in a solute strongly inhibits their dissolution in bituminous coals. Bituminous coals behave as if extensive parallel packing of structures occurs. Often, they can accept very large planar groups but have a low capacity for branched groups.     

Application of a multi-channel system for continuous monitoring and an early warning system.

A multi-channel continuous toxicity monitoring system developed in our laboratory, based on two-stage mini-bioreactors, was successfully implemented in the form of computer-based data acquisition. The multi-channel system consists of a series of a two-stage minibioreactor systems connected by a fiber optic probe to a luminometer, and uses genetically engineered bioluminescent bacteria for the detection of the potential toxicity from the soluble chemicals. This system can be stably and continuously operated due to the separation of the culture reactor from the test reactor and accomplish easy and long-term monitoring without system shut down by abrupt inflows of severe polluting chemicals. Four different recombinant bioluminescent bacteria were used in different channels so that the modes of the samples toxicities can be reasonably identified and evaluated based upon the response signature of each channel. The bioluminescent signatures were delivered from four channels by switching one at once, while the data is automatically logged to an IBM compatible computer. We also achieved the enhancement of the system through the manipulation of the dilution rate and the use of thermo-lux fusion strains. Finally, this system is now being implemented to a drinking water reservoir and river for remote sensing as an early warning system.     

Effect of grain boundaries on isothermal solidification during transient liquid phase brazing

The influence of liquid penetration at grain boundary regions on the rate of advance of the solid-liquid interface during isothermal solidification of transient liquid phase (TLP) brazed nickel joints has been examined. The test samples used in this study were Ohno-cast nickel with a grain size of >4 mm and a fine-grained nickel with a grain size of around 40 μm. Both Ni-base materials had the same chemical composition. The rate of isothermal solidification was greater when fine-grained nickel was employed during TLP brazing using Ni-11 wt pct P filler metal at 1200 °C. Liquid penetration at grain boundaries accelerates the isothermal solidification process by increasing the effective solid-liquid interfacial area and increasing the rate of solute diffusion into the base material. An analysis of electron channeling patterns has confirmed that random high-angle boundaries have a greater influence on the rate of isothermal solidification than ordered boundaries including small-angle or twin boundaries. Formerly Visiting Scientist, Department of Metallurgy and Materials Science, University of Toronto. Formerly Postdoctoral Fellow, Department of Metallurgy and Materials Science, University of Toronto     

Direct adaptive control of nonminimum phase systems using integralaction

A direct adaptive control scheme is proposed for nonminimum-phase systems in which controller parameters are estimated from the recursive least-squares algorithm and additional auxiliary parameters are obtained from the proposed polynomial identity. A local convergence is guaranteed without any extra condition. Integral action is incorporated into the adaptive controller to eliminate the steady-state error and to satisfy a condition of the unique solution for the polynomial identity. The control law used in this scheme is based on the set-point-on-I-only proportional-integral-derivative (PID) structure     

Expressive Facial Gestures From Motion Capture Data

Human facial gestures often exhibit such natural stochastic variations as how often the eyes blink, how often the eyebrows and the nose twitch, and how the head moves while speaking. The stochastic movements of facial features are key ingredients for generating convincing facial expressions. Although such small variations have been simulated using noise functions in many graphics applications, modulating noise functions to match natural variations induced from the affective states and the personality of characters is difficult and not intuitive. We present a technique for generating subtle expressive facial gestures (facial expressions and head motion) semi‐automatically from motion capture data. Our approach is based on Markov random fields that are simulated in two levels. In the lower level, the coordinated movements of facial features are captured, parameterized, and transferred to synthetic faces using basis shapes. The upper level represents independent stochastic behavior of facial features. The experimental results show that our system generates expressive facial gestures synchronized with input speech.     

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.     

Effects of surfactant/silica and silica/cerium ratios on the characteristics of mesoporous Ce-MCM-41

Using the surfactant CTMABr (cetyltrimethyl ammonium bromide) and cerium(IV) sulfate, mesoporous Ce-MCM-41 molecular sieves were produced under a hydrothermal condition with various surfactant/silica (surfactant/Si) and silica/cerium (Si/Ce) ratios. Changes to the structural traits caused by changing the molar ratios of both surfactant/Si and Si/Ce were investigated. XRD (X-ray diffraction), FT-IR (fourier transform infrared spectroscopy), and SEM (scanning electro microscopy) were used for the characterization of prepared mesoporous samples. Among the tested molar ratios, surfactant/Si ratio of 0.5 and 0.2 showed highest values of d_1 0 0 and intensity, respectively, for the Si-MCM-41. XRD analysis also identified a quintessential hexagonal structure of Ce-MCM-41 for the Si/Ce molar ratio higher than 40 (maintaining the surfactant/Si ratio at 0.2). When cerium content was increased to have the Si/Ce molar ratio of 20, the hexagonal structure of Ce-MCM-41 was collapsed due to the structural stress of substituted cerium. FT-IR results confirmed calcination of Ce-MCM-41 and the incorporation of Ce⁴⁺ ions of cerium sulfate into the silica surface with proper removal of the surfactant. Rod-like shape with rounded edges of the prepared Ce-MCM-41 samples was identified by SEM. These results suggest surfactant/Si ratio of 0.2 and Si/Ce ratio of 40 for the production of Ce-MCM-41 with the highest level of crystallinity.     

The relationship between photo-catalytic performance and optical property over Si-incorporated TiO2

This study focuses on the relationship between photo-catalytic performance and optical property over Si-incorporated TiO₂. The Si-incorporated TiO₂ particles exhibited a pure structure of anatase having a particle size of less than 20 nm and surface area of more than 190 m²/g. The absorbance did not shift to a higher wavelength in spite of the incorporation of the Si ions, but the intensity of the photoluminescence (PL) curve was the smallest in the case of the 2.0 mol% Si-TiO₂, which was related to the recombination between the excited electrons and holes. Based on these results, the photodecomposition of methyl orange in the liquid reaction was enhanced over the 2.0 mol% Si-incorporated TiO₂ compared with that over pure TiO₂: Methyl orange at 10.0 ppm was completely decomposed after 100 min when 1.0 g of the 2.0 mol% Si-incorporated TiO₂ was used.