Preparation of stable polyurethane-polystyrene copolymer emulsions via RAFT polymerization process

Stable polyurethane-polystyrene (PU-PS) copolymer emulsions were prepared by the polymerization of 2-hydroxyethyl acrylate (HEA)-capped PU macromonomer and styrene, using azobis(isobutyronitrile) (AIBN), a radical initiator, and 4-((benzodithioyl)methyl)benzoic acid, a reversible addition-fragmentation chain transfer (RAFT) agent. As the molar ratio of the RAFT agent to AIBN increased, the zeta potential of the resulting copolymer emulsion increased, but the average size and size distribution of the emulsion droplets decreased. A living polymerization of HEA end-capped PU macromonomer and styrene was characterized by a linear increase in the molecular weight and decrease in the molecular weight distribution with consumption of monomers. The tensile strength, hardness and water-resistance of the copolymer films, prepared from the PU-PS copolymer emulsions, were much greater than those of the films prepared from the pure PU emulsion. The copolymer emulsions, prepared via the RAFT polymerization process, are expected to exhibit better storage stability than those prepared via the conventional free radical polymerization process, due to the presence of carboxyl groups derived from the RAFT agent at the PS block termini.     

Kinetics of cellobiose decomposition under subcritical and supercritical water in continuous flow system

The effects of reaction temperature, pressure and residence time were investigated with a flow apparatus. Cellobiose decomposition kinetics and products in suband supercritical water were examined at temperatures from 320 to 420 °C at pressures from 25 to 40 MPa, and at residence times within 3 sec. Cellobiose was found to decompose via hydrolysis and pyrolysis. The yield of desired hydrolysis product, glucose, was the maximum value of 36.8% at 320 °C, 35 MPa, but the amount of 5-(hydroxymethyl)furfural (HMF), fermentation inhibitor increased too because residence time increased in the subcritical region owing to decrease of reaction rate. Meanwhile, though the yield of glucose is low in the supercritical region, the yield of HMF decreased compared with the subcritical region; and at the minimum yield of HMF (380 °C, 25 MPa), the yield of glucose was 21.4%. The decomposition of cellobiose followed first-order kinetics and the activation energy for the decomposition of cellobiose was 51.05 kJ/mol at 40MPa.     

Electrochemical cell current requirements for toxic organic waste destruction in Ce(IV)-mediated electrochemical oxidation process

The electrochemical cell for cerium oxidation and reactor for organic destruction are the most important operation units for the successful working mediated electrochemical oxidation (MEO) process. In this study, electrochemical cells with DSA electrodes of two types, single stack and double stack connected in series, were used. The performances towards the electrochemical generation of Ce(IV) in nitric acid media at 80 °C were studied. The current-voltage curves and cerium electrolysis kinetics showed the dependence on number of cell stacks needed to be connected in series for the destruction of a given quantity of organic pollutant. The presence of an optimum region for Ce(III) oxidation with a contribution of oxygen evolution, especially at low Ce(III) concentration (high conversion ratios), was found. The cells were applied for the Ce(IV) regeneration during the organic destruction. The cell and reactor processes were fitted in a simple model proposed and used to calculate the current needed in terms of Ce(III) oxidation rate and the number of cell stacks required for maintaining Ce(IV)/Ce(III) ratio at the same level during the organic destruction. This consideration was based on the kinetic model previously developed by us for the organic destruction in the MEO process.     

Constraint release effects on the dynamics of polymer melts

The dynamical behavior of polymers with molecular weight distribution is analyzed from the standpoint of reptation and tube renewal. In a binary blend where the entanglements between longer chains are prominent, the shorter chain relaxes only by reptation, whereas the longer chain shows more complex behavior, i.e., reptation in the original tube, short-range tube renewal causing the tube enlargement, and thereafter reptation again in the expanded tube. Dynamic moduli data from literature are used for determining the compositional dependence of the relaxation times. Also on the basis of the relaxation mechanism considered here, the critical composition due to the onset of entanglements between different longer chains is proposed as a function of their component molecular weighl ratio.     

Control of the photorefractive effect using a low Tg sol-gel glass

Summary We prepared the photorefractive sol-gel glass based on organic-inorganic hybrid materials containing a charge transporting molecule, second-order nonlinear optical chromophore, photosensitizer, and plasticizer. Carbazole and 2-{ 4-[(2-hydroxyethyl) methylamino]benzylidene}malononitrile were reacted with 3-isocyanatopropyl triethoxysilane and the functionalized silanes were employed to fabricate the efficient photorefractive media including 2,4,7-trinitrofluorenone (TNF) to form a charge transfer complex. The simplest way to vary the composition in the matrix was to mix the desired amount of the functionalized alkoxysilane. The prepared sol-gel glass samples contained a large amount of nonlinear optical (NLO) chromophore compared to that of the charge transporting molecules. They showed a large net gain coefficient and high diffraction efficiency at certain conditions. Received:27 May 2002/Revised version:23 August 2002/Accepted:7 September 2002 Correspondence to Dong Hoon Choi E-mail: dhchoi@khu.ac.kr     

Effect of Twin-Plane Reentrant Edge on the Coarsening Behavior of Barium Titanate Grains

When BaTiO₃ ceramics were sintered at relatively low temperatures (≤1250°C), the grains with reentrant edges caused by a (111) double twin grew exclusively. As a result, a microstructure with a bimodal grain-size distribution composed of platelike large grains and fine matrix grains was obtained. In contrast, at the usual sintering temperature between 1250° and 1350°C, grains containing a (111) double twin did not exhibit any growth advantage. In this case, a coarse and uniform microstructure was obtained. When this coarse-grained specimen was further heat-treated at 1365°C, the grains possessing a double twin were observed to grow exclusively again. The results were explained in terms of a coarsening process controlled by two-dimensional nucleation.     

Rotational diffusion coefficient of rod-like polymer with a slight flexibility in semidilute and concentrated solutions

Summary A confined stiff chain model is suggested for the prediction of the rotational diffusion coefficient of a rigid rodlike polymer with a slight flexibility above the region of dilute solution (c1/L³). It shows a fairly good agreement with the experimental data of various polymers. Among them, PBLG and PBT with more rigidity are more consistent with the model when the log-jamming effect is considered. The predicted rotational diffusivity shows approximately the inverse seventh-power of length, which is less than 9 of Doi-Edwards tube model, but larger than the experimental value 5.7 of M-virus, while it shows the inverse power of concentration is a little larger than the value 2 of tube model except for the rodlike virus M-13.     

High-Resolution Electron Microscopy Observations of Stacking Faults in β-SiC

Structural images of the stacking faults in β-SiC were obtained with a high-resolution electron microscope. Stacking faults initially present in β-SiC powder particles were eliminated as grain growth proceeded at elevated temperatures.     

Enhanced surface morphologies of screen-printed carbon nanotube films by heat treatment and their field-emission properties

A heating process for obtaining free-standing carbon nanotube emitters is presented with the aim of improving field-emission properties from the screen-printed multiwalled carbon nanotube (MWCNT) films. Using an atmosphere with an optimum combination of nitrogen and air for heat treatment of CNT films, the CNT emitters can be made to protrude from the surface. This allows for a high emission current and the formation of very uniform emission sites without special surface treatment. The morphological change of the CNT film by this technique has eliminated additional processing steps, such as surface treatment which may result in secondary contamination and damage to the film. Despite its simplicity the process provides a high reproducibility in emission current density which makes the films suitable for practical applications.     

Preparation and characterization of eugenol‐grafted chitosan hydrogels and their antioxidant activities

The hydrogels composed of chitosan and eugenol were prepared to enhance and sustain antioxidant activities. The vinyl groups of eugenol monomer were directly grafted on the amino groups of chitosan, using ceric ammonium nitrate. The graft of eugenol onto chitosan was confirmed by using Fourier‐transform infrared and proton nuclear magnetic resonance spectroscopies. Results from the swelling behavior, thermal stability, and wide‐angle X‐ray diffraction revealed that the equilibrium water content decreased with increase of graft yields, because of the hydrophobicity of eugenol, although the introduction of eugenol as a side chain disturbed the ordered arrangement of chitosan's crystalline structure. The eugenol‐grafted chitosan hydrogels showed lower pH sensitivity in comparison with chitosan alone, because the amino groups, which were pH sensitive, of chitosan were grafted with eugenol. The scavenging activity of the tested hydrogels increased with graft yield of eugenol, because phenolic groups in the eugenol could play a major role as potent free‐radical terminators, in the results of improved antioxidant activity in eugenol‐grafted chitosan hydrogel in comparison with chitosan alone. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 99:3500–3506, 2006