Low‐temperature photoinitiation solution polymerization behavior of N‐vinylcarbazole in tetrahydrofuran

N‐Vinylcarbazole (VCZ) was solution‐polymerized in tetrahydrofuran (THF) at ?20, 0, and 20°C using the photoinitiation method; the effects of the amount of solvent, polymerization temperature, and photoinitiator concentration were investigated. On the whole, the experimental results corresponded to predicted ones. Low polymerization temperature using photoinitiation proved to be successful in obtaining poly(N‐vinylcarbazole) (PVCZ) of a high molecular weight with a smaller temperature rise during polymerization; nevertheless of free radical polymerization by 2,2′‐azobis(2,4‐dimethylvaleronitrile) (ADMVN). The photo‐solution polymerization rate of VCZ in THF was proportional to the 0.47 power of ADMVN concentration. The molecular weight was higher and the molecular weight distribution was narrower with PVCZ polymerized at lower temperatures. For PVCZ prepared in THF at ?20°C using a photoinitiator concentration of 0.00005 mol/mol of VCZ, a weight‐average molecular weight of 510,000 was obtained, with a polydispersity index of 1.73, and a degree of lightness converged to about 99%. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 3667–3672, 2002     

Numerical simulation of fixed-bed catalytic reactor for isopropyl alcohol synthesis

The mathematical model and the method of its numerical analysis for fixed-bed catalytic reactors were developed and were applied to the pilot reactor of isopropyl alcohol (IPA). The experimental results from pilot test runs were used to test and verify the simulation results. The numerical simulation gives the IPA concentration and temperature profiles in the reactor. The production of IPA from a commercialized ethanol rector was examined. The operation conditions of IPA synthesis were established.     

Migration of Intergranular Liquid Films and Formation of Core-Shell Grains in Sintered TiC–Ni Bonded to WC–Ni

When TiC–20 wt% Ni powder mixtures are sintered at 1400°C, relatively large TiC grains possibly containing some Ni form with near-equilibrium shapes. When these specimens are heat-treated again at 1400°C in contact with sintered WC–20 wt% Ni pieces, the liquid films between the TiC grains in the contact region migrate against their increasing curvatures, forming (Ti,W)C solid solution behind them. These migrating liquid films reverse their directions on further heat-treatment. As in other alloys, this liquid film migration must be driven by the coherency strain energy produced by W diffusion at the surface of the dissolving TiC grains. Shells of (Ti,W)C solid solution also form around the cores of TiC grains near the contact region, and this process is probably driven by both coherency strain energy and free energy of mixing. At some contact regions, (Ti,W)C precipitates nucleate and grow, probably driven mainly by the free energy of mixing. In powder mixtures, the formation of core-shell grains is expected to be driven by the coherency strain energy, the free energy of mixing, and the capillary effect.     

Polyurethane–poly(methyl methacrylate) block copolymer dispersions through polyurethane macroiniferters

Polyurethane macroiniferter/poly(methyl methacrylate) block copolymer dispersions with inverse core‐shell morphologies were obtained from 1,1,2,2,‐tetraphenylethane‐1,2‐diol, dimethylol propionic acid, 4,4′‐diphenylmethane diisocyanate, and poly(propylene glycol) via a living radical mechanism. Molecular weight, particle size and dispersion viscosity, and thermal, mechanical, and dynamic mechanical properties of the dispersion cast films are reported as a function of copolymerization time. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 1971–1975, 2003     

Effect of clinoptilolite addition and solids retention time on the extracellular polymeric substances composition and soluble chemical oxygen demands in activated sludge

This study was carried out to compare EPS (Extracellular Polymeric Substances) composition between conventional activated sludge (AS) and activated sludge dosed with clinoptilolite (CAS). Additionally, those were compared with organic removal efficiency in the effluent in conjunction with EPS concentrations. The experiments were conducted at SRT (Solids Retention Time) ranging from 5 to 100 d. For the CAS, proteins were more readily observed for SRT 20 and 100 d compared to that of the AS. Polysaccharide concentration in the sludge was greatly increased for the CAS, but it was significantly diminished when the SRT was extended. The level of EPS concentration observed from the effluent had the same pattern of variation for the two different types of systems. Regardless of type of reactor, the ratio of proteins for sludge versus effluent was independent of SRT, but the ratio of polysaccharides diminished as SRT increased. In the long run, the degree of protein synthesis directly ascribed to concurrent enhancement of SCOD removal efficiency was slightly more in the CAS. It was decided that clinoptilolite added system could be more reliably retrofitted to a conventional activated sludge process.     

Microwave Dielectric Properties of (1−x)(Na1/2Nd1/2)TiO3−xLa(Mg1/2Ti1/2)O3 via Ordering and Far IR Reflectivity Spectra

Microwave dielectric properties of (1− x )(Na_1/2Nd_1/2)TiO₃(NNT)− x La(Mg_1/2Ti_1/2)O₃(LMT) system have been investigated with focus on structural ordering and far IR reflectivity spectra. A single perovskite phase was found to exist with various superlattice reflections over the entire compositional range. 1:1 ordering observed in the (111) reflection of X-ray diffraction patterns was found to progress significantly in the specimens above x =0.8. The ordering characteristics that presumably related to B-site Mg/Ti ordering were assumed to affect favorably the quality factor at microwave frequencies. The increase of the quality factor also could be explained in terms of the decrease of lattice anharmonicity with LMT by analysis of far IR reflectivity spectra. As expected from the values of pure NNT and LMT, the dielectric constant and the temperature coefficient of frequency tended to gradually decrease with increasing LMT content.     

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.     

Development of modified stokes expression to model the behavior of expanded beds containing polydisperse resins for protein adsorption

Expanded bed behavior was modeled by using the Richardson-Zaki correlation between the superficial velocity of the feed stream and the void fraction of the bed. A polydisperse material, Chelating excellose® (70-210 Μm in diameter, 1.21 g/cm³ in density), which has Ni²⁺ ions for the selective binding of histidine-tagged proteins, was used as the resin. A method to modify the Stokes expression to express the terminal settling velocity of the resins by introducing two empirical parameters, the effective diameter of the resins and an exponent for(ρ _p -ρ)/Μ term, was developed. Combined use of the Richardson-Zaki correlation and the modified Stokes expression was successful in modeling the bed expansion by incorporating physical properties of feed streams and the resins.     

Catalytic characteristics of various rubber-reinforcing carbon blacks in decomposition of methane for hydrogen production

Carbon black has recently been reported to act as an effective catalyst for methane decomposition and to exhibit stable catalytic behavior despite carbon deposition, and thus it can be used for CO₂-free production of hydrogen from natural gas. In this work, various carbon blacks with different primary particle size were investigated with respect to methane decomposition under atmospheric pressure from 1123 to 1223 K. Catalytic characteristics, such as activity, activation energy and reaction order, were investigated and compared. It was observed that with decreasing primary particle size (or increasing specific surface area), the specific activity increased and the activation energy decreased. The reaction orders for various pelletized, rubber-reinforcing carbon blacks were 0.6–0.7, about the same regardless of the primary particle size, while they were near 1 for fluffy carbon blacks. Fluffy carbon black showed higher activity and activation energy than the pelletized carbon black of the same primary particle size. Changes of the surface morphology during carbon deposition were observed by TEM. Variations of the number of active sites were discussed in regard of the primary particle size, carbon deposition and binder. The presence of different types of active sites was also suggested.