Radiation-induced polymerization of ethylene in pilot plant. III. Heavy-phase recycling process

Radiation-induced polymerization of ethylene using aqueous tert-butyl alcohol as medium was carried out in a large-scale pilot plant with a 50-liter central source-type reactor at a pressure of 105 to 395 kg/cm², temperature of 30° to 80°C, mean dose rate of 4.5 × 10⁴ to 1.9 × 10⁵ rads/hr, ethylene feed rate of 5.5 to 23.5 kg/hr, and medium feed rate of 21 to 102 l./hr. The space–time yield and molecular weight of the polymer were in the range of 4.7 to 16.8 g/l.-hr and 1.3 × 10⁴ to 8.9 × 10⁴, respectively. The space–time yield and molecular weight increased with mean residence time at 30°C, whereas at 80°C they became almost independent of the time. The space–time yield increased with pressure and dose rate, slightly decreased with temperature, and was maximum at ethylene molar fraction of 0.5. The polymer molecular weight increased with pressure and ethylene molar fraction, and decreased with dose rate and temperature. The total amount of deposited polymer on the reactor wall, source case wall, and scraping blades was usually less than 1 kg, which was negligibly small for the analysis of polymerization. Continuous discharge of the polymer slurry and production of fine-powder polyethylene were successfully carried out. In the central source-type reactor, a dose rate of 1.9 × 10⁵ rads/hr was obtained with a ⁶⁰Co source of ca. 12 kCi.     

Control of molecular weight distribution of isotactic polypropylene obtained by a MgCl2-supported TiCl4 catalyst

It is of great importance in propene polymerization to control molecular weight and molecular weight distribution as well as isotacticity. Propene polymerization was carried out with an isospecific MgCl₂/TiCl₄-Cp₂TiMe₂ catalyst in the presence of various kinds of external Lewis bases. It was found that the molecular weight distribution of the isotactic polymer could be controlled while retaining high activity, high isospecificity and high molecular weight only by changing the kind and/or amount of the Lewis bases. © 1997 Elsevier Science Ltd.     

Reaction of sodium perborate with a chlorinated cyclic hindered amine (TMP-Cl): I. Quantitative evaluation of active oxygen species in fabric bleaching

The reaction of N-chloro-4-hydroxy-2,2,6,6-tetramethylpiperidine (TMP-Cl) with sodium perborate (PB) was investigated with special reference to the generation of singlet oxygen and the possible application to a new oxidative bleaching process. Generation of the singlet oxygen (¹O₂), the hydroxyl radical (HO·) and superoxide anion radical (O₂·⁻) in the PB/TMP-Cl mixed solution was confirmed by the trapping reagent method. From the results of another experiment, in which the bleaching abilities of each active oxygen species were confirmed, the main active oxygen species contributing to the bleaching of purpurogallin, the skeleton of black tea pigment, in the PB/TMP-Cl system was concluded to be¹O₂.     

Polymeric phosphonium salts as a novel class of cationic biocides. VII. Synthesis and antibacterial activity of polymeric phosphonium salts and their model compounds containing long alkyl chains

Various polymeric phosphonium salts containing long alkyl chains (C₁₀? C₁₈) and their corresponding model compounds were prepared, which possess the same hydrophobic structure as that of the common disinfectants (quaternary ammonium salts), and their antibacterial activities were evaluated by means of the viable cell counting method against Staphylococcus aureus (Gram-positive) and Escherichia coli (Gram-negative). The polymer with the decyl group exhibited a higher activity than that of the corresponding model compound, particularly against the Gram-positive strain. Furthermore, antibacterial activity of the polymers was found to decrease as the chain length increased. In contrast with the polymers, the antibacterial activity of the corresponding model compounds increased as hydrophobicity of the substituents increased. The antibacterial activity was strongly dependent on the structure, particularly on the length of the alkyl chain. © 1994 John Wiley & Sons, Inc.     

A model for the complex permittivity of water at frequencies below 1 THz

Experimental permittivity data of liquid water, compiled from the open literature, were selectively applied to support a modeling strategy. Frequencies up to 1 THz and atmospheric temperatures are covered with an expression made up by two relaxation (Debye) terms. The double-Debye model reduces to one term when the high frequency limit is set at 100 GHz, and the model can be extended to 30 THz by adding two resonance (Lorentzian) terms. The scheme was carried out by employing nonlinear least-squares fitting routines to data we considered reliable.     

Immobilization of multicopper oxidase from Pyrobaculum aerophilum onto an electrospun-aligned single-walled carbon nanotube surface via a carbon-nanotube-binding peptide for biocathode

Biofuel cells (BFCs) that produce electrical energy from organic resources through enzymatic reactions have been attracting significant attention. Owing to the high electrical conductivity of carbon nanotubes (CNTs), their modification on the electrode surface of a BFC is expected to increase the current, and their high specific surface area may be useful in increasing the power output. Previously, we constructed a biocathode by immobilizing multicopper oxidase from Pyrobaculum aerophilum (McoP) with a carbon nanotube binding peptide (CBP) sequence on the CNTs. This resulted in higher current densities than when using enzymes without CBP sequences. However, owing to the randomly stacked CNTs on the surface of the electrodes, their conductive properties were impaired and performance as biocathodes was poor. Herein, we constructed a biocathode in which single-walled CNTs (SWCNTs) were oriented one-dimensionally and McoP is immobilized on the surface of an SWNCT via CBP. The current density was successfully increased by two-fold by orienting the CNTs and orienting and immobilizing McoP on their surfaces. This technology provides insights into the development of biodevices with controlled orientation of both the SWCNTs and enzymes immobilized on their surfaces.     

Spatial distribution of silica fillers in phase-separated rubber blends investigated by three-dimensional elemental mapping

The distribution of nano-sized silica in binary rubber blends is characterized by scanning transmission electron microscopy (STEM) tomography combined with energy dispersive X-ray spectrometry (EDX). 3D distribution of silica is visualized by STEM-EDX tomography with the tilt-series of silicon elemental maps, while the phase-separated morphologies of polyisoprene rubber (IR) and styrene-butadiene rubber (SBR) are visualized by STEM-tomography in high-angle-annular-dark field (HAADF) mode. The combination of STEM-EDX and STEM-HAADF tomography enables us to determine the distribution of silica between the two rubber phases quantitatively even with high contents of silica up to 70 phr (weight parts per hundred rubber). It is found that silica is preferentially distributed in the SBR phase, but it is also distributed in the IR phase when the IR fraction in the total rubber components is higher than 40 wt%. The preferential distribution of silica in the SBR phase improves the dispersion of the IR domains. This is the first use of this technique for a multicomponent polymer system, showing the advantage to characterize the complicated multicomponent polymer composite morphologies.     

Quantitative determination of corrosion products and adsorbed water on copper in humid air containing SO2 by IR-RAS measurements

The time dependency of the amounts of corrosion products and co-existing adsorbed water on copper in humid air containing SO₂ was estimated from a series of in situ time-resolved IR-RAS spectra on the basis of the relations between the band intensities and the mass changes of the corrosion products, which were determined by simultaneous measurement of IR-RAS and QCM. The amounts of both corrosion products increased slowly at the initial stage and later increased rapidly. Although the relative humidity was kept constant, the amount of adsorbed water increased nearly the same behavior as that of corrosion products in the stage of relatively small amounts of corrosion products and later increased rapidly when the amounts of corrosion products increased. In humid air without SO₂, sulfite gradually decomposed and some of it changed into sulfate.     

Optimum combination of operating parameters in abrasive cut-off

For optimization of abrasive cut-off operation, wheel wear equation must be identified before the operation is optimized. The equation is obtained by using GMDH algorithm with successive determination of trends containing interactive terms. In the model equation factors of grinding fluid are taken into consideration in addition to the factors of wheel, work material, feed (table speed) and wheel speed. For the identification of the model wheel wear tests are performed under the experimental design treating the above-mentioned factors as independent variables. The grinding ratio (output in the model) can be predicted for combinations of various factors using the model. With the wheel wear equation and machining cost model, the optimum combination of wheel, fluid, feed and wheel speed can be selected for a given work material. The relationships between these variables and the costs are investigated.     

Activity measurements of Al and Cu in Si–Al–Cu melt at 1273 and 1373 K by the equilibration with molten Pb

For the effective control of Al introduction to solidified Si during the solidification refining of Si with the Si–Al-based melt for the solar cell material or the LPE Si film growth processes from the Si–Cu–Al solvent, thermodynamic properties of the Si–Al–Cu melt were investigated at 1273 and 1373 K. Activities of Al and Cu in the Si–Al–Cu melt were measured by the equilibration with molten Pb. Also, the excess Gibbs energy of the melt was studied by the ternary regular solution model.

The evaluated thermodynamic properties of the Si–Al–Cu melt indicated that Cu addition to the Si–Al melt brings the smaller activity coefficient of Al and is effective for reducing the Al content of solidified Si from the melt more effectively than its dilution effect for Al.