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.     

Effect of steric hindrance on hydrogen‐bonding interaction between polyesters and natural polyphenol catechin

The phase behaviors for the blends of poly(3‐hydroxypropionate) (PHP), poly(L ‐lactide) (PLLA), poly(D ‐lactide) (PDLA), and poly(D,L ‐lactide) (PDLLA) with catechin were investigated by differential scanning calorimetry. In PLLA/catechin, PDLA/catechin, and PDLLA/catechin blends, two glass transitions were detected when the catechin content was ≥40 wt %, whereas in PHP/catechin blends only one glass transition was observed over the whole range of blend compositions. The former and the latter results should reflect the inhomogeneous and the homogeneous nature of the blends, respectively, in the amorphous phase. These different phase behaviors should arise from the differences in the chemical structures between PHP and PLLA/PDLA/PDLLA, which dominates the strength and the number of intermolecular hydrogen‐bonding interactions between the ester carbonyl groups of polyesters and the phenol groups of catechin. As detected by FTIR spectroscopy, in comparison with PHP, the steric hindrance of side‐chain methyl groups of PLLA, PDLA, and PDLLA might restrain the formation of hydrogen bonds between their ester carbonyl groups and the phenol hydroxyl groups of catechin, even weakening the strength of such hydrogen bonds. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 91: 3565–3573, 2004     

Preparation of regioisomers of structured TAG consisting of one mole of CLA and two moles of caprylic acid

TAG (MLM) with medium-chain FA (MCFA) at the 1,3-positions and long-chain FA (LCFA) at the 2-position, and TAG (LMM) with LCFA at the 1(3)-position and MCFA at 2,3(1)-positions are a pair of TAG regioisomers. Large-scale preparation of the two TAG regioisomers was attempted. A commercially available FFA mixture (FFA-CLA) containing 9-cis, 11-trans (9c, 11t)- and 10t,12c-CLA was selected as LCFA, and caprylic acid (C₈FA) was selected as MCFA. The MLM isomer was synthesized by acidolysis of acyglycerols (AG) containing two CLA isomers with C₈FA: A mixture of AG-CLA/C₈ FA (1∶10, mol/mol) and 4 wt% immobilized Rhizomucor miehei lipase was agitated at 30°C for 72 h. The ratio of MLM to total AG was 51.1 wt%. Meanwhile, LMM isomer was synthesized by acidolysis of tricaprylin with FFA-CLA: A mixture of tricaprylin/FFA-CLA (1∶2, mol/mol) and 4 wt% immobilized R. miehei lipase was agitated at 30°C for 24 h. The ratio of LMM to total AG was 51.8 wt%. MLM and LMM were purified from 1,968 and 813 g reaction mixtures by stepwise short-path distillation, respectively. Consequently, MLM was purified to 92.3% with 49.1% recovery, and LMM was purified to 93.2% with 52.3% recovery. Regiospecific analyses of MLM and LMM indicated that the 2-positions of MLM and LMM were 95.1 mol% LCFA and 98.3 mol% C₈ FA, respectively. The results showed that a process comprising lipase reaction and short-path distillation is effective for large-scale preparation of high-purity regiospecific TAG isomers.     

Preparation of Aragonite Whiskers

A simple synthetic method for preparing aragonite whiskers has been developed. A suspension of CaCl₂-MgCl₂-Mg(OH)₂ with pH ∼9 has been prepared by adding Ca(OH)₂ to MgCl₂ aqueous solution. CaCO₃ whiskers (aragonite phase) have been prepared easily by blowing CO₂-containing gas into the suspension. The whiskers have high aspect ratios ranging from 20 to 80 with diameters of 0.5–1 μm .     

Monte Carlo simulation of the sol-gel process for the hydrolysis and polycondensation of tin tetra-n-butoxide

The sol-gel process for the hydrolysis and polycondensation of tin tetra-n-butoxide in butanol was followed by viscosity measurements. The precipitation of tin-containing ultrafine particles was observed without any variation in the solution viscosity in the absence of diethylene glycols, while the viscosity increase was made without any precipitation by the addition of diethylene glycol. The induction period and the rate of the viscosity increase after the induction period was independent of the diethylene glycol content but depended upon the water content. The Monte Carlo simulation data were consistent with data for the viscosity experiment. The simulation was based on a kinetic model of the slow hydrolysis of tin tetra-n-butoxide, the reverse reaction of hydrolysis, and the polycondensation of the hydroxy derivatives.     

Ceramic fibres from polymer precursor containing Si-O-Ti bonds

Polycarbosilanes containing titanium alkoxide as pendant groups (atom ratio Ti/Si = 0.07 and 0.15) were synthesized. These polymers were melt-spun and then heat-treated in a vacuum, in oxygen or ammonia gas flow, resulting in Si-Ti-C-O, Si-Ti-0 and Si-Ti-O-N fibres, respectively. The pyrolysis process of the polymer is discussed in connection with the mechanical properties and the structure of the fibre. At high heat-treatment temperatures, -SiC and TiC (in Si-Ti-C-O fibre), anatase (in Si-Ti-O fibre) and TiN (in Si-Ti-O-N fibre) crystallized, which may be closely related to the decomposition of the Si-O-Ti bond in the fibre.     

COLOURING OF PURE IRON AFTER Ti~＋-O~＋ DUAL ION IMPLANTATION

用电化学的方法对经Ｔｉ~＋－Ｏ~＋二重离子注入后的钝铁表面进行处理，可呈现出深蓝、海蓝、褐、紫、金黄、淡黄等颜色用Ｘ射线光电子能谱（ＸＰＳ）对着色表面进行分析，发现表层有ＴｉＯ＿２富集，证明存在钛的氧化物是着色的必要条件．同时着色后的表面存在Ｔｉ的浓化层，着色的深浅程度与钛的浓度有关     

Note: Accuracy of velocity correction for impact of a laser-accelerated miniature flyer with lithium fluoride shock-compressed along the [100] axis

We performed miniature flyer impact experiments to investigate the relationship between the apparent (u(a)) and actual (u(A)) particle velocities measured by a velocity interferometer in single-crystal lithium fluoride (LiF) that was shock-compressed along the [100] axis. The miniature flyer was accelerated to velocities in the range 652.5-1937.6 m/s by a tabletop pulsed laser. An empirical relationship of u(a) = (1.2749 ± 0.0102)u(A) was obtained. The obtained relationship agreed well with the results of a previous study within the experimental errors and its uncertainty was less than ±1%. This result indicates that the present experimental technique is effective for measuring the relationship between u(a) and u(A) of shocked transparent materials with a comparable accuracy to conventional methods.     

A selective conductive polymer-based sensor for volatile halogenated organic compounds (VHOC)

A novel poly(p-xylylene), PPX, derivative bearing alkoxyphenyl side groups was electrochemically synthesized in 87% yield. The polymer, poly(4′-hexyloxy-2,5-biphenyleneethylene) (PHBPE), presented a fraction (92%) soluble in common organic solvents. It showed to be thermally resistant up to 185 °C. UV–vis analysis revealed an E_gap of 3.5 eV. Gas sensors made from thin films of 10-camphorsulfonic acid-doped PHBPE deposited on interdigitated electrodes exhibited significant changes in electrical conductance upon exposure to five VHOCs: 1,2-dichloroethane, bromochloromethane, trichloromethane, dichloromethane and tetrachloromethane. The conductance decreased after exposure to tetrachloromethane and increased after exposure to all the other VHOCs. Three-dimensional plots of relative response versus time of half response versus time of half recovery showed good discrimination between the five VHOCs tested.     

A combined approach for modeling particle behavior in granular impact damper using discrete element method and cellular automata

A particle impact damper is a vibration absorber type that consists of a container attached to a primary vibrating structure. It also contains many particles that are constrained to move inside the container, whereby the damping effect can be obtained by collision between particles and the container. The discrete element method (DEM) has been developed for modeling granular systems, where the kinematics of each particle are calculated numerically using the equations of motion. However, the computational time is significant since the algorithm checks for particle contacts for all possible particle combinations. The use of a cellular automata (CA) modeling technique may provide increased computational efficiency due to the local updating of variables, and the discrete treatment of time and space. In this study, we propose a new approach combining DEM with CA for modeling a granular damper under a forced excitation. We use DEM to describe the particle motion according to the equations of motion, while CA is introduced for the particle contact checks in discrete space. We also investigate the effect of simplification in the contact force model, which allows the unit time step of numerical integration to become larger than that used in the strict model. It is shown that the suggested particle contact scanning method and the force approximation model contribute to the reduction of the computational time, and neither degenerates the calculation accuracy nor causes the numerical instability.