Morphology and activity of nanosized NdCl3 catalyst for 1,3‐butadiene polymerization

The binary lanthanide catalyst for 1,3‐butadiene was invented for 40 years ago. However, it has not been employed in commercial application due to its poor solubility and low activity. Nanosized neodymium chloride (NdCl₃) was prepared in tetrahydrofuran (THF) medium through dissolution, chelation, and colloidal formation steps. Anhydrous NdCl₃ was dissolved in THF, and ca. 1.5 THF molecules were coordinated. In the colloidal formation step, THF was slowly replaced with the addition of cyclohexane, and pale blue nuclei, nanosize below 200 nm, were formed. The structural studies for NdCl₃ · xTHF using X‐ray powder diffraction (XRD) and scanning electron microscope (SEM) indicate that high ordered crystallinity is decreased with reduced particle size from trigonal prismatic to porous sphere structure. Nano NdCl₃, obtained as colloidal state in cyclohexane, was activated with Al(iBu)₃ and Al(iBu)₂H at room temperature and employed for 1,3‐butadiene solution polymerization. The nanosized Nd catalysts showed high activity (1.0 ～ 1.3 × 10⁵ g/Nd mol · h), which is comparable to that of the ternary neodymium catalyst Nd(neodecanoate)₃/AlEt₂Cl/Al(iBu)₃. The microstructures of polybutadiene, cis, trans, and vinyl, are about 96.0, 3.5, and 0.5%, respectively. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 1279–1283, 2005     

Novel positive‐working aqueous‐base developable photosensitive polyimide precursors based on diazonaphthoquinone‐capped polyamic esters

Novel positive‐working aqueous‐base developable photosensitive polyimide (PSPI) precursors based on partially diazonaphthoquinone (DNQ)‐capped polyamic esters bearing phenolic hydroxyl groups and a DNQ photosensitive compound (PIC‐3) were developed. The partially DNQ capped polyamic esters were prepared from an esterification reaction of 1,2‐naphthoquinone diazide‐5‐sulfonyl chloride with the polyamic esters. The partially DNQ capped polyamic esters decreased the dark film loss effectively in the aqueous‐base developer and were able to make thicker film resists compared to the uncapped polyamic esters. The 25 mol % DNQ‐capped BisAPAF–PMDA polyamic ester and BisAPAF–ODPA polyamic ester containing 25 wt % PIC‐3 photosensitive compound showed a sensitivity of 176 and 185 mJ/cm², and a contrast of 1.68 and 1.02, respectively, in a 3‐μm film with 1.25 wt % tetramethylammonium hydroxide developer. A pattern with a resolution of 5 μm was obtained from both PSPI precursor compositions. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 2293–2300, 2003     

Polymerization of styrene in a continuous filled tubular reactor

Free radical solution polymerization of styrene has been studied using a binary mixture of symmetrical bifunctional initiators in a filled tubular reactor packed with static mixers. Owing to intensive radial mixing induced by the static mixers, a near plug flow pattern was obtained in the reactor with some axial dispersion effect. The axial mass dispersion coefficient was determined from the residence time distribution experiment and a dynamic axial dispersion model has been developed and solved to investigate steady state and transient behavior of the filled tubular reactor. With a solvent volume fraction of 0.3, the monomer conversion up to 70% was obtained without fouling problems in the temperature range 90 to 120°C. The experimental filled tubular reactor was operated under various reaction conditions and a reasonably good agreement between the model and the experimental data was obtained without using any adjustable parameters.     

THERMAL CONVECTIVE INSTABILITY IN TRANSLUCENT POROUS MEDIA WITH RADIATIVE HEAT TRANSFER

The onset of thermal convection in a translucent porous layer is considered. Attention is focused on the effect of radiative heat transfer on the critical Rayleigh-Darcy number and the convection cell shape. If we consider the contribution of radiative heat transfer, the basic temperature profile is non-linear and the thermal convective instability is influenced by the ratio of conduction to radiation heat flux, the temperatures at the boundary surfaces, and radiative parameters such as wall emissivity, scattering albedo and extinction coefficient as well as the usual Rayleigh-Darcy number. Effects of these parameters on the onset of convective instability are investigated with the help of linear stability theory employing the Darcy's law and the radiative transport equation simplified by the P₁ approximation. The increased effective thermal conductivity due lo the radiation inhibits the onset of convection and causes increased critical Rayleigh-Darcy number and decreased convection cell size. The results of the present work may be exploited to find out the optimal diameter of aerogel pellets and the air pressure in the double pane window filled with the translucent silica aerogel granules to suppress natural convection.     

Effect of molecular weight on two smectic polyesters

The liquid crystalline transitions of two kinds of smectic polyesters with different molecular weights were investigated by DSC, polarized microscopy and X-ray diffraction. The molecular weight affects the transitions significantly for these two kinds of polyesters. With a high enough molecular weight, both poly (pentamethylenep,p-bibenzoate) and poly(hexamethylenep,p-bibenzoate) exhibit an enantiotropic smectic phase, but the two endothermic transition peaks of the DSC heating curve seem to overlap. The polyesters tend to exhibit a monotropic smectic phase as the molecular weight decreases. From the DSC cooling curve, the isotropic-smectic transition can be seen more clearly. As the molecular weight decreases, the smectic order decrease significantly. The molecular weight affects the transitions in a different way for these two different kinds of polyesters.     

Quantitative Analysis of Zinc Vaporization from Manganese Zinc Ferrites

Zinc vaporization of Mn-Zn ferrites was quantitatively characterized in terms of oxygen partial pressure P _O2, temperature, grain size and sample geometry. The amount of zinc loss was measured as a function of time at various temperatures by a thermogravimetric method. The weight loss due to irreversible zinc vaporization showed a linear behavior with time and increased exponentially with temperature. The observed weight loss due to zinc evaporation at 1100°C was small, whereas a significant weight change was detected at 1200°C. The weight loss was even greater in a reducing atmosphere ( P _O2= 5 × 10⁻⁵). Below 1300°C, the diffusion of elemental zinc was sufficiently fast to compensate the zinc loss at the interface region, resulting in a linear dependence on time. At temperatures ≥1400°C, the weight change no longer followed the linear dependence and showed a rather parabolic behavior with a concave upward slope. The core shape and the gas flow around ferrite cores were important factors that affected the rate of zinc vaporization, but not the grain size.     

Synthesis and characterization of new aromatic polyimides containing well‐defined conjugation units

A series of aromatic polyimides composed of well‐defined conjugation units were synthesized form 5,5′‐bis(4‐aminophenyl)‐2,2′‐bifuryl (PFDA) and 2,2′‐bis(furyl) benzidine (FurylBZ) with various dianhydrides. The synthesized polyimides emit blue to green light with a quantum yield of 7.3–14.9%, depending on the polymer backbone. In particular, PFDA‐based polymers exhibit extremely narrow photo‐luminescence. The structure, thermal stability, refractive index and dielectric properties of the polymer films were also determined.     

Solid circulation characteristics in an internally circulating fluidized bed with orifice-type draft tube

Effects of superficial gas velocities to a draft tube, to an annulus section and particle size on the solid circulation rate (G,) have been determined in an internally circulating fluidized bed (0.28 m I.D. × 2m high) with an orifice type draft tube. The solid circulation rate from the draft tube to an annulus section increases with increasing gas velocities to the draft tube(U _d ) and annulus section (U_a) and consequent increase in pressure drop across the orifice (ΔP_or). However, the values ofG _s decrease by 7–21% with increasing particle size from 86 to 288 μm. The pressure drop across the orifice increases with increasingU _d andU _a . However, ΔP_or decreases by 5–23% with increasing particle size. To predictG _s in an internally circulating fluidized bed, a correlation is proposed as a function of ΔP_or This paper is dedicated to Professor Dong Sup Doh on the occasion of his retirement Korea University.     

A novel layered Li [Li0.12NizMg0.32−zMn0.56]O2 cathode material for lithium-ion batteries

Layered Li[Li_0.12Ni_zMg_0.32−zMn_0.56]O₂ oxide cathodes containing lithium atoms in the transition metal layers were synthesized and characterized using X-ray diffraction (XRD), galvanostatic cycling, and differential scanning calorimetry (DSC). The Li[Li_0.12Ni_zMg_0.32−zMn_0.56]O₂ cathodes deliver a specific discharge capacity of about 190 mAh/g at room temperature and 236 mAh/g at 55 °C when cycled between 2.7 and 4.6 V versus Li/Li⁺. Excellent capacity retention and smooth potential profiles at room and elevated temperatures over extended cycles suggest that this material does not convert into a spinel structure.     

Esters of hydroxystearic acids as primary low-temperature plasticizers for a vinyl chloride—Vinyl acetate copolymer

Summary Thirty-one acyloxy or aryloxy esters prepared from hydroxystearic acids have been evaluated as plasticizers for a vinyl chloride-vinyl acetate copolymer (95∶5). Many of them were found to be primary plasticizers, having outstanding low-temperature performance when employed at the 35% level. Formulations with these compounds compared quite favorably in tensile properties with those containing the di-2-ethylhexyl esters of phthalic, sebacic, azelaic, and adipic acids. Volatility losses were similar to those of the four di-2-ethylhexyl esters. The loss of plasticizer through migration was equal to or less than that from compositions containing the esters of sebacic, azelaic, and adipic acids but was greater than that of the phthalate ester. A mechanistic scheme of plasticizer-polymer interaction has been presented, proposing that the rate of diffusion of plasticizer through the polymer mass is a controlling factor in both good low-temperature performance and the resulting high migration losses. Methyl esters, some aromatic esters, and esters containing three or more polar centers have improved permanence but show a more rapid change in torsional modulus as the temperature is lowered during the determination of the Clash-Berg stiffening temperature. Eastern Utilization Research and Development Division, Agricultural Research Service, U. S. Department of Agriculture.