Monomer concentration effect on the phase behavior of poly(propyl acrylate) and poly(propyl methacrylate) with supercritical CO2 and C2H4

Experimental cloud-point data to temperature of 186 °C and pressure of ~2,500 bar are presented for ternary mixtures of poly(propyl acrylate)(PPA)-CO₂-propyl acrylate (PA) PPA-C₂H₄-PA and poly(propyl methacrylate) (PPMA)-CO₂-propyl methacrylate (PMA) systems. Cloud-point pressures of PPA-CO₂-PA system were measured in the temperature range of 32 °C to 175 dgC and to pressures as high as 2,070 bar with PA concentrations of 0.0, 5.0, 11.7 and 30.4 wt%. Adding 34.1 wt% PA to the PPA-CO₂ mixture significantly changes the phase behavior. This system changes the pressure-temperature slope of the phase behavior curves from U-LCST region to LCST region as the PA concentration increases. Cloud-point data to 170 °C and 1,400 bar are presented for PPA-C₂H₄-PA mixtures and with PA concentration of 0.0, 5.7, 15.5 and 22.2 wt%. The cloud-point curve of PPA-C₂H₄ system shows relatively flat at 730 bar for temperatures between 41 and 150 °C. With 15.5 and 22.2 wt% PA the cloud-point curve exhibits a positive slope that extends to 35 °C and ~180 bar. Also, the ternary PPMA-CO2-PMA system was measured below 186 °C and 2,484 bar, and with cosolvent of 5.2-20.1 wt%. PPMA does not dissolve in pure CO₂ to 233 °C and 2,500 bar. Also, when 41.5 wt% PMA is added to the PPMA-CO₂ solution, the cloud-point curve shows the typical appearance of a lower critical solution temperature (LCST) boundary.     

Effect of oxygen flow rate on the structural and electrochemical properties of lithium nickel oxides synthesized by the sol–gel method

The structural and electrochemical properties of LiNiO₂ powders were investigated as a function of the oxygen flow rate employed in the preparation of lithium nickel oxide. It was found that oxygen played an important role in the synthesis of highly crystallized LiNiO₂(R3¯m). In the crystallization process of LiNiO₂, a deficiency of oxygen in the calcination reactor induced the formation of impurities and cubic rock-salt structure (Fm3m) in LiNiO₂ powders. For LiNiO₂ prepared at higher oxygen flow rates, the electrode delivered high discharge capacities with relatively good retention rates. But very low electrode capacity was obtained from LiNiO₂ prepared at lower oxygen flow rates.     

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.     

Asymmetric Epoxidation of Styrene on the Heterogenized Chiral Salen Complexes Prepared from Organo-Functionalized Mesoporous Materials

Organosilane-modified mesoporous materials have been prepared under mild and acidic conditions by a solvent evaporation method using C₁₆TMABr surfactant as a template. The mesoporous samples synthesized in ethanol solvent by using this evaporation method showed a fully disordered pore system, but those obtained under hydrothermal conditions had highly ordered pores. The chiral salen Mn(III) complexes were immobilized on these organosilane-functionalized mesoporous silicas by a grafting method. The catalysts used in the asymmetric epoxidation of styrene and cis-stilbene and the effect of different mesoporous structures on the reactivity was investigated. Similar enantioselectivities were observed by using these heterogenized salen complexes as compared with reaction under homogeneous conditions.     

Migration characteristics of some chemical species in a granite fracture according to their chemical properties

Migration experiments were carried out in artificial rock fractures of 50×50 cm scale in order to understand the transport phenomena of contaminants in deep geological environment. The tracers used in this experiments were tritiated water, anion, polymers, and sorbing cations. The experimental study was focused on the interpretation of the retardation and matrix diffusion of the tracer in the fracture. To visualize migration phenomena, an organic dye, eosine, was used as a tracer. The migration plumes were taken with a digital camera as a function of time and stored as a digital image file. Computer simulation was performed not only for the hydraulic behavior such as distributions of pressure and flow vectors in the fracture but also for the migration plume and the elution curves. These simulation results were interpreted by comparing experimental ones, thus providing a way to understand migration behavior of tracers and interaction between rock and chemical species.     

Absorption characteristics of ammonia-water system in the cylindrical tube absorber

Experimental analysis was performed in a cylindrical tube absorber which is considered to be suitable for the bubble mode. Characteristics such as concentration, temperature, and pressure were measured and they reflected the condition of absorber well. The variation of characteristics was conspicuous near the inlet region of the ammonia gas. The ammonia gas and the solution flowed cocurrently and countercurrently and the results were compared. Presented at the Int’l Symp. on Chem. Eng. (Cheju, Feb. 8–10, 2001) dedicated to Prof. H. S. Chun on the occasion of his retirement from Korea University.     

Preparation and Characterization of Sol—Gel-Derived Lead Magnesium Niobium Titanate Thin Films with Pure Perovskite Phase and Lead Oxide Cover Coat

A sol–gel-derived Pb(Mg_1/3Nb_2/3)_0.7Ti_0.3O₃ (PMNT) thin film was prepared using spin coating and a PbO cover coat technique. The amount of lead excess in the precursor solution had significant effects on the phase development and microstructure of the PMNT film. The PbO cover coat proved to be effective on suppressing the formation of pyrochlore phases. PMNT thin films with a pure perovskite structure were obtained by adding 30 mol% excess lead in the precursor solution and coating the PbO layer on the top of the film. The remnant polarization ( P _r), the dielectric constant (ɛ_r), and the dissipation factor (tan δ) of these thin films, which had a thickness of 150 nm, were determined to be 9 μC/cm², 1370, and 0.031, respectively.     

Abnormal Grain Growth of Pb(Mg1/3Nb2/3)O3-35 mol% PbTiO3 Ceramics Induced by the Penetration Twin

Pb(Mg_1/3Nb_2/3)O₃-35 mol% PbTiO₃ (PMN-35PT) specimens with a 5 mol% excess PbO were prepared by excessive heat treatment at 1150°C to induce abnormal grain growth. Through electron backscatter diffraction analysis and the observation of a three-dimensional morphology, the abnormally grown PMN-35PT grains were found to be twinned crystals with penetration characteristics. The morphology of the PMN-35PT twinned crystal was crystallographically analyzed. The abnormal grain growth of PMN-35PT is suggested to be due to preferential growth at the reentrant angles formed by twins.     

Selective hydrogenation of 4-isobutylacetophenone over a sodium-promoted Pd/C catalyst

The effect of sodium promotion on the selective hydrogenation of 4-isobutylacetophenone, 4-IBAP, was investigated over a Pd/C catalyst. A precipitation and deposition method was used to prepare the catalyst, and sodium was promoted on the Pd/C catalyst via post-impregnation while varying the sodium content. The sodium-promoted Pd/C catalyst resulted in a significantly improved yield greater than 96% of the desired product, 1-(4-isobutylphenyl) ethanol (4-IBPE), compared with the non-patented literature results under a mild hydrogenation condition. A detailed hydrogenation network over the Pd/C catalyst was suggested. The reaction mechanism for the yield and selectivity enhancement of 4-IBPE induced-by the promoted Pd/C was elucidated in relation to the geometric and electronic effects of reactant molecules in the microporous support depending on the reaction steps.