Decomposition of chlorofluorocarbons on TiO2ZrO2

The decomposition of chlorofluorocarbons (CFCs) in the presence of water was examined over a variety of solid acid catalysts. The TiO₂ZrO₂ catalyst was found to have the highest activity and longest life among the catalysts examined. The activity of the TiO₂ZrO₂ catalysts depended upon the content of TiO₂. At the contents of TiO₂ from 58 to 90 mole%, the TiO₂ZrO₂ catalysts exhibited high activity, and these catalysts were proven to contain TiZrO₄ crystal. From the study of the XRD peak intensity of the TiZrO₄ crystal, it was highest on the TZ-58 which contained 58 mole% of TiO₂, and decreased with increasing the content of TiO₂. Furthermore, the conversion of CFC113 measured at 673 K was highest at TZ-58, and decreased gradually with increasing TiO₂ content. Therefore, the TiZrO₄ crystal influences the activity of decomposition of CFC113. However, the TiO₂ZrO₂ catalyst was gradually deactivated during the reaction due to the elimination of titanium atoms. A good relationship was found between the activity on TiO₂ZrO₂ catalyst and bond energy of CCl in the compounds of chlorofluorocarbons and hydrochlorocarbons, suggesting that the rate controlling step was the cleavage of CCl bond.     

Consideration on the Relationship Between Dielectric Breakdown Voltage and Water Content in Fatty Acid Esters

Mineral oil is commonly used as an electrical insulating oil in transformers because of its relatively high electrical insulating ability and fluidity. Considering the depletion of resources and environmental problems, however, fatty acid esters synthesized from natural plant oils are attracting attention as an environmentally friendly insulating oil. In addition, fatty acid esters such as methyl octanoate, methyl dodecanoate, 2-ethylhexyl octanoate, and 2-ethylhexyl dodecanoate have high fluidity, and also show excellent moisture tolerance against dielectric breakdown compared to mineral oil. In the present study, to clarify the reason for the superior moisture tolerance of fatty acid esters, the status of dissolved water in esters is investigated with IR spectroscopic measurements and density functional theory (DFT) calculations. It is revealed that water molecules in fatty acid esters are trapped by the ester moiety of fatty acid esters. As a result, fatty acid esters have a higher moisture tolerance against dielectric breakdown than mineral oil.     

Electrochemical conversion of carbon dioxide to methane in aqueous NaHCO3 solution at less than 273 K

The electrochemical reduction of CO₂ on a Cu electrode was investigated in aqueous NaHCO₃ solution, at low temperature. A divided H-type cell was employed, the catholyte was 0.65 mol dm⁻³ NaHCO₃ aqueous solution and the anolyte was 1.1 mol dm⁻³ KHCO₃ aqueous solution. The temperature during the electrolysis of CO₂ was decreased stepwise to 271 K. Methane and formic acid were obtained as the main products. The maximum Faradaic efficiency of methane was 46% at −2.0 V and 271 K. The efficiency of hydrogen formation, a competing reaction of CO₂ reduction, was significantly depressed with decreasing temperature. Based on the results of this work, the proposed electrochemical method appears to be a viable means for removing CO₂ from the atmosphere and converting it into more valuable chemicals. The synthesis of methane by the electrochemical method might be of practical interest for fuel production and the storage of solar energy.     

Conversion of methane to syngas in a solid oxide fuel cell with Ni-SDC anode and LSGM electrolyte

A solid oxide fuel cell constructed from Ni-SDC anode and LSGM electrolyte was applied to the partial oxidation of methane to syngas (CO+H₂) at 700-800 °C with the merits of co-generation of electricity and controllable O₂ supply. It was found that the co-generated syngas at H₂/CO ratio of 1.4-2.0 varied with applied current densities, CH₄ flow rates and operating temperatures. The cell voltage at 100 mA cm⁻² and 800 °C was 0.90 V, i.e. about 90 mW cm⁻² power density could be obtained. The cell operating at 50 mA cm⁻² for 24 h almost showed no degradation of the cell performance. The observed carbon deposition seemed mainly taking place by CH₄ cracking reaction.     

Size dependence of crystallization within spherical microdomain structures

We have investigated the size dependence of crystallization within spherical microdomains formed in various poly(ε-caprolactone)-block-polybutadiene diblock copolymers (PCL-b-PB). The crystallinity (χ) and melting temperature (T_m) of the PCL block are considerably lower than those of PCL homopolymer, and χ decreases steadily and T_m decreases only slightly with decreasing radius of PCL spheres (R) for a series of PCL-b-PB with a same molecular weight (M_n). When PCL-b-PB is compared with the similar R but different M_n, χ is significantly different, suggesting that the sphere size is not the unique factor to control crystallization within spherical microdomains.     

Intrinsic Elastic, Dielectric, and Piezoelectric Losses in Lead Zirconate Titanate Ceramics Determined by an Immittance-Fitting Method

The material coefficients of "soft" and "hard" lead zirconate titanate (PZT) ceramics were determined as complex values by the nonlinear least-squares-fitting of immittance data measured for length-extensional bar resonators. The piezoelectric d -constant should be a complex value to obtain a best fitting between observed and calculated results. Because the elastic, dielectric, and piezoelectric losses determined in this process were not "intrinsic" losses, a calculation process to evaluate the "intrinsic" losses was proposed. It was confirmed that the intrinsic losses were smaller than the corresponding extrinsic losses. The intrinsic piezoelectric loss existed in both soft and hard PZTs; ∼50% of the loss of piezoelectric d -constant was derived from the elastic and dielectric losses. The most notable difference between the soft and hard PZTs was observed in their elastic losses.     

Free energy perturbation study on a Trp-binding mutant (Ser88 ->Cys) of the trp-repressor

The Ser⁸⁸Cys mutant of the trp-repressor showed a lower affinityfor the corepressor than the wild-type repressor [G = 1.7 ±0.3 kcal/mol, Chou and Matthews (1989) J. Biol. Chem., 264,18314–18319].A molecular dynamics/free energy cycle perturbation study wasperformed to understand the origin of the decreased affinity.A value (G = 1.58 ± 0.28 kcal/mol) comparable with theexperimental value was obtained by the simulation. Free energycomponent analysis revealed that destabilization of the vander Waals interaction between Ser⁸⁸ and Trp¹⁰⁹ (corepressor)mainly contributed to the decreased affinity of the mutant.The rotational transition of the hydroxyl (sulfhydryl) groupof Ser⁸⁸ (Cys⁸⁸) during the simulations affected the contributionsof Arg⁸⁴ and water to the free energy change in the aporepressorand those of Arg⁸⁴ and Trp ¹⁰⁹ to that in the holorepressor.However, the contributions from different residues compensatedeach other, and the total free energy changes were almost invariablein the various simulations.     

Structure of microporous polypropylene sheets containing CaCO3 filler

The microporous polypropylene sheets were prepared by biaxially stretching polypropylene sheets containing CaCO₃ filler (particle size, 0.08–3.0 μm), when the CaCO₃ filler content was 59% by weight and the stretching ratio was 2.8 × 1.8. The microstructure of the sheets were investigated in relation to the CaCO₃ particle size by a N₂ gas permeation method. (1) Effective porosity increases with decreasing mean particle size of filler. (2) The tortuosity factor of the pore is in the range of 25–40 and becomes relatively smaller with decreasing mean particle size of filler. (3) The equivalent pore size becomes relatively smaller with decreasing mean particle size of filler.     

Catalytic performance of K-promoted Rh/USY catalysts in preferential oxidation of CO in rich hydrogen

K-promoted Rh/USY (molar ratio: K/Rh=3) catalyst was found to exhibit high performance in preferential oxidation of CO in rich hydrogen. Such high performance was maintained in the presence of steam and CO₂. The CO oxidation activity of the K-Rh/USY catalyst was independent of the partial pressure of H₂, while the activity of the unpromoted Rh/USY catalyst was decreased significantly in hydrogen-rich stream. The effect of potassium addition on the catalyst structure was investigated and is discussed in terms of the differences in the catalytic performance.     

Morphology,thermal, and mechanical properties of vinylester resin nanocomposites with various organo‐modified montmorillonites

New nanocomposites based on a vinylester resin (VER) and the organo‐montmorillonites (ODA‐M, BHL‐M, DEM‐M, BHLV‐M) modified with octadecylammonium, bis(2‐hydroxyethyl)lauryl ammonium, diethyl[2‐(methacryloyloxyl)ethyl]ammonium, and bis(2‐hydroxyethyl)lauryl(vinylbenzyl)‐ammonium chlorides, respectively, were prepared by dispersing the organoclays in VER, and subsequent crosslinking at finally 120°C. X‐ray diffraction studies and morphological studies using transmission electron microscopy revealed that exfoliation occurs for the VER/ODA‐M and BHL‐M composites, intercalation occurs for the VER/BHLV‐M composite, and neither intercalation nor exfoliation occur for the VER/DEM‐M and unmodified montmorillonite composites. On the whole, although the enhancement in flexural modulus was observed for the exfoliated ODA‐M and BHL‐M composites, the flexural strength was rather lowered. Dynamic viscoelastic measurement revealed that the ODA‐M, BHL‐M, and BHLV‐M nanocomposites have significantly higher storage modulus at the rubbery state than the other composites. Polym. Eng. Sci. 44:2041–2046, 2004. © 2004 Society of Plastics Engineers.