Characteristics of polypyrrole chemically synthesized by various oxidizing reagents

Polypyrrole was chemically synthesized using various oxidizing reagents and examined as a positive electrode material. Physical properties, morphologies and electrochemical characteristics of polypyrrole were greatly influenced by the oxidizing reagent used for polymerization. In general, polypyrrole with a smaller particle size and a larger specific surface area showed better discharge performance than that with a larger particle size and a smaller specific surface area. Polypyrrole was also synthesized on various conducting and nonconducting substrates using Fe(C10₄)₃ as an oxidizing reagent. By using PP nonwoven fabric as a substrate material, a high discharge capacity of 72 mA h g^–1 was obtained. Polypyrrole synthesized on only one side of PP nonwoven fabric was able to be used as an electrode.     

Effect of Ratio of Surface Area to Volume on Oxygen Self-Diffusion Coefficients Determined for Crushed MgO-Al2O3 Spinels

Oxygen self-diffusion coefficients for single-crystal MgO-Al₂O₃ spinels previously determined for crushed particles were recalculated using the microscopic suface area of the sample, as was done for alumina. The corrected results agree well with those of Reddy and Cooper .     

Role of Acetic Acid Added to the Reaction Media for the Enantio-differentiating Hydrogenation of Methyl Acetoacetate Over a Tartaric Acid-modified Nickel Catalyst

The role of acetic acid added to the reaction media for the enantio-differentiating hydrogenation of methyl acetoacetate over a (R,R)-tartaric acid-in-situ-modified nickel catalyst was studied from the viewpoint of the hydrogenation rate during repeated runs. The hydrogenation of methyl acetoacetate on the “enantio-differentiating sites” of a tartaric acid-modified nickel catalyst was specifically accelerated by the acetic acid added to the reaction media to increase the enantio-differentiating ability of the catalyst. In order to increase the enantio-differentiating ability, the addition of acetic acid to the reaction media was required in each run during the repeated use of the catalyst.     

Simple chemical syntheses of TAG monohydroperoxides

For the purpose of synthesizing standards to be used in the quantification of TAG hydroperoxides, three TAG (1,2-dioleoyl-3-palmitoylglycerol, 1-oleoyl-2-linoleoyl-3-palmitoylglycerol, and triolein) monohydroperoxides were chemically synthesized as authentic specimens. TAG were prepared by using a simple condensation in pyridine of glycerol and the corresponding acid chlorides. These TAG were then converted into monohydroperoxides by a photosensitized peroxidation. The synthesized monohydroperoxides were analyzed by normal-phase and RP-HPLC. The results of normal-phase HPLC analysis showed that monohydroperoxides from a corresponding TAG were a mixture of regioisomers. In RP-HPLC, however, the regioisomers of monohydroperoxides were not separated and gave a single peak, which may improve the sensitivity for the detection of TAG monohydroperoxides. In this study TAG monohydroperoxide standards were synthesized; these will be useful for the study of yet unknown biological and pathological roles of TAG hydroperoxides.     

Isotachophoretic analysis of surfactants

The qualitative and quantitative determination of anionic surfactants (sodium and lithium alkylsulfate, sodium dodecylbenzenesulfonate, sodium di-2-ethylhexyl sulfosuccinate, sodium and lithium perfluoroalkylcarboxylate, and lithium perfluorooctanesulfonate) were investigated by a capillary tube isotachophoresis using a potential gradient detector. The leading electrolyte solution was the mixture of acetonitrile and aqueous solution of histidine buffer containing calcium chloride. The terminating electrolyte solution was the aqueous solution of sodium octanoate. These electrolytes were effective for the analysis of the mixtures of strongly acidic surfactants.     

Design of new catalysts for ecological high-quality transportation fuels by combinatorial computational chemistry and tight-binding quantum chemical molecular dynamics approaches

Recently, we introduced a concept of combinatorial chemistry to computational chemistry and proposed a new method called “combinatorial computational chemistry”, which enables us to perform a theoretical high-throughput screening of catalysts. In the present paper, we reviewed our recent application of our combinatorial computational chemistry approach to the design of new catalysts for high-quality transportation fuels. By using our combinatorial computational chemistry techniques, we succeeded to predict new catalysts for methanol synthesis and Fischer–Tropsch synthesis. Moreover, we have succeeded in the development of chemical reaction dynamics simulator based on our original tight-binding quantum chemical molecular dynamics method. This program realizes more than 5000 times acceleration compared to the regular first-principles molecular dynamics method. Electronic- and atomic-level information on the catalytic reaction dynamics at reaction temperatures significantly contributes the catalyst design and development. Hence, we also summarized our recent applications of the above quantum chemical molecular dynamics method to the clarification of the methanol synthesis dynamics in this review.     

Effect of Agglomeration on Mechanical Properties of Porous Zirconia Fabricated by Partial Sintering

Porous ZrO₂ ceramics were fabricated by compacting a fine ZrO₂ powder, followed by pressureless sintering. Two unidirectional pressures of 30 and 75 MPa were used to prepare the green compacts. The strength and the fracture toughness of porous ZrO₂ specimens sintered from the compacts prepared by 75 MPa were substantially higher than those by 30 MPa, especially for the specimens with low porosity. However, the corresponding Young's moduli were identical. This caused the strain to failure of these porous bodies to increase significantly with increasing compaction pressure. Microstructural analyses showed that a number of voids and small flaws existed in the green compacts prepared by the lower pressure, due to the agglomeration of fine ZrO₂ grains. It was revealed that the ZrO₂ agglomeration resulted in a localized nonuniform shrinkage and degraded the mechanical properties of porous ZrO₂ ceramics.     

Sintering of the Mechanochemically Activated Powders of Hexagonal Boron Nitride

Pressureless sintering of hexagonal boron nitride (BN) was performed using a powder activated by mechano-chemical treatments. Physical properties of the sintered BN bodies depend on the type of starting powder and the conditions of the treatments. The BN body, which was obtained at 2000°C using an appropriate activated powder, was 99 wt% pure and was excellent in mechanical and physical properties, in spite of its low density (1.64 g/cm³).     

Production of finely ground natural graphite particles with high electrical conductivity by controlling the grinding atmosphere

Natural graphite particles with high crystallinity sieved to obtain a particle size range of under 63 μm were ground with a ball mill, under various well-controlled grinding atmospheres such as N₂, O₂, He, H₂, and vacuum. The ratio, X_dif50/X_st50, i.e. between the 50 wt.% Stokes diameter and the 50 wt.% laser diffraction diameter, of the ground particles, was used as an index of the flakiness of the particles. The specific resistance of films composed of the ground graphite particles was systematically measured. The rate of reduction in the size of the particles by grinding was slow under an O₂-rich atmosphere such as 100% O₂ and dry air. On the other hand, it was relatively fast in vacuum, or under an N₂ or He atmosphere, and a gas mixture of 99% N₂ and 1% O₂. The rate of size reduction by grinding under a H₂ atmosphere was intermediate. In our experimental conditions, the flakiness of the ground particles increased with the decrease in the particles’ sizes. The electrical conductivity of the ground particles, however, tended to decrease with the decrease in their sizes. Under the condition that the Stokes diameter of the ground particles remains constant, the electrical conductivity of films made from the ground particles increases with the increase in the flakiness of the particles. It was finally determined from our systematic grinding experiments that small flaky particles, which had a size, X_st of ∼1 μm, with a high electrical conductivity can be produced by grinding in a gas mixture of 99% N₂ and 1% O₂. In this case, the flaky shape of the ground particles was visually confirmed by scanning electron microscopy.     

Effect of pressure on phase transition and morphology of bulk poly(trans-1,4-butadiene)

The effect of pressure on the melting, solid-solid transition, and crystallization of poly(trans-1,4-butadiene) (PTBD) was investigated using the pressure range of 1–3000 kg/cm². D.t.a. measurements showed that, the melting and transition temperatures increase with increasing pressure, whose pressure coefficients are 38°C per 1000 kg/cm² and 22°C per 1000 kg/cm², respectively. These values were in fairly close agreement with those calculated from the Clausius-Clapeyron equation. Morphological studies using electron microscope and small-angle X-ray scattering method revealed that, the samples crystallized with relatively small supercoolings under normal or high pressure, are formed of distinct lamellae 400–800 Å thick. The lamellar thickness was inappreciably dependent on crystallization pressure. The significant effect of pressure on crystallization was recognized in a tendency of the crystallinity to increase, with increasing crystallization pressure. This pressure effect was explained by the mechanism that, the increased pressure might make the packing of molecular chains in liquid, more dense and that the secondary crystallization might be accelerated, to increase the lateral dimensions of lamellae.