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.     

Thermal strain of high strength polyethylene fiber in low temperature

High strength polyethylene fiber (Toyobo, Dyneema® fiber: hereinafter abbreviated to DF) has a negative thermal expansion coefficient. Relation between fiber structure and thermal strain of DF used as reinforcement of DF reinforced plastic (DFRP) for cryogenic use was investigated. The crystallinities and orientation angles of several kinds of polyethylene fibers having different modulus from 15 to 134Gpa (herein after abbreviated to DFs) were measured by NMR and X‐ray. We obtained the parameters of the mechanical series‐parallel model composed of crystal and amorphous by crystallinity and modulus. Thermal expansion coefficients of DFs were estimated by mechanical series‐parallel model. All DFs having different modulus showed negative thermal expansion coefficients in the temperature range from 180 to 300K, and absolute values of those markedly increased by increasing tensile modulus of DF. The estimated thermal expansion coefficients showed negative values, and thermal strains showed a similar curve to observed ones mostly. Average thermal expansion coefficients in the temperature range from 180 to 300K estimated by mechanical model agreed with the observed ones. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 2918–2925, 2004     

Alternative technologies for biotechnological fuel ethanol manufacturing

The challenges of implementing biorefineries on a global scale include socioeconomic, financial, and technological constraints. In particular, the development of biorefineries is tightly linked to the continued availability of fermentation raw materials. These constraints can be relaxed by the use of diverse raw materials, while advances that confer higher flexibility would enable biotechnological plant managers to swiftly react to volatile markets. In conventional processes, Saccharomyces cerevisiae grows on a relatively limited range of substrates, and produces only a single product—ethanol. Given the observed maturity of the S. cerevisiae fermentation technology, alternatives to baker's yeast may be needed to tip the economic balance in favour of biotechnological ethanol. These alternative fermentation technologies may allow a greater diversity of substrates to be used to produce an individually tailored mix of ethanol and other chemicals. Copyright © 2007 Society of Chemical Industry     

Influence of activated carbon pore structure on oxygen reduction at catalyst layers supported on rotating disk electrodes

Carbon materials are often used as catalyst supports, and for catalysts in electrodes of a polymer electrolyte fuel cell, carbon black has been used. Recently, it was found, however, that activated carbon could replace carbon black and besides, significantly improve the activity of the electrode catalyst layer for oxygen reduction. In the present study, to optimize the pore structure of activated carbon for further activity improvement, the influence of the pore structure on the activity was investigated using activated carbon of various specific surface areas and mean pore diameters. A catalyst layer was formed from activated carbon loaded with platinum and a polymer electrolyte. The activity of the layer was measured in an oxygen-saturated perchloric acid solution, supporting the layer on a rotating glassy carbon disk electrode. We found that increases in the specific surface area and mean pore diameter increased the activity and that the latter was more effective than the former mainly due to the enhanced mass-transfer in the pores; the catalyst layer formed from activated carbon with the largest mean pore diameter was the most active. Unless pores excessively develop and lose connections between particles, a large pore diameter is therefore desired for the fuel cell electrodes.     

The electrocatalytic activities of the Pd-doped MnO2 for the chlorine evolution reaction

The anodic evolution of chlorine on the massive β-MnO₂ doped with various amounts of Pd was investigated in acidic chloride solution. A second-order relation was found between the rate of the chlorine evolution reaction and the number of active Pd sites at the electrode surface. And it was confirmed that, in the relatively low doped electrodes, the active sites are more effectively dispersed on the surface with microscopic homogeneity. From the activation energies, it was also suggested that the reaction mechanism on the MnO₂ doped with relatively small amounts of Pd is somewhat different from that on the pure PdO electrode.     

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.     

Synthesis and electrode performance of layered nickel dioxide containing alkaline ions

Several polymorphs of layered nickel dioxide were prepared by using the chemical insertion of alkaline ions into Li_0.10NiO₂. We used aqueous AOH (A = Li, Na, K) solutions as reducing agents. Sodium and potassium insertion resulted in hydrated layered compounds that can be classified as γ-NiOOH with high crystallinity, while lithium insertion occurred without hydration. We discuss the coordination environment around the A⁺ ions for these inserted compounds. The thermal behavior, analyzed using high temperature (HT) X-ray diffraction (XRD) and thermogravimetric (TG) measurements, indicated that heating the hydrate at 150 °C yielded its dehydrate. The electrode performance of the nickelate was studied in lithium cells. We discuss the effect of interlayer water on cell rechargeability and the similarity between these nickelate and hydrated manganese dioxide (birnessite).     

Influence of the nigrosine dye on the thermal behavior of polyamide 66

To reveal the effect of the nigrosine dye, that the addition of the dye lowers the crystallization point (T_c) of molten polyamide resins with substantially no shift in the melting point (T_m), thus suppressing the crystallization enhancement of the crystalline nucleation agents, the characteristics of polyamide 66 (PA‐66) containing nigrosine dye EX (N‐EX) were investigated. Differential scanning calorimetry (DSC) analysis showed that the addition of N‐EX reduced the crystallization rate and T_c of molten PA‐66 with substantially no shift in T_m, and the crystallization enthalpy per unit of weight of PA‐66 was substantially constant. T_c of molten PA‐66 was lowered with an increase in the amount of N‐EX and reached its maximum at 13 wt % N‐EX. Dynamic mechanical analysis showed that the glass‐transition temperature and the secondary glass‐transition temperature increased with an increasing amount of the dye. On the other hand, the DSC and X‐ray diffraction results indicated that no dye molecule was present in the crystal structure of PA‐66. This effect of the nigrosine dye on PA‐66 is in contrast to those of crystalline nucleation agents, plasticizers, and antiplasticizers. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 3270–3274, 2006     

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.     

Granulation of a hardmetal powder for spark plasma sintering

A fluidized bed granulation method, pressure swing granulation (PSG), was applied to granulation of a hardmetal powder without pressing lubricants for making the upstream process of spark plasma sintering (SPS) more efficient.

The properties of the granules were examined and compared with those of spray dried granules and extruded ones under the present system using a sieve.

Spherical granules between 0.15 and 0.84 mm in diameter difficult to obtain by the spray drying were obtained with high yield. The flowability of the granules was far better than that of spray dried granules and similar to that of extruded ones. Iron contamination and oxidization during pressure swing granulation were tolerable to the real production.