Hypoiodite‐Mediated Catalytic Cyclopropanation of Alkenes with Malononitrile

An efficient synthetic procedure for dicyano‐cyclopropanation of alkenes using catalytic amounts of molecular iodine as a precatalyst and tert‐butyl hydroperoxide (TBHP) as a terminal oxidant under mild conditions has been developed. This catalytic reaction works especially well for the aryl‐substituted double bond affording products of cyclopropanation in high yields. A catalytic cycle based on the generated in situ hypoiodite species has been proposed.

     

A novel hetero-junction Tunnel-FET using Semiconducting silicide–Silicon contact and its scalability

A new type of silicon-based Tunneling FET (TFET) using semiconducting silicide Mg₂Si/Si hetero-junction as source-channel structure is proposed and the device simulation has been presented. With narrow bandgap of silicide and the conduction and valence band discontinuous at the hetero-junction, larger drain current and smaller subthreshold swing than those of Si homo-junction TFET can be obtained. Structural optimization study reveals that low Si channel impurity concentration and the alignment of the gate electrode edge to the hetero-junction lead to better performance of the TFET. Scaling of the gate length increases the off-state leakage current, however, the drain voltage (V_d) reduction in accordance with the gate scaling suppresses the phenomenon, keeping its high drivability.     

Catalyst-free synthesis of silicon nanowires by oxidation and reduction process

A new process has been developed to grow silicon (Si) nanowires (NWs), and their growth mechanisms were explored and discussed. In this process, SiNWs were synthesized by simply oxidizing and then reducing Si wafers in a high temperature furnace. The process involves H₂, in an inert atmosphere, reacts with thermally grown SiO₂ on Si at 1100 °C enhancing the growth of SiNWs directly on Si wafers. High-resolution transmission electron microscopy studies show that the NWs consists of a crystalline core of ~25 nm in diameter and an amorphous oxide shell of ~2 nm in thickness, which was also supported by selected area electron diffraction patterns. The NWs synthesized exhibit a high aspect ratio of ~167 and room temperature phonon confinement effect. This simple and economical process to synthesize crystalline SiNWs opens up a new way for large scale applications.     

Thermal expansion coefficient and thermal fatigue of discontinuous carbon fiber-reinforced copper and aluminum matrix composites without interfacial chemical bond

Fully dense carbon fiber-reinforced copper and aluminum matrix (Cu–CF and Al–CF) composites were fabricated by hot press without the need for an interfacial chemical compound. With 30 vol% carbon fiber, the thermal expansion coefficients (TECs) of pure Cu and Al were decreased to 13.5 × 10^?6 and 15.5 × 10^?6/K, respectively. These improved TECs of Cu–CF and Al–CF composites were maintained after 16 thermal cycles; moreover, the TEC of the 30 vol% Cu–CF composite was stable after 2500 thermal cycles between ?40 and 150 °C. The thermal strain caused by the TEC mismatch between the matrix and the carbon fiber enables mechanical enhancement at the matrix/carbon fiber interface and allows conservation of the improved TECs of Cu–CF and Al–CF composites after thermal cycles.     

Comparative study of photoinduced wettability conversion between [PW12O40]/brookite and [SiW12O40]/brookite hybrid films

Two tungsten-based Keggin-type heteropolyacids (PW₁₂: ([PW₁₂O₄₀]³⁻) and SiW₁₂: ([SiW₁₂O₄₀]⁴⁻)) were hybridized with brookite-type TiO₂. Then photocatalytic decomposition activity, photoinduced hydrophilicity, and sustainability of the hydrophilicity in the dark were evaluated using gaseous 2-propanol (IPA) decomposition and sessile drop method. The obtained films were transparent in the visible wavelength range. Both hybrid films exhibited higher photocatalytic decomposition activity and had higher photoinduced hydrophilicizing rates than pure brookite films under UV illumination. The PW₁₂/TiO₂ film exhibited better photocatalytic performance than the SiW₁₂/TiO₂ film did. Atmosphere dependence, XPS analysis, and electrochemical experiments indicated the cause of these two films' different levels of sustainability of hydrophilicity to be differences in their electron storage capability. Results show that the electron scavenger capability and reoxidation efficiency of the heteropolyacid are key factors affecting the overall performance of wettability conversion of this hybrid film system before and after UV illumination.     

Utilization of oxygen flask combustion method for the determination of mercury and sulfur in coal

By use of oxygen flask combustion (OFC), a rapid and convenient determination method for mercury (Hg) and sulfur (S) in coal was developed. For the determination of Hg in coal, the OFC method with a KMnO₄ solution as an absorbent was carried out, and the resulting solution was analyzed by cold vapor atomic fluorescence spectrometry (CVAFS). For six certified reference material coals, the Hg concentrations obtained by this method were in good accordance with the certified or reference values. In addition, nine brands of Japanese standard coals (SS coals) were analyzed by the present method, and the data were compared to those from the authentic microwave-acid digestion (MW-AD) method. For the determination of total S in coal, the OFC method with H₂O₂ solution as an absorbent followed by ICP-AES or precipitation titration was successfully applied.     

CAL: A theoretical background of constraint logic programming and its applications

Constraint logic programming (CLP) is an extension of logic programming by introducing the facility of writing and solving constraints in a certain domain. CAL (Contrainte avec Logique) is a CLP language in which (possibly non-linear) polynomial equations can be written as constraints, while almost all the other CLP languages proposed so far have concentrated only on linear equations and inequations. This paper describes a general semantics of CLP including CAL, and shows the validity of CAL in this framework.     

Characterization of liquid product from the reaction of coal with hydrogen atoms

An oily product formed by the reaction of a domestic subbituminous coal (Taiheiyo coal) with hydrogen atoms at 200 °C, has been characterized. The material is essentially composed of C₅-C₂₂ alkanes and cycloalkanes. The $\text{H}\text{C}$ ratio, specific gravity and refractive index were 1.81, 0.855 and 1.447, respectively. The absence of heteroatoms, alkenes and aromatics in the product is the outstanding feature of the coal liquefaction induced by hydrogen atoms.     

Recent progress of Cat-CVD research in Japan—bridging between the first and second Cat-CVD conferences

We review the recent progress of Cat-CVD research in Japan since the 1st Cat-CVD conference in Kanazawa in 2000. Some groups, including ours, succeeded in realizing large-area deposition of amorphous silicon (a-Si) of approximately 1 m size, and thin film transistors (TFTs) with a mobility over several 10s of cm² V⁻¹ s⁻¹ are fabricated using Cat-CVD polycrystalline silicon (poly-Si) films. Extensive studies of in situ cleaning methods revealed that a high rate of chamber cleaning is possible in Cat-CVD systems. Solar cell research is now carried out within the New Energy and Industrial Technology Development Organization (NEDO) project, and the study of Cat-CVD Si₃N₄ films prepared at lower than 100 °C is now a Japan Science and Technology Corporation (JST) project to use them as coatings on organic devices. The feasibility of Cat-CVD for various applications has been widely demonstrated, along with further understanding of the fundamental mechanism of the Cat-CVD process.     

Effect of sequence distribution of poly(vinyl alcohol-vinyl acetate) on the coloring reaction with iodine

Red complex formation between poly(vinyl alcohol-vinyl acetate) with iodine was investigated from the standpoint of its application as a measure of sequence distribution in the copolymer. Defining a parameter Y which means a ratio of the bound triiodide ion to the VAc unit in a copolymer, we could relate the Y value to the sequence probabilities. Sequence probabilities have also been evaluated by differential thermal analysis. Comparing the probabilities obtained from both methods, the iodine complexation method is concluded to be a complementary method with thermal analysis, that is, the iodine complexation method is applicable to the VAc unit-rich copolymers, in which the melting point cannot be measured by the thermal analysis.