Improvement of Selectivity for Partial Hydrogenation of Benzene by Rare Earth Nitride Upon NH3 Treatment

For the liquid-phase partial hydrogenation of benzene at 483 K, the selectivity toward cyclohexene was greatly improved upon treating rare earth nitride with ammonia. For YbN obtained by thermal decomposition of Yb(NH₂)₂ at 1173 K, the selectivity of the NH₃-treated YbN was 75%, in contrast to nil for the untreated YbN.     

Preparation of regioisomers of structured TAG consisting of one mole of CLA and two moles of caprylic acid

TAG (MLM) with medium-chain FA (MCFA) at the 1,3-positions and long-chain FA (LCFA) at the 2-position, and TAG (LMM) with LCFA at the 1(3)-position and MCFA at 2,3(1)-positions are a pair of TAG regioisomers. Large-scale preparation of the two TAG regioisomers was attempted. A commercially available FFA mixture (FFA-CLA) containing 9-cis, 11-trans (9c, 11t)- and 10t,12c-CLA was selected as LCFA, and caprylic acid (C₈FA) was selected as MCFA. The MLM isomer was synthesized by acidolysis of acyglycerols (AG) containing two CLA isomers with C₈FA: A mixture of AG-CLA/C₈ FA (1∶10, mol/mol) and 4 wt% immobilized Rhizomucor miehei lipase was agitated at 30°C for 72 h. The ratio of MLM to total AG was 51.1 wt%. Meanwhile, LMM isomer was synthesized by acidolysis of tricaprylin with FFA-CLA: A mixture of tricaprylin/FFA-CLA (1∶2, mol/mol) and 4 wt% immobilized R. miehei lipase was agitated at 30°C for 24 h. The ratio of LMM to total AG was 51.8 wt%. MLM and LMM were purified from 1,968 and 813 g reaction mixtures by stepwise short-path distillation, respectively. Consequently, MLM was purified to 92.3% with 49.1% recovery, and LMM was purified to 93.2% with 52.3% recovery. Regiospecific analyses of MLM and LMM indicated that the 2-positions of MLM and LMM were 95.1 mol% LCFA and 98.3 mol% C₈ FA, respectively. The results showed that a process comprising lipase reaction and short-path distillation is effective for large-scale preparation of high-purity regiospecific TAG isomers.     

Novel SiC synthesis method applicable to SiC solid phase sintering

Most of the present production processes of SiC sintered bodies require some powder mixing using a mechanical milling process (ball milling, and so on). In this case, relatively long hours are required, and there is the problem of contamination during the preparation process. To avoid these problems, we developed a new process for obtaining a self-sinterable, stoichiometric SiC powder, whose precursor material is water-soluble; the precursor material was synthesized from aqueous silica and citric acid containing a small amount of aluminum compound. In order to obtain the stoichiometric SiC composition, the above aqueous precursor material was adequately cured in air (200°C-400°C); subsequently carbonization reaction (~800°C) in nitrogen atmosphere, carbothermal reduction (~1600°C) in argon atmosphere, and pressureless sintering (~1900°C) were performed. Among these processes, the curing process (cross-linking process) is very important for obtaining the equivalent composition (silica and carbon) for the subsequent carbothermal reduction. In this study, the adequate curing temperature and suitable preparation condition for the carbothermal reduction were investigated for the production of stoichiometric self-sinterable SiC powder. The pressureless sintered body achieved using the obtained SiC powder demonstrated a desirable trans-crystalline fracture behavior.     

Humidity Sensor Characteristics of Woodceramics

The humidity sensor characteristics of Woodceramics were investigated. The Woodceramics used in this experiment were prepared at 650–900°C. The size of specimens selected was 1 × 1 × 10 mm . One was used as-cut and the other was polished. Above 700°C, the resistance of the specimen was below 50 and the decrease of resistance with increasing relative humidity was small. The specimen prepared at 650°C had a resistance of about 1 k. The resistance of as-cut specimens decreased with increase in relative humidity, but that of the polished specimen did not change significantly. The difference between as-cut and polished samples was explained by the differences in surface micro-structure.     

Electromagnetic Shielding Properties of Woodceramics Made from Wastepaper

Woodceramics are new porous carbon materials, which are made by impregnating woody materials with phenol resin and then thermoformed in a vacuum furnace and these have been shown to have electromagnetic shielding properties. In the recycling of wastepaper, ways of using the wastepaper other than for paper pulp are needed to be developed. In this study, we made Woodceramics from handbill advertisement paper and telephone directory paper, and measured their electromagnetic shielding properties in order to find new uses for wastepaper. The results showed that the Woodceramics made from wastepaper had an electric shielding effectiveness of 30 dB for 100 MHz and 40 to 43 dB for 300 MHz or higher, and had a magnetic shielding effectiveness of 30 dB for 100 MHz and 37 dB for about 400 MHz. An electric equivalent circuit of the pore model in the Woodceramics is introduced. In addition, it is proposed that the excellent electromagnetic shielding effectiveness of the Woodceramics is caused by dielectric loss.     

Characterization of a Silk‐Resinified Compact Fabricated Using a Pulse‐Energizing Sintering Device

Pulse electric current sintering is used to prepare a compact from resinificated hydrous silk powder. Compacts with no remnant silk powders are formed with 20 wt% added water, 20–40 MPa molding pressure, and >353 K molding temperature. The latter two are much lower than those used for conventional hot pressing. No dependence on molding pressure and temperature are found in XRD or FT‐IR analysis, except for a compact molded at 473 K, for which silk fibroin decomposition is confirmed by DSC, EGA‐MS, and molecular weight measurements. The compact's three‐point bending strength depends on the molding temperature, except for the temperature at which silk fibroin decomposes. The maximum three‐point bending strength resembles that of general‐purpose epoxy resin and is much higher than that of PLA.

     

Thermodynamic stability of hydrogen+tetra-n-butyl phosphonium bromide mixed semi-clathrate hydrate

Three-phase equilibrium (pressure–temperature) relation of hydrate+aqueous+fluid phases for the hydrogen (H₂)+tetra-n-butyl phosphonium bromide (TBPB)+water ternary system was investigated in a temperature range of 281.90–295.94 K and a pressure range up to 170 MPa. The behavior of the three-phase coexisting curve indicates no structural transition in the present experimental region. The Raman spectra obtained in the H₂+TBPB mixed semi-clathrate hydrate crystal reveal that H₂ molecule occupies only small cage compartmentally and the TBPB molecule is encaged with a set of other large cages.     

Easy formation process of anatase-TiO2 coating layer strongly bonded to titanium metal surface

Because of the formation of a surface passive film (rutile TiO₂) on its surface layer, titanium metal shows adequate corrosion resistance. As the surface layer (passive film) of titanium metal is very stable, any functionalization of the titanium metal has been generally performed using relatively complicated methods. This is because any direct oxidation of titanium metal only leads to the formation of rutile TiO₂ over the entire temperature range. Chemical reactions using titanium chemicals can easily produce anatase TiO₂ at temperatures of ≤600°C. Using precursors is one of the ways of producing an anatase TiO₂ coating on titanium metal. However, in previous studies, anatase TiO₂ layers easily peeled off when they were used in flowing water. Herein, we describe a simple process for obtaining an anatase TiO₂ coating layer strongly bonded to the titanium metal surface. In our process, titanium metal was pretreated with a reducing agent to create a surface TiH₂ layer, whose condensation reaction easily proceeds with a precursor (composed of oxalic acid and tetra-butoxy titanium). Subsequently, the treated titanium metal was calcinated at 550°C in air to achieve strong bonding between the anatase TiO₂ coating layer and titanium metal surface. The treated titanium metal exhibited excellent photocatalytic activity.     

A novel spectroelectrochemical cell for in situ surface X-ray scattering measurements of single crystal disk electrodes

A newly designed spectroelectrochemical cell was constructed for surface X-ray scattering (SXS) to study single crystal electrodes. Electrochemical characteristics of a specific face of a single crystal electrode can be investigated in the meniscus mode, and SXS measurement can be easily carried out using the spectroelectrochemical cell. The usefulness of the present cell was demonstrated by studying the electrochemical deposition of thin Pd layers on Au(111) and Au(100) that require precise amounts of Pd deposits.     

Fractionation and enrichment of CLA isomers by selective esterification with Candida rugosa lipase

A commercial product of CLA contains almost equal amounts of cis-9,trans-11 (c9,t11)-CLA and trans-10,cis-12 (t10,c12)-CLA. We attempted to enrich the two isomers by a two-step selective esterification using Candida rugosa lipase that acted on c9,t11-CLA more strongly than on t10,c12-CLA. An FFA mixture containing CLA isomers was esterified with an equimolar amount of lauryl alcohol in a mixture of 20% water and the lipase. When the esterification of total FA reached 50%, two isomers were fractionated in a good yield: t10,c12-CLA was enriched in FFA, and c9,t11-CLA was recovered in lauryl esters. The FFA were esterified again to enrich t10,c12-CLA. At 27.3% esterification of total FA, the t10,c12-CLA content in FFA increased to 64.8 wt% with 89.3% recovery: The ratio of the content of t10,c12-CLA to that of two isomers was 95.9%. Lauryl esters obtained by the single esterification were employed for enrichment of c9,t11-CLA. After the esters were hydrolyzed, the resulting FFA were esterified again with lauryl alcohol. At 62.0% esterification of total FA, the c9,t11-CLA content in lauryl esters increased to 73.3 wt% with 79.4% recovery: The ratio of the content of c9,t11-CLA to that of two isomers was 95.6%. In a 600-g-scale purification, molecular distillation was effective in separating the reaction mixture into lauryl alcohol, FFA, and lauryl ester fractions.