Structure Evolution of Highly Crystallized BaWO4 Film Prepared by an Electrochemical Method at Room Temperature

Highly crystallized BaWO₄ films have been prepared on a tungsten substrate in an alkaline solution containing barium ions by an electrochemical method with a constant direct current density of 1 mA/cm² at room temperature (25°C). The average grain size was about 13 μm, and the thickness about 9 μm after a treatment time of 35 min. The dependence of cell voltage on deposition time was divided into three steps: conduction, anodic oxidation, and breakdown steps. The BaWO₄ film formed during the first step. Electrochemical dissolution of metal tungsten occurred with an accompanying positive change of overpotential in the first step. The crystallization of BaWO4 was characterized by three-dimensional nucleation. In the second step, an amorphous tungsten oxide film formed, thereby increasing the potential. An electrical breakdown occurred in the third step, and the breakdown voltage (about 90 V) was practically the same as those of anodic tungsten oxide films.     

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.     

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.     

Electrochemical decomposition of CO2 and CO gases using porous yttria-stabilized zirconia cell

Electrochemical decomposition of CO₂ and CO gases using a porous cell of Ru-8 mol% yttria-stabilized zirconia (YSZ) anode/porous YSZ electrolyte/Ni–YSZ cathode system at 400–800 °C was studied by analyzing the flow rate and composition of outlet gas, current density, and phases and elementary distribution of the electrodes and electrolyte. A part of CO₂ gas supplied at 50 ml/min was decomposed to solid carbon and O₂ gas through the cell at the electric field strengths of 0.9–1.0 V/cm. The outlet gas at a flow rate of 3 ml/min included 61–63% CO₂ and 37–39% O₂ at 700–800 °C and the outlet gas at a flow rate of 50 ml/min included 73–96% (average 85%) CO₂ and 4–27% (average 15%) O₂ at 800 °C. On the other hand, the supplied CO gas was also decomposed to solid carbon, O₂ and CO₂ gases at 800 °C. The fraction of outlet gas at a flow rate of 50 ml/min during the CO decomposition at 800 °C for 5 h was 11–36% CO, 59–81% O₂ and 2–9% CO₂. The detailed decomposition mechanisms of CO₂ and CO gases are discussed. Both Ni metal in the cathode and porous YSZ grains under the DC electric field have the ability to decompose CO gas into solid carbon and O²⁻ ions or O₂ gas.     

Synthesis of stable and soluble one-handed helical poly(substituted acetylene)s without chiral pendant groups via polymer reaction in membrane state

A soluble and stable one-handed helical conjugated polymer without the coexistence of any other chiral moieties was successfully synthesized by asymmetric-induced polymerization of a chiral monomer having two hydroxyl groups followed by desubstitution of the chiral groups in a solid membrane state. The reason for the success was the polymer reaction was carried out in the membrane state. This is an alternative method to obtain such a unique chiral polymer which was obtained only by the helix-sense-selective polymerization (HSSP) we reported before. In addition the efficiency of the chiral induction was higher than that of the HSSP. It is interesting that the “Membrane state” acted like as if a protecting group.     

Polyhydrides of Sc,Zr and Hf and Their Proposed Formation.

Hydrogenation at 500 psi of (PNP)Sc(CH₃)₂ results in formation of a trinuclear polyhydride complex [(PNP)Sc]₃(μ₂-H)₄(μ₃-H)₂ ( 1 ) in 55 % yield. The solid-state structure shows a non-symmetric trinuclear species resulting from one pincer phosphine arm being demetallated, and where two hydrides bridge all three Sc centers, whereas the other four bridge two. Hydrogenation of (PNP)Zr(CH₃)₃ at 200 psi results instead in formation of a dinclear polyhydride species [(PNP)Zr(H)]₂(μ₂-H)₄ ( 2 ). Conducting the hydrogenation at atmospheric pressure, resulted instead in formation of the bridging methylidene complex [(PNP)Zr(CH₃)]₂(μ₂-H)₂(μ₂-CH₂) ( 3 ), which cleanly converted to 2 , upon hydrogenation at higher pressure. Both 2 and 3 were also structurally characterized. Hydrogenation of (PNP)Hf(CH₃)₃ at 200 psi resulted in incomplete hydrogenation with some formation of dinuclear mono- and dimethyl-polyhydride complexes [(PNP)Hf(CH₃)]₂(μ₂-H)₄ ( 4 ) and [(PNP)Hf(CH₃)][(PNP)Hf(H)](μ₂-H)₄ ( 5 ), which were identified by solid-state X-ray structural studies. Based on these results, we propose a pathway for the complete hydrogenation of (PNP)Zr(CH₃)₃ to 2 .     

Photocatalytic Synthesis of p-Anisaldehyde in a Mini Slurry-Bubble Reactor under Solar Light Irradiation

Dense photocatalyst slurry was employed for the synthesis of p-anisaldehyde under solar light irradiation. An Fe-modified rutile TiO ₂ (Fe-TiO _2, 34.5 m ²/g) photocatalyst was used as a visible-light-responsive photocatalyst. A conventional TiO ₂ (P25, 35 m ²/g) photocatalyst was also examined as a reference catalyst. XRD patterns and diffuse reflectance spectra showed that Fe-TiO ₂ consists of 100 % rutile phase and absorbs more visible light compared to P25, respectively. The catalyst powder was suspended in an ethyl acetate solution of p-methoxytoluene in the mini-reactor, with oxygen bubbling, under a solar simulator, visible light, and UV LEDs. p-anisaldehyde, as a reaction product, was analyzed by sampling using gas-chromatograph. Regardless of the light source, Fe-TiO ₂ always outperformed P25 in terms of both generation rates (GR) of p-anisaldehyde and energy requirements (ER). It was demonstrated that the highly dense Fe-TiO ₂ slurry was efficient for the synthesis under solar light owing to the small size of the reactor. The small amount of Pt and ZrO ₂ cocatalysts significantly enhanced the GR under solar light. By adopting a visible light responsive Fe-TiO ₂ photocatalyst, the mini slurry-bubble reactor under solar light achieved a high GR per catalyst mass (CM), which is one to two orders higher than that reported by most previous studies with high-power lamps.     

Improvement of the surface quality of foam injection molded products from a material property perspective

Microcellular injection molding is an attractive method. However, their surface imperfections have been a major problem hindering wide industrial applications. Several methods have been proposed to improve the surface appearance of foams. In this study, we proposed a method to improve the surface appearance of polypropylene (PP) foams from the material property perspective, especially with regard to crystallization and viscosity. The basic idea of the surface improvement is to reduce the size of bubbles generated at the flow front, delay the solidification behavior of the polymer at the mold interface, squeeze the bubbles existing at the mold–polymer interface, and redissolve the bubbles into the polymer by holding pressure. Blending a low-modulus PP delays the crystallization of the polymers at the skin layer and solidification, taking enough time to squeeze the bubbles smaller. A sorbitol-based gelling agent, bis-O-([4 methylphenyl]methylene)-D-Glucitol, was used to increase the viscosity at a low strain rate to reduce the size of the bubbles generated at the flow front during the filling stage. The foam injection molding experiments demonstrated that the proposed method effectively improved the surface appearance of the foams. In particular, the surface appearance of the foams became almost equivalent to that of solid samples using low-modulus PP.     

Roles of inherent metallic species in secondary reactions of tar and char during rapid pyrolysis of brown coals in a drop-tube reactor

Two pairs of raw and acid-washed coal samples were prepared from Yallourn and Loy Yang brown coals, and subjected to rapid pyrolysis in a drop-tube reactor at 1073-1173 K in a stream of N₂ or H₂O/N₂ mixture. Examinations were made on the roles of the inherent metallic species in the secondary reactions of nascent tar and char that were formed by the intraparticle primary reactions. The experimental results revealed that the inherent metallic species were essential for vary rapid steam reforming/gasification of the nascent tar/char and simultaneous suppression of soot formation. In the absence of the metallic species, the soot formation from the tar accounted as much as 15-19 and 6-13% of the carbon in coal in N₂ and H₂O/N₂, respectively. The metallic species reduced the yield of soot to 6-8% in N₂ by enhancing the reforming of tar by H₂O generated from the pyrolysis of coal. In the H₂O/N₂ stream, instead of soot formation, a net gasification conversion up to 17% within 4.3 s was observed in the presence of the metallic species as a result of catalytic gasification of the nascent char. Moreover, the metallic species catalyzed the steam reforming of the nascent tar, giving its conversion up to 99%. Over the range of the conditions employed, a one-to-one stoichiometry was established between the steam consumption and the yield of carbon oxides formed by the steam reforming/gasification and water-gas-shift reaction.