Gravity consolidation-sedimentation behaviors of concentrated TiO2 suspension

Consolidation-sedimentation behaviors of consolidated sediment under action of gravity were investigated using highly concentrated suspension of titanium dioxide particles under conditions of various pHs, initial heights, and initial concentrations. The average consolidation ratio of the consolidated sediment was analyzed on the basis of the simplified analytical solution obtained using the modified Terzaghi's model under the moving Lagrangian coordinate system. Although the solution pH strongly affects consolidation-sedimentation behaviors, the modified average consolidation coefficient was little influenced by the solution pH. Also, the consolidation coefficient increased in almost direct proportion to the total volume of solids per unit cross-sectional area, which changes the driving force of consolidation-sedimentation due to the overlying weight of the solid particles. The variations with time of the height of the consolidated sediment were adequately described using the analytical solution describing the average consolidation ratio with the aid of the relation that the equilibrium height was represented by a power function of the total volume of solids for a specified pH.     

Active Polymer Gel Actuators

Many kinds of stimuli-responsive polymer and gels have been developed and applied to biomimetic actuators or artificial muscles. Electroactive polymers that change shape when stimulated electrically seem to be particularly promising. In all cases, however, the mechanical motion is driven by external stimuli, for example, reversing the direction of electric field. On the other hand, many living organisms can generate an autonomous motion without external driving stimuli like self-beating of heart muscles. Here we show a novel biomimetic gel actuator that can walk spontaneously with a worm-like motion without switching of external stimuli. The self-oscillating motion is produced by dissipating chemical energy of oscillating reaction. Although the gel is completely composed of synthetic polymer, it shows autonomous motion as if it were alive.     

Reaction mechanism in Ti–SiC–C powder mixture during pulse discharge sintering

During pulse discharge sintering (PDS) of Ti/SiC/C powder mixture, combustion synthesis reactions occurred at heating rates above 20 °C/min. With an increase in heating rate, combustion synthesis occurred at higher temperatures. The essential of this combustion reaction is the liquid reaction between Ti and formed Ti₅Si₃. The exothermic TiC formation during PDS process promotes this liquid reaction. We have found that the combustion reactions alone did not finish the formation reactions for Ti₃SiC₂, and further heating following the combustion reactions is necessary for the synthesis process of Ti₃SiC₂.     

Materials for global carbon dioxide recycling

CO₂ emissions, which induce global warming, increase with the development of economic activity. It is impossible to decrease the CO₂ emissions by suppression of the economic activity. Global CO₂ recycling can solve this problem. The global CO₂ recycling consists of three district: The electricity is generated by solar cells on deserts. At desert coasts, the electricity is used for H₂ production by seawater electrolysis and H₂ is used for CH₄ production by the reaction with CO₂. CH₄ which is the main component of liquefied natural gas is liquefied and transported to energy consuming districts where CO₂ is recovered, liquefied and transported to the desert coasts. A CO₂ recycling plant for substantiation of our idea has been built on the roof of the Institute for Materials Research in 1996. Key materials necessary for the global CO₂ recycling are the anode and cathode for seawater electrolysis and the catalyst for CO₂ conversion. All of them have been tailored by us. They have very high activity and selectivity for necessary reactions in addition to excellent durability. A pilot plant consisting of minimum units in an industrial scale is going to be built in three years.     

The alkylation of biphenyl over three-dimensional large pore zeolites: The influence of zeolite structure and alkylating agent on the selectivity for 4,4′-dialkylbiphenyl

Catalytic properties of three-dimensional zeolites, Y (FAU), Beta (BEA), and CIT-1 (CON) zeolites were examined in the alkylation, isopropylation, sec-butylation, and tert-butylation, of biphenyl (BP), and compared to those of H-mordenite (MOR). The selectivities for 4,4′-dialkylbiphenyl (4,4′-DABP) varied with the types of zeolite and of alkylating agent. FAU, BEA, and CON gave only low selectivities for 4,4′-diisopropylbiphenyl (4,4′-DIPB) in the isopropylation, and predominant isomers were bulky and thermodynamically unstable 2,x′-DIPB (2,2′-, 2,3′-, and 2,4′-) at lower temperatures, and bulky and thermodynamically stable 3,4′- and 3,3′-DIPB at higher temperatures: this is quite different from catalytic features over MOR, which gave 4,4′-DIPB with high selectivities at moderate temperatures. These results suggest that FAU, BEA, and CON have no shape-selective nature in the isopropylation, and that the reaction is principally controlled kinetically at lower temperatures, and thermodynamically at higher temperatures. The sec-butylation gave similar results to the isopropylation. Although the selectivities for 4,4′-di-sec-butylbiphenyl (4,4′-DSBB) were higher than those in the isopropylation, predominant isomers were 2,x′-DSBB (2,2′-, 2,3′-, and 2,4′-) at lower temperatures, and 3,4′- and 3,3′-DSBB at higher temperatures. The tert-butylation gave 4,4′-di-tert-butylbiphenyl (4,4′-DTBB) in moderate to high selectivities over all zeolites at moderate temperatures: the selectivity for 4,4′-DTBB was higher than 80% over BEA and CON; however, it still remained at 50% over FAU. FAU channels with super cages are too large for selective formation of 4,4′-DTBB.

From these results, it is concluded that the selectivity for 4,4′-DABP in the alkylation over MOR, FAU, BEA, and CON is determined by the exclusion of bulky isomers at their transition states, and that the exclusion is caused by the steric restriction at the transition states of bulky isomers by the zeolite channels.     

Direct synthesis of H2O2 acid solutions on carbon cathode prepared from activated carbon and vapor-growing-carbon-fiber by a H2/O2 fuel cell

Direct synthesis of H₂O₂ acid solutions was studied using a gas-diffusion cathode prepared from activated carbon (AC), vapor-growing-carbon-fiber (VGCF) and poly-tetra-fluoro-ethylene (PTFE) powders, with a new H₂/O₂ fuel cell reactor. O₂ reduction to H₂O₂ was remarkably enhanced at the three-phase boundary (O₂(g)-electrode(s)-acid(l)) at the [AC + VGCF] cathode. Fast diffusion processes of O₂ to the active surface and of H₂O₂ to the bulk acid solutions were essential for H₂O₂ accumulation. Synergy of AC and VGCF was observed for the H₂O₂ formation. RRDE and cyclic voltammetry studies indicated that the surface of AC functioned as the active phase for O₂ reduction to HO₂, and VGCF functioned as an electron conductor and a promoter to convert HO₂ to H₂O₂. A maximum H₂O₂ concentration of 353 mM (1.2 wt%) was accomplished under short-circuit conditions (current density 12.7 mA cm⁻², current efficiency 40.1%, geometric area of cathode 1.3 cm², reaction time 6 h).     

Effect of superfine particles of alumina incorporated in the cavities of mordenite in enhancing selectivity

Alumina has been incorporated in the cavities of mordenite by the hydrolysis of Al³⁺ ions in the cavities with moist ammonia gas, following calcination at 450°C. The incorporation of the superfine particles of alumina into the cavities of the mordenite is assessed on the basis of the data of MAS ²⁷Al NMR measurements, X-ray powder diffraction and the amount of saturated adsorption of nitrogen for FAL/MZ. The acid properties, assessed using NH₃ TPD and FTIR studies, show the presence of Brønsted and Lewis acid sites on the catalyst, and an increase in acidic sites on incorporating alumina. The dehydrogenation selectivities of FAL/MZ, Al³⁺/MZ, H⁺/MZ, and Na⁺/MZ have been investigated. Brønsted acid sites largely enhance the ring-cleavage, whereas this incorporation of superfine particles of alumina significantly suppresses the ring-cleavage. Therefore, the incorporation of the superfine particles increases remarkably in the cyclohexene selectivity.     

Spatial distribution of silica fillers in phase-separated rubber blends investigated by three-dimensional elemental mapping

The distribution of nano-sized silica in binary rubber blends is characterized by scanning transmission electron microscopy (STEM) tomography combined with energy dispersive X-ray spectrometry (EDX). 3D distribution of silica is visualized by STEM-EDX tomography with the tilt-series of silicon elemental maps, while the phase-separated morphologies of polyisoprene rubber (IR) and styrene-butadiene rubber (SBR) are visualized by STEM-tomography in high-angle-annular-dark field (HAADF) mode. The combination of STEM-EDX and STEM-HAADF tomography enables us to determine the distribution of silica between the two rubber phases quantitatively even with high contents of silica up to 70 phr (weight parts per hundred rubber). It is found that silica is preferentially distributed in the SBR phase, but it is also distributed in the IR phase when the IR fraction in the total rubber components is higher than 40 wt%. The preferential distribution of silica in the SBR phase improves the dispersion of the IR domains. This is the first use of this technique for a multicomponent polymer system, showing the advantage to characterize the complicated multicomponent polymer composite morphologies.