Solidification in a water‐saturated porous medium when convection is present (response of solid‐liquid interface due to time‐varying cooling temperature)

A fundamental study on solidifying phenomenon in a rectangular space filled with water‐saturated porous medium has been carried out with a system, cooled from the upper boundary and heated from below, where vigorous convection develops in the un‐solidified liquid layer. The dynamic response of the solid‐liquid interface to the periodical cooling temperature with the bottom boundary kept at constant temperature T_H = 20°C, is investigated experimentally. In particular, the amplitude of the interface and the phase lag in respect to the oscillating cooling temperature have been monitored for various periods and average temperatures. A one‐dimensional numerical model, based on an assumption of constant heat flux from the vigorously convecting liquid regime has been also developed. The numerical model predicts quite well the time‐dependent behavior of the horizontally averaged ice‐layer thickness observed in the experiments. Our general findings are that the amplitude increases proportionally to the temperature fluctuation period and that both the thicker solid layer and the shorter period cause greater phase lags. © 2006 Wiley Periodicals, Inc. Heat Trans Asian Res, 35(4): 294–308, 2006; Published online in Wiley InterScience ( www.interscience.wiley.com ). DOI 10.1002/htj.20109     

Solar to chemical conversion using metal nanoparticle modified microcrystalline silicon thin film photoelectrode

Microcrystalline silicon (μc-Si:H) thin films, which are prospective low-cost semiconductor materials, are used as photoelectrodes for the direct conversion of solar energy to chemical energy. An n-type microcrystalline cubic silicon carbide layer and an intrinsic μc-Si:H layer are deposited on glassy carbon substrates using the hot-wire cat-CVD method. The μc-Si:H electrodes are modified with platinum nanoparticles through electroless displacement deposition. The electrodes produce hydrogen gas and iodine via photoelectrochemical decomposition of hydrogen iodide with no external bias under solar illumination. Surface modification with platinum nanoparticles and surface termination with iodine improve the conversion efficiency.     

Preliminary study on the thorium-loaded accelerator-driven system with 100 MeV protons at the Kyoto University Critical Assembly

At the Kyoto University Critical Assembly (KUCA), spallation neutrons generated by high-energy proton beams are injected into the thorium-loaded systems on March 2010. By combining the Fixed Field Alternating Gradient (FFAG) accelerator with the thorium-loaded system at KUCA, a series of the ADS experiments is carried out under conditions whereby the spallation neutrons are generated at a tungsten target by 100 MeV protons at an intensity of 30 pA. Prompt neutron behavior in the time evolution is observed and thorium fission reactions are attained through the experiments and calculations, respectively. And the effects of neutron leakage and spectrum softening are experimentally observed through the neutron multiplication and reaction rate analyses. From the experimental and numerical analyses, in the future, experimental conditions need to be improved to attain further neutron multiplication using the variation of fuels (thorium, highly-enriched and natural uranium) and moderators (graphite, polyethylene, aluminum and beryllium).     

Catalytic combustion of methane over Pt and PdO-supported CeO<Subscript>2</Subscript>–ZrO<Subscript>2</Subscript>–Bi<Subscript>2</Subscript>O<Subscript>3</Subscript>/γ-Al<Subscript>2</Subscript>O<Subscript>3</Subscript> catalysts

Catalytic combustion of methane was investigated on Pt and PdO-supported CeO₂–ZrO₂–Bi₂O₃/γ-Al₂O₃ catalysts prepared by a wet impregnation method in the presence of polyvinylpyrrolidone. The catalysts were characterized by X-ray fluorescence analysis, X-ray powder diffraction, X-ray photoelectron spectra, transmission electron microscopy, and BET specific surface area measurements. The Pt/CeO₂–ZrO₂–Bi₂O₃/γ-Al₂O₃ and PdO/CeO₂–ZrO₂–Bi₂O₃/γ-Al₂O₃ catalysts were selective for the total oxidation of methane into carbon dioxide and steam, and no by-products such as HCHO, CO, and H₂ were obtained. The catalytic activities of the PdO/CeO₂–ZrO₂–Bi₂O₃/γ-Al₂O₃ catalysts were relatively higher than those of the Pt-supported catalysts, due to the facile re-oxidation of metallic Pd into PdO based on lattice oxygen supplied from the CeO₂–ZrO₂–Bi₂O₃ bulk. A decrease in the calcination temperature during the preparation process was found to be effective in enhancing the specific surface area of the catalysts, whereby particle agglomeration was inhibited. Optimization of the PdO amount and calcination temperature enabled complete oxidation of methane at temperatures as low as 320 °C on the 11.6 wt% PdO/CeO₂–ZrO₂–Bi₂O₃/γ-Al₂O₃ catalyst prepared at 400 °C.     

Effect of Bi and Ti substitutions for Na and Nb on ferroelectric properties of oriented (Bi4.5+xNa0.5−x)(Ti2xNb2−2x)WO15 compounds

(Bi_4.5+xNa_0.5−x)(Ti_2xNb_2−2x)WO₁₅ (BNTNW) compounds were synthesized and their ferroelectric properties were characterized. The X-ray powder diffraction patterns of the compounds revealed that they have a single phase over the whole composition range. The linear variations of the lattice parameters with composition indicate the formation of solid solutions, resulting in a reduction in the orthorhombicity of the compounds. The remnant polarization of the BNTNW decreased from 8.5 to 5.1 μC/cm² with increasing x, which may be related to the orthorhombicity of the compounds. By using hot forging, an oriented BNTNW compound at x = 0 was obtained. Strong reflections from (0 0 l) were observed for sample // in which the measurement direction is parallel and the orientation factor of such sample was approximately 0.72. A remarkable increase in the remnant polarization (P_r) of the compound was observed for the sample ⊥ in which the direction of applied pressure is perpendicular to the measurement direction; the highest P_r value was 18 μC/cm².     

Influence of polymer infiltration and pyrolysis process on mechanical strength of polycarbosilane-derived silicon carbide ceramics

In this article, strength evaluation of silicon carbide (Si–C) ceramics fabricated from polycarbosilane (PCS) precursor is described. Si–C ceramics was prepared by firing a green body made of the mixture of Si–C nano-powders and a PCS solution at 1,273 K in N₂ gas for an hour. To obtain dense Si–C, the solution was infiltrated into the produced body, and then it was fired again. The polymer infiltration and pyrolysis (PIP) process was conducted up to 12 cycles. Si–C ceramics was diced to be rectangle shape measuring 1.0 mm × 3.0 mm × 0.5 mm, and was subjected to the three-point bending test for measurement of the Young’s modulus and bending strength. Si–C specimens fabricated through PIP processes less than 2 cycles showed non-linear force–displacement curves like a polymer, whereas those through the processes more than 3 cycles showed linear relations and fractured in a brittle manner. The Young’s modulus of 12-cycles-PIPs specimen was found to be 56 GPa on average, which was approximately 22-fold of non-PIP specimen. The bending strength was also increased with an increase in the number of PIP process. The maximum value was found to be 157 MPa. The cause of the influence of PIP process on the mechanical characteristics is discussed using a PCS-derived Si–C model.     

Cobalt oxide (Co3O4) nanorings prepared from hexagonal β-Co(OH)2 nanosheets

Hexagonal cobalt hydroxide (β-Co(OH)₂) nanosheets over a size range from 100 nm to 1 μm were synthesized using a very simple hydrothermal route with cobalt naphthenate as the cobalt source. Additionally, hexagonal cobalt oxide (Co₃O₄) nanorings over a size range from 100 nm to 1 μm consisting of cubic nanocrystals were obtained via a hydrothermal method using as-prepared β-Co(OH)₂ nanosheets as the precursors. A probable mechanism of formation of the hexagonal Co₃O₄ nanorings is proposed on the basis of time-dependent experimental results.     

Radical-initiator-Induced solid-state polymerization of butadiyne nanocrystals in water and their dispersion stabilization

Butadiyne nanocrystals in water are usually polymerized by UV or gamma-ray irradiation to give polydiacetylene (PDA) nanocrystals. In this study, we confirmed that solid-state polymerization of 1,6-di(N-carbazolyl)-2,4-hexadiyne (DCHD) and 5,7-dodecadiyn-1,12-diyl bis[N-(butoxycarbonyl-methyl)carbamate] (4BCMU) could be stimulated by water-soluble radical initiators. The radical initiators used were potassium peroxodisulfate, three kinds of azo-type compounds and a redox initiator. In all cases, the solid-state polymerization was confirmed by color change into blue indicating that PDA modified by the radical residues at the end was formed. However, nanocrystal cohesion occurred especially when the concentration of the initiators was high or the dispersion was kept for a long time. In order to improve the dispersion stability, two kinds of surfactants, i.e., sodium dodecyl sulfate (SDS) or dodecyltrimethylammonium chloride (DTMAC), were added to the DCHD nanocrystal aqueous dispersion. As a result, when anionic SDS was added, the solid-state polymerization of nanocrystals proceeded without coagulation and quantitative conversion was confirmed for all initiators. Cationic DTMAC has no effect on dispersion stabilization. PDA nanocrystal surfaces in water are negatively charged in nature and electric interaction of nanocrystals with the cations results in decrease of surface charge and aggregation of nanocrystals.     

N-nitrosamine rejection by reverse osmosis membranes: A full-scale study

This study aims to provide longitudinal and spatial insights to the rejection of N-nitrosamines by reverse osmosis (RO) membranes during sampling campaigns at three full-scale water recycling plants. Samples were collected at all individual filtration stages as well as at a cool and a warm weather period to elucidate the impact of recovery and feed temperature on the rejection of N-nitrosamines. N-nitrosodimethylamine (NDMA) was detected in all RO feed samples varying between 7 and 32 ng/L. Concentrations of most other N-nitrosamines in the feed solutions were determined to be lower than their detection limits (3–5 ng/L) but higher concentrations were detected in the feed after each filtration stage. As a notable exception, in one plant, N-nitrosomorpholine (NMOR) was observed at high concentrations in RO feed (177–475 ng/L) and permeate (34–76 ng/L). Overall rejection of NDMA among the three RO systems varied widely from 4 to 47%. Data presented here suggest that the feed temperature can influence rejection of NDMA. A considerable variation in NDMA rejection across the three RO stages (14–78%) was also observed. Overall NMOR rejections were consistently high ranging from 81 to 84%. On the other hand, overall rejection of N-nitrosodiethylamine (NDEA) varied from negligible to 53%, which was considerably lower than values reported in previous laboratory-scale studies. A comparison between results reported here and the literature indicates that there can be some discrepancy in N-nitrosamine rejection data between laboratory- and full-scale studies probably due to differences in water recoveries and operating conditions (e.g. temperature, membrane fouling, and hydraulic conditions).