Highly oriented growth of titanate nanotubes (TNTs) in micro and confinement spaces on sol–gel derived amorphous TiO2 thin films under moderate hydrothermal condition

Synthesis of titanate nanotubes (TNTs) from sol–gel derived amorphous TiO₂ thin films under moderate hydrothermal condition has been reported. TNTs from film possess a tubular morphology that is the same crystalline phase as one synthesized from TiO₂ powder so far. TNTs obtained in this study are not entangled one another but oriented and isolated on the substrate. Growth of highly oriented TNTs is observed in micro grooves of amorphous TiO₂ thin film. Their orientation is also maintained with the growth of TNTs.     

Dynamical study of femtosecond-laser-ablated liquid-aluminum nanoparticles using spatiotemporally resolved x-ray-absorption fine-structure spectroscopy

We study the temperature evolution of aluminum nanoparticles generated by femtosecond laser ablation with spatiotemporally resolved x-ray-absorption fine-structure spectroscopy. We successfully identify the nanoparticles based on the L-edge absorption fine structure of the ablation plume in combination with the dependence of the edge structure on the irradiation intensity and the expansion velocity of the plume. In particular, we show that the lattice temperature of the nanoparticles is estimated from the L-edge slope, and that its spatial dependence reflects the cooling of the nanoparticles during plume expansion. The results reveal that the emitted nanoparticles travel in a vacuum as a condensed liquid phase with a lattice temperature of about 2500 to 4200 K in the early stage of plume expansion.     

Synergistic Spin Transition between Spin Crossover and Spin‐Peierls‐like Singlet Formation in the Halogen‐Bonded Molecular Hybrid System: [Fe(Iqsal)2][Ni(dmit)2]⋅CH3CN⋅H2O

To introduce halogen‐bond interactions between a cation and an anion, a novel Fe^III complex from iodine‐substituted ligands involving a paramagnetic nickel dithiolene anion was prepared and characterized. The compound exhibited the synergy between a spin‐crossover transition and a spin‐Peierls‐like singlet formation. The halogen‐bond interactions between the iodine and the sulfur atoms stabilized the paramagnetic state of π‐spins and played a crucial role in the synergistic magnetic transition between d‐ and π‐spins. In addition, the compound showed the light‐induced excited spin state trapping effect.     

Plasma production by helicon and slow waves

The observation of slow-wave sustained (SW) discharge in a whistler- or helicon-wave range of frequency is made using high-frequency and very-high-frequency bands of rf. The SW discharge occurs at an extremely low rf power and plasma density, which are lower than a capacitive-coupling discharge region.     

SmI2-promoted tandem desulfurization and reductive coupling reactions of aromatic lactams with carbonyl compounds

Treatment of sulfur-substituted aromatic lactams with carbonyl compounds in the presence of samarium(II) diiodide was found to undergo novel tandem desulfurization and reductive coupling reactions to generate -hydroxyalkylated lactams in high yield. Stereochemistry of the coupling products was researched and the results that decreasing the steric bulkiness of the N-substituents as well as raising the reaction temperature leads to an increase of the erythro-selectivity were observed. The mechanistic origins of this stereoselectivity are also briefly documented.     

Structural characterization of hierarchically porous alumina aerogel and xerogel monoliths

Detailed nanostructures have been investigated for hierarchically porous alumina aerogels and xerogels prepared from ionic precursors via sol–gel reaction. Starting from AlCl₃·6H₂O and poly(ethylene oxide) (PEO) dissolved in a H₂O/EtOH mixed solvent, monolithic wet gels were synthesized using propylene oxide (PO) as a gelation initiator. Hierarchically porous alumina xerogels and aerogels were obtained after evaporative drying and supercritical drying, respectively. Macroporous structures are formed as a result of phase separation, while interstices between the secondary particles in the micrometer-sized gel skeletons work as mesoporous structures. Alumina xerogels exhibit considerable shrinkage during the evaporative drying process, resulting in relatively small mesopores (from 5.4 to 6.2 nm) regardless of the starting composition. For shrinkage-free alumina aerogels, on the other hand, the median mesopore size changes from 13.9 to 33.1 nm depending on the starting composition; the increases in PEO content and H₂O/EtOH volume ratio both contribute to producing smaller mesopores. Small-angle X-ray scattering (SAXS) analysis reveals that variation of median mesopore size can be ascribed to the change in agglomeration state of primary particles. As PEO content and H₂O/EtOH ratio increase, secondary particles become small, which results in relatively small mesopores. The results indicate that the agglomeration state of alumina primary particles is influenced by the presence of weakly interacting phase separation inducers such as PEO.     

Traveling disturbance appearing in boundary layer transition in a Yawed cylinder

Boundary layers that develop over a body in fluid flow are in most cases three-dimensional owing to the spin, yaw, or surface curvature of the body. Therefore, the study of three-dimensional (3D) boundary-layer transition is essential to work in practical aerodynamics. The present investigation is concerned with the problem of 3D boundary layers over a yawed body. A yawed cylinder model that represents the leading edge portion of a swept wing and the mechanism of crossflow instability are investigated in detail using hot-wire velocimetry and a flow visualization technique. As a result, traveling disturbances having frequencies f₁ and f₂, which differ by about one order of magnitude, are detected in the transition region. The phase velocities and directions of travel of those disturbances are measured. Results for the low-frequency disturbance f₁ show qualitative coincidence with results numerically predicted for a crossflow unsteady disturbance. Nameley, F₁ travels nearly spanwise to the yawed cylinder and very close to the cylinder wall. The results for the high-frequency disturbance f₂ good agreement with the existing experimental results. The ₂ disturbance is found to be the high-frequency inflectional secondary instability that appears in 3D boundary layer transition in general. A two-stage transition process, where stationary crossflow vortices appear as the primary instability and a traveling inflectional disturbance is generated as a secondary instability, was observed. Secondary instability seems to play a major role in turbulent transition.     

Gasification characteristics of woody biomass in the packed bed reactor

Gasification technology is recognized as one of the possibilities for utilizing biomass effectively. This study focused on woody biomass gasification fundamentals, using a bench-scale packed-bed reactor. In this experiment, pellets of black pine were gasified, using air as the oxidizing agent. Gasification tests were carried out under both updraft and downdraft conditions. Temperature distributions and compositions of syngas inside the gasifier were continuously monitored during gasification experiments at several ports on the wall of the reactor. The syngas at the exit of the gasifier was also sampled to estimate the amount of tar. Lower heating values of the syngas under updraft and downdraft conditions were 4.8 and 3.8 MJ/m³N, respectively. It was easier to control the height of the packed bed under the downdraft condition than under the updraft condition. Under the updraft condition, a bridging phenomenon occurred. Tar generation under the downdraft condition was lower than that under the updraft condition. This is because tar passes through a partial combustion zone or higher temperature zone in the downdraft gasifier.     

Persistent hole burning in semiconductor nanocrystals

The persistent spectral hole burning (PSHB) phenomenon was found to occur in many kinds of nanocrystalline semiconductors, such as CdSe, CdS, CuCl, CuBr and CuI, embedded in crystals, glass or polymers. In inhomogeneously broadened exciton absorption spectra of these nanocrystals, the spectral hole and its associated structure were created by the narrow-band laser excitation and were conserved for more than several hours at 2 K. Hole depth grew in proportion to the logarithm of the burning fluence. Thermally-annealing and light-induced hole-filling phenomena were observed. The hole burning takes place by the tunneling process through potential barriers with broadly distributed barrier height and thickness. Unusual luminescence behaviors related to the PSHB phenomena were also observed. They are luminescence elongation with increase of the light exposure and hole burning in the luminescence spectrum. The observed PSHB phenomena are explained by the exciton localization and the succeeding ionization of nanocrystals. The energy of the photoionized nanocrystal is released from the original energy and the new energies depend on the spatial arrangement of the trapped carriers. Quantum confinement of carriers and resulting strong Coulomb interaction between confined carriers and trapped carriers are essential for the energy change. Possible applications of the PSHB phenomenon is discussed.