Photocatalytic Property and Electronic Structure of Lanthanide-based Oxysulfides

Lanthanide-based oxysulfides and sulfide, LnTaO_3.5S_0.5, Ln₁₀OS₁₄ (Ln = La, Pr, Nd, Sm) and La₄In₅S₁₃, were successively synthesized by sulfurization in a flowing H₂S. The sulfurization decreased the band-gap energies from >4 eV to <3eV, because of the formation of occupied S3p orbitals on the top of valence band. In accordance with the small band gap, the H₂ evolution from a 0.01 M Na₂S and 0.01 M Na₂SO₃ solution system was observed under irradiation of light up to >500 nm. The rate of H₂ evolution under light irradiation of >500 nm increased in the order of Ni/LaTaO_3.5S_0.5 < Ru/La₁₀OS₁₄ < Pt/La₄In₅S₁₃.     

Oxidative coupling of methane over LaCoO3−δ-based mixed oxides

The catalytic activity of LaCoO_3–-based mixed oxides for the oxidative coupling of methane has been tested by TPR and cyclic reaction. Characterization has been done by XRD, TGA and Mössbauer spectrometry. It is likely that the perovskite-crystal structure containing hypervalent metal ions has an important role and that unique structural oxygen species in the perovskite contribute to the partial oxidation of methane.     

Enhanced thermal stability of poly(lactide)s in the melt by enantiomeric polymer blending

Poly(l-lactide) (i.e. poly(l-lactic acid) (PLLA)) and poly(d-lactide) (i.e. poly(d-lactic acid) (PDLA)) and their equimolar enantiomeric blend (PLLA/PDLA) films were prepared and the effects of enantiomeric polymer blending on the thermal stability and degradation of the films were investigated isothermally and non-isothermally under nitrogen gas using thermogravimetry (TG). The enantiomeric polymer blending was found to successfully enhance the thermal stability of the PLLA/PDLA film compared with those of the pure PLLA and PDLA films. The activation energies for thermal degradation (ΔE_td) were evaluated at different weight loss values from TG data using the procedure recommended by MacCallum et al. The ΔE_td values of the PLLA/PDLA, PLLA, and PDLA films were in the range of 205-297, 77-132, and 155-242 kJ mol⁻¹ when they were evaluated at weight loss values of 25-90% and the ΔE_td value of the PLLA/PDLA film was higher by 82-110 kJ mol⁻¹ than the averaged ΔE_td value of the PLLA and PDLA films. The mechanism for the enhanced thermal stability of the PLLA/PDLA film is discussed.     

Microporous carbons prepared from cationic surfactant-resorcinol/formaldehyde composites

Microporous carbons have been synthesized by the carbonization of cationic surfactant-resorcinol/formaldehyde (RF) composites, which were themselves formed by electrostatic organic-organic interaction. The porous structure produced by the decomposition of the surfactant plays an important role for the gasification of the RF polymer at higher temperatures. The pore size of the carbon prepared from tetrapropylammonium bromide (TPAB)-RF, cetyltrimethylammonium bromide (C₁₆TAB)-RF and decyltrimethylammonium bromide (C₁₀TAB)-RF mixtures can be estimated as 0.53 nm from the Horvath-Kawazoe method using N₂ adsorption isotherms. Their pore size distributions were very narrow, showing that the microporous carbons derived from surfactant-RF mixture may have promise as adsorbents and membrane materials.     

One-Step Synthesis of Luminescent Nanoparticles of Complex Oxide, Strontium Aluminate

An organic aqueous solution of metal acetylacetonate precursors was subjected to spray pyrolysis in order to fabricate SrAl₂O₄:Eu (SAO) nanoparticles. Non-agglomerated luminescent SAO nanoparticles, having a spherical shape with a size of 10–30 nm, were achieved in a single step, while only submicrometer-sized SAO particles were obtained from the conventional ultrasonic pyrolysis of the metal nitrates. Without any post-annealing process, the as-prepared SAO nanoparticles were observed to exhibit a strong photoluminescence, which is comparable with that of the submicrometer-sized SAO particles. A mechanism for the formation of the nanoparticles is also discussed.     

Electro-rheological effect and dynamic rheological properties of a blend composed of two liquid crystalline materials with different molecular weight

Electro-rheological (ER) effect of a blend composed of two liquid crystalline materials with different molecular weights is described in this article. The results indicated that ER effect of the blend was observed at the temperature range where each neat sample did not show ER effect. Furthermore, both storage modulus (G′) and loss modulus (G″) decreased drastically at the temperature range for the blend in dynamic viscoelastic measurements. We show that steady ER effect could be obtained by using a blend made up of two liquid crystalline components, whereas remarkable increment in shear stress was not observed for each component under applied electric field.     

Hydrothermal Formation of Hydroxyapatite Layers on the Surface of Type-A Zeolite

Type-A zeolite evenly covered with hydroxyapatite thin layers was prepared using hydrothermal treatment at 120°C for 8 h under autogenous pressure. The hydroxyapatite needlelike nanocrystals, 100–200 nm in diameter and 30 nm in thickness, were grown under the reaction between discharged Ca²⁺ ions from type-A zeolite and PO₄³⁻ ions in (NH₄)₃PO₄ solution. The preferential orientations of the c -axis of hydroxyapatite crystals perpendicular to a zeolite surface were observed using transmission electron microscopy. The crystal structure of type-A zeolite was not destroyed under the reaction, but the surface morphology was changed only with complete covering of scaly hydroxyapatite particles.     

Synthesis and luminescence properties of Pr3+ doped CaxBa1?xTiO3 (0.3?x<1) fine particles

Ca _x Ba_1−x TiO₃ (CBT) fine particles doped with red luminescence center of Pr³⁺ ions (Pr: CBT) were successfully synthesized by salt assisted spray pyrolysis (SASP) process. Scanning electronic microscope (SEM) and laser scattering analysis demonstrate that salt can be removed from the surface of particles by washing with Milli-Q water and the particles can be further separated by ball-milling to get well-dispersed Pr³⁺ ions doped CBT fine particles. The luminescence properties, such as photoluminescence (PL) and mechanoluminescence (ML), of as-synthesized Pr: CBT particles were investigated. For Pr: CBT fine particles with different Ca molar ratios, all the samples show one emission at 612 nm, with increasing Ca molar ratio, PL intensity of Pr: CBT fine particles become stronger and stronger. When pressure was loaded on the Pr: CBT pellet, mechanoluminescence(ML) emission was measured. The results show that the ML intensity is proportional to the applied pressure.     

Microstructures of functionally graded materials fabricated by centrifugal solid-particle andin-situ methods

Functionally graded materials (FGMs) belong to a relatively new class of inhomogeneous composite materials, in which the composition and/or microstructure undergo a gradual change along some directions. In this review article, the microstructures and composition gradients in Al/SiC, Al/Shirasu (volcanic eruptions commonly found in south Kyushu in Japan), Al/Al₃Ti, Al/Al₃Ni, Al/Al₂Cu FGMs have been investigated. The Al/SiC, Al/Shirasu and Al/Al₃Ti FGMs are fabricated by the centrifugal solid particle method where the distribution particles of SiC, Shirasu and Al₃Ti are solids in the melts. On the other hand, Al/Al₃Ni and Al/Al₂Cu FGMs are fabricated by the centrifugalin-situ method where Al/Al₃Ni and Al/Al₂Cu systems have lower liquidus temperatures than the processing temperatures. The feature of Al/(Al₃Ti−Al₃Ni) hydrid FGM, which is fabricated by a method combining both the centrifugal solid-particle andin-situ methods, is also shown.