Synthesis and photoinduced surface relief grating formation of novel photo-responsive amorphous molecular materials, 4-[bis(9,9-dimethylfluoren-2-yl)amino]-4′-cyanoazobenzene and 4-[bis(9,9-dimethylfluoren-2-yl)-amino]-4′-nitroazobenzene

Novel azobenzene-based photo-responsive amorphous molecular materials, 4-[bis(9,9-dimethylfluoren-2-yl)amino]-4′-cyanoazobenzene and 4-[bis(9,9-dimethylfluoren-2-yl)amino]-4′-nitroazobenzene, have been synthesized and the formation of surface relief grating on their amorphous films has been investigated. It was found that a relatively large surface relief grating could be inscribed on both amorphous films upon interference exposure to the writing laser beams. The modulation depth of the surface relief grating inscribed on the amorphous film of the cyano-substituted material was found to be larger than that inscribed on the film of the nitro-substituted one and seemed to be comparable to that inscribed on the amorphous film of the parent material, 4-[bis(9,9-dimethylfluoren-2-yl)amino]azobenzene. These results were discussed from the viewpoint of their trans–cis photoisomerizations as amorphous films and glass-transition temperatures.     

High-pressure studies on Tc and crystal structure of iron chalcogenide superconductors

The superconducting transition temperature, T_c, in iron-based solids can be enhanced by applied pressure: T_c increases from 8 to 37 K for the 11-type FeSe when the pressure is raised from 0 to 4 GPa. High-pressure studies can elucidate the mechanism of superconductivity in such novel materials. In this paper, we present a high-pressure study of Fe(Se_1−xTe_x) and Fe(Se_1−xS_x). In the case of Fe(Se_1−xTe_x), the maximum T_c under high pressure did not exceed the T_c of FeSe, which can be attributed to the structural transition to the monoclinic phase. For Fe(Se_1−xS_x) (0 < x < 0.3), T_c exhibited a significant increase with pressure; however, the maximum T_c under high pressure did not exceed the T_c of FeSe. This may be due to the disorder induced by substituting S for Se, which is similar to the pressure effect on T_c for the 1111-type superconductor Ca(Fe_1−xCo_x)AsF. The T_c of Fe(Se_1−xS_x) showed a complex behavior below 1 GPa, first decreasing and then increasing with increasing pressure. From high-pressure x-ray diffraction measurements, the T_c (P) curve was correlated with the local structural parameter.     

Novel photoactive aggregates of rhodamine 6G: dequenched and quasi-stable aggregates induced by a dewetting process

Self-organized rhodamine 6G particles prepared by wetting/dewetting process of an ethanol solution on a hydrophilic glass surface exhibits fluorescence without quenching, showing a sharp linewidth of 2nm with a large redshift, which indicates an existence of dye aggregates, similar to J-aggregates, inside the particle. Polarized evanescent field excitation showed that the dye molecule's transition moment along the pi-conjugation was oriented unidirectionally within particles and parallel to the substrate surface. This deduced dye orientation showed correlation between adjacent, but separated, particles and pointed roughly 45 degrees off the dewetting direction. In contrast, the particles of another pi-conjugated NK1420 dye, J-aggregates of which grows easily from an oversaturated solution, showed dye orientation along the dewetting direction preferably, still indicating the effect of self-organization, however based on a different mechanism. An annealing procedure revealed that both aggregates are in quasi-stable states, which is consistent with the rapidness of the dewetting process that may lead to crystallization in nonequilibrium.     

Effect of Support Materials on the Selective Methanation of CO over Ru Catalysts

Selective methanation of CO in the reformate gas (CO/CO₂/H₂/H₂O = 0.175/17.9/70.9/11.1) proceeded over Ru catalysts supported on metal oxides and zeolites. CO was selectively methanated at wide temperature ranges (200–275 °C) over Ru/γ-Al₂O₃, Ru/TiO₂ Ru/H-Y and Ru/H-beta catalysts. Higher Ru contents in Ru/γ-Al₂O₃ improved the selective CO methanation rate.     

Enhanced activity and stability of Pt/C fuel cell anodes by the modification with ruthenium-oxide nanosheets

Ruthenium-oxide nanosheet (RuO₂ns) crystallites with thickness less than 1 nm were prepared via chemical exfoliation of a layered potassium ruthenate and deposited onto carbon supported platinum (Pt/C) as a potential co-catalyst for fuel cell anode catalysts. The electrocatalytic activity towards carbon monoxide and methanol oxidation was studied at various temperatures for different RuO₂ns loadings. An increase in electrocatalytic activity was evidenced at temperatures above 40 °C, while little enhancement in activity was observed at room temperature. The RuO₂ns modified Pt/C catalyst with composition of RuO₂:Pt = 0.5:1 (molar ratio) exhibited the highest methanol oxidation activity. CO-stripping voltammetry revealed that RuO₂ns promotes oxidation of adsorbed CO on Pt. In addition to the enhanced initial activity, the RuO₂ns modified Pt/C catalyst exhibited improved stability compared to pristine Pt/C against consecutive potential cycling tests.     

Synthesis and characterization of dextrin derivatives by heterogeneous esterification

A series of fully-acylated dextrin esters (DS = 3) with varying side-chain lengths (C2–12) were synthesized by heterogeneous esterification using trifluoroacetic anhydride/carboxylic acid. The influence of side-chain lengths on structure and properties of dextrin esters were investigated by structural, thermal, mechanical and hydrophobic analysis. The thermal stability of dextrin was enhanced by esterification, presenting ca. 40–60 °C higher decomposition temperatures than that of neat-dextrin. The transition temperatures of melting and crystallization were not observed for all dextrin esters because they were amorphous polymers. The glass transition temperature (T_g) was not observed in dextrin but was observed in dextrin esters. As increasing side-chain length, T_gs of dextrin esters decreased ranged from 162.2 °C (C2) to 49.2 °C (C12). Colorless and transparent dextrin ester films were prepared to measure the film properties. Tensile strength of dextrin ester films tended to decrease with increasing side-chain lengths, whereas the elongation at break increased. And, dextrin ester films showed significantly increased hydrophobicity with a contact angle of up to 102° (C12).     

Influence of LiBO2 addition on the microstructure and lithium-ion conductivity of Li1+xAlxTi2−x(PO4)3(x = 0.3) ceramic electrolyte

Concerning the safety problems of conventional Li-ion batteries with liquid electrolytes, it is crucial to develop reliable solid-state electrolytes with high ionic conductivity. Li_1+xAl_xTi_2?x(PO₄)₃ (LATP, x = 0.3) is regarded as one of the most promising solid electrolytes due to its high ionic conductivity and excellent chemical stability to humidity.Herein, a new strategy is proposed for improving the sintering behavior and enhancing the ionic conductivity of LATP by using LiBO₂ as the sintering aid via liquid phase sintering. The as-prepared sample LATP with homogeneous microstructure and high relative density of 97.1% was successfully synthesized, yielding high total ionic conductivity of 3.5 × 10^?4 S cm^?1 and low activation energy of 0.39 eV at room temperature. It was found that the addition of LiBO₂ could effectively enhance the densification and increase the ionic conductivity of LATP electrolyte, proving an effective way to synthesis LATP ceramics by a simple and reliable route.     

Fabrication of 0.24Pb(In1/2Nb1/2)O3-0.42Pb(Mg1/3Nb2/3)O3-0.34PbTiO3 transparent ceramics by conventional sintering technique

0.24Pb(In_1/2Nb_1/2)O₃-0.42Pb(Mg_1/3Nb_2/3)O₃-0.34PbTiO₃ transparent ceramics were fabricated by a conventional sintering technique. Through optimization of sintering conditions of calcination and sintering temperatures and time, the obtained ceramics showed high optical transmittance of 53% and 71% at light wavelengths of 1300 and 2000 nm, respectively. The ceramics showed a rhombohedral to tetragonal phase transition at ~120°C and a tetragonal to cubic phase transition at 222°C. These transition temperatures were higher than those of 0.67Pb(Mg_1/3Nb_2/3)-0.33PbTiO₃ ceramics. In addition, the ceramics had a ferroelectric hysteresis loop, a large piezoelectric constant d₃₃ of 407 pC/N, and a planar electromechanical coupling factor k_p of 52%. These results suggest that the transparent ceramics may be used as a temperature-stable, linear electro-optic material.     

Combustion synthesis of AlN doped with carbon and oxygen

Carbon-and-oxygen-doped AlN specimens were prepared by combustion synthesis using Al, graphite, and AlN. Graphite addition changed the product color from white to blue. By XRD, the lattice constant increased slightly with increasing carbon content. Blue AlN powder was synthesized with a molar ratio of the diluent AlN of 0.2-0.5 with a fixed graphite content of 0.05. At an AlN molar ratio exceeding 0.6, carbon was not successfully incorporated due to the lower reaction temperature. Calcination at 800°C in air removed residual graphite without changing the crystal structure or product color. Oxygen, nitrogen, and carbon analyses revealed that blue AlN powders contained 0.45-0.54 mass% carbon and 1.4-1.6 mass% oxygen, while the undoped AlN contained 0.021 mass% carbon and 0.94 mass% oxygen. The origin of the white-to-blue color change was investigated via reflection measurements. Blue AlN exhibits an absorption peak at 634 nm (1.96 eV). From first-principles electronic structure calculations, the C-doped AlN and carbon-and-oxygen-doped AlN with a 1:1 ratio could be classified as p-type, whereas the O-doped AlN and 1:3 carbon-and-oxygen-doped AlN were n-type. One reason for the absorption peak at 634 nm may be a transition from the conduction band to an upper unoccupied state. These results suggest the possible control of optical and electronic properties of AlN via carbon-and-oxygen doping.     

Conductive and flexible multi-walled carbon nanotube/polydimethylsiloxane composites made with naphthalene/toluene mixture

Conventional conductive materials face challenges when utilizing them for flexible and wearable electronics and soft robotics. Carbon nanotube/polydimethylsiloxane (CNT/PDMS) composites are a promising alternative to the conventional hard conductors because they are light and can realize large deformation. To date, well dispersion of CNTs into PDMS to increase conductivity while maintaining flexibility remains challenging. We aimed at developing highly electrically conductive and flexible multi-walled carbon nanotube/PDMS (MWCNT/PDMS) composites. To this end, we proposed a method to enhance the dispersion of MWCNTs into PDMS using naphthalene and toluene. Our results showed that the addition of naphthalene and toluene into the composites improved dispersion of the MWCNTs and increased the direct current (DC) electrical conductivity. We also found that the morphology of primary aggregates of the MWCNTs influenced the DC electrical conductivity of the composites. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 48167.