Dehydrogenation of ethane to ethylene via radical pathways enhanced by alkali metal based catalyst in oxysteam condition

The dehydrogenation of ethane to ethylene in the presence of oxygen and water was conducted using Na₂WO₄/SiO₂ catalyst at high temperatures. At 923 K, the conversion rate without water was proportional to ethane pressure and a half order of oxygen pressure, consistent with a kinetically relevant step where an ethane molecule is activated with dissociated oxygen on the surface. When water was present, the ethane conversion rate was drastically enhanced. An additional term in the rate expression was proportional to a quarter of the oxygen pressure and a half order of the water pressure. This mechanism is consistent with the quasi‐equilibrated OH radical formation with subsequent ethane activation. The attainable yield can be accurately described by taking the water contribution into consideration. At high conversion levels at 1073 K, the C₂H₄ yield exceeded 60% in a single‐pass conversion. The C₂H₄ selectivity was almost insensitive to the C₂H₆ and O₂ pressures. © 2016 American Institute of Chemical Engineers AIChE J, 63: 105–110, 2017     

Scandium-Doped Anatase (TiO2) Nanoparticles Directly Formed by Hydrothermal Crystallization

Anatase-type TiO₂ solid solutions doped with 0–10 mol% scandium were formed by hydrothermal crystallization under weak basic conditions above 180°C for 5 h from amorphous co-precipitates that were obtained from the aqueous precursor solutions of TiOSO₄ and Sc(NO₃)₃ using aqueous ammonia. The anatase particles were spindle-like and consisted of nanosized-crystallites (23–25 nm). The lattice parameter c ₀ of anatase and the length and width of the spindle-like anatase gradually increased when the scandium content was increased. The diffuse reflectance spectra of the as-prepared TiO₂ doped with scandium showed that the onset of absorption slightly shifted to longer wavelengths with increasing scandium content. The band gap of anatase was slightly increased by making solid solutions with scandium oxide.     

Further Improvement in Mechanical Properties of Highly Anisotropic Silicon Nitride Ceramics

Si₃N₄ceramics were fabricated by tape casting of a raw-powder slurry seeded with three types of rodlike β-Si₃N₄particles. The effects of seed size on the microstructure and mechanical properties of the sintered specimens were investigated. All the seeded and tape-cast silicon nitrides presented an anisotropic microstructure, where the elongated grains grown from seeds were preferentially oriented parallel to the casting direction. The orientation degree of these grains, f ₀, was affected by seed size, and small-seed addition led to the highest f ₀value. This material exhibited high bending strength (∼1.4 GPa) and high fracture toughness (∼12 MPa^.m^1/2) in the direction normal to the grain alignment, which were attributed to the highly anisotropic and fine microstructure.     

Responsiveness of electric resistance of polymer-grafted carbon black/alumina gel composite against solvent vapor and solute in solution

The carbon black/alumina gel composites were prepared by sol-gel reaction of aluminum isopropoxide in the presence of polymer-grafted carbon black. The electric resistance of the alumina gel composite from polymer-grafted carbon black was very sensitive to vapor of good solvent for grafted polymer on carbon black: the electric resistance of the alumina gel composite suddenly decreased in solvent vapor and returned to initial resistance when it was transferred into dry air. The effect of surface area and particle size of carbon black on the responsiveness was also investigated. In addition, the electric resistance of the alumina gel composite was found to respond to water and methanol in n-hexane and diethyl ether.     

Improvement of Pt/ZrO2 by CeO2 for high pressure CH4/CO2 reforming

CH₄/CO₂ reforming over Pt/ZrO₂, Pt/CeO₂ and Pt/ZrO₂ with CeO₂ was investigated at 2 MPa. Pt/ZrO₂, which shows stable activity under 0.1 MPa, and Pt/CeO₂ showed gradual deactivation with time at the high pressure. The deactivation was suppressed drastically on Pt/ZrO₂ with CeO₂ prepared by different impregnation order (co-impregnation of Pt and CeO₂ on ZrO₂, and consecutive impregnation of Pt and CeO₂ on ZrO₂). The amount of coke deposition was found insignificant and similar among all the catalysts (including Pt/ZrO₂ and Pt/CeO₂). Catalytic activity after the reaction for 24 h was in agreement with Pt particle size after the reaction for same period, indicating that the difference of the catalytic stability is mainly dependent on the extent of Pt aggregation through catalyst preparation, H₂ reduction, and the CH₄/CO₂ reforming. Pt aggregation and the amount of coke deposition were least pronounced on (Pt–Ce)/ZrO₂ prepared by impregnation of CeO₂ on Pt/ZrO₂ and the catalyst showed highest stability.     

Multi-walled carbon nanotube-reinforced copper nanocomposite coating fabricated by low-pressure cold spray process

Multi-walled carbon nanotube (MWCNT)-reinforced copper (Cu) nanocomposite coatings were successfully deposited on aluminum (Al) substrate by a cold spraying process at a low pressure. The microstructure and the Raman spectrum of the low-pressure-cold-sprayed MWCNT–Cu nanocomposite coating showed that the MWCNTs maintained their tube structure in the Cu matrix, even though structural damage to the MWCNTs increased slightly. MWCNT–Cu nanocomposite-coated Al exhibits higher thermal diffusivity than pure-Cu-coated Al with a comparable hardness. The higher thermal diffusivity of the MWCNT–Cu coating could be explained by the dispersion of MWCNTs within the clean and closed CNT/Cu interfaces, which were achieved with the aid of compressive stress during the cold spraying.     

Electron spin resonance of thin films of organic light-emitting material tris(8-hydroxyquinoline) aluminum doped by magnesium

We have successfully observed electron spin resonance (ESR) signals of radical anions in thin films of tris(8-hydroxyquinoline) aluminum (Alq₃), a compound widely used as electron transporting and luminescent layers in organic light-emitting diodes. To obtain definitely defined radical-anion states in Alq₃, we doped Alq₃ with Mg by co-evaporating these materials. The obtained g value and peak-to-peak ESR linewidth ΔH_pp of Alq₃ radical anions are 2.0030 and 2.19 mT, respectively. Theoretical g value and hyperfine interactions were calculated by density functional theory method, which are in good agreement with the experimental results. A quantitative evaluation of doping concentration was performed. We confirmed that doped charges are localized at deep trapping sites by the lineshape analysis and temperature dependence of the ESR signals. Morphological investigation using transmission electron microscopy clarified that the co-evaporated Mg atoms form clusters.     

Bovine serum albumin-sugar conjugates through the maillard reaction: effects on interfacial behavior and emulsifying ability

Bovine serum albumin (BSA) was employed as a model protein emulsifier to conjugate with aldohexose (D-glucose (Glc) or D-allose (All)) and sugar fatty acid ester (6-O-octanoyl-D-glucose (GlcC8)) through the Maillard reaction. It was found during the reaction that rate of decrease of free amino groups in BSA was almost the same for the BSA-sugar mixtures whereas browning and protein aggregation developed in the following order: Glc < All < GlcC8. It was thought that the rate of degradation of the Amadori compound could have been influenced by the OH-group stereochemistry at the C3 position of aldohexose, while denaturation of BSA by GlcC8 enhanced the browning and protein aggregation. To understand the emulsifying ability of the BSA-sugar conjugates, hexadecane-water interfacial tension and the oil droplet size of emulsions prepared by homogenizing hexadecane and aqueous solution of the conjugates were examined. BSA-GlcC8 showed greater improvement in interfacial and emulsifying activity than did BSA-Glc and -All. However, no improvement in emulsion stability was observed for any of the BSA-sugar conjugates, suggesting the weakness of the film formed at the oil droplet interface.     

The effect of electro-degradation processing on microstructure of polyaniline/single-wall carbon nanotube composite films

Mesostructured polyaniline/single-wall carbon nanotube (PAni/SWCNT) composite film has been prepared through electrochemical polymerization/degradation processing. The microstructures of the films are observed before and after electro-degradation. Initial twisty SWCNT bundles are broken down and linked by the polymerization of PAni. Both crystalline and disordered PAni regions coexist in the PAni/SWCNT composite nanowires. The disordered regions are gradually dissolved while the crystalline regions are basically preserved after electro-degradation. The formation mechanism of the composite with special construction has been proposed. In addition, cyclic voltammetry measurements demonstrate that the electroactive performance of PAni/SWCNT composite is enhanced after electro-degradation. It is found that the specific capacitance of electro-degraded composite reaches up to 848.7 F/g, more than twice over the untreated film, which is ascribed to its profitable charge accessible interface and increased available crystalline PAni regions.