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     

Phase transformation and interface segregation behavior in Si3N4 ceramics sintered with La2O3–Lu2O3 mixed additive

Microstructure and mechanical property of silicon nitride (Si₃N₄) ceramic are strongly dependent on the selection of sintering additives. When rare‐earth (RE) oxide is used as the sintering additive, segregation of RE ions at interface between Si₃N₄ grain and intergranular glassy film (IGF) is believed to play a critical role. Although the ionic radius of RE ion is known to be an empirical parameter to modify the mechanical property, the correlation between the segregated ions and their ionic radii is still under controversy. In order to address this issue, (i) rate of α‐β phase transformation and (ii) segregation behavior at the interface were studied for Si₃N₄ ceramics sintered using mixture of La₂O₃ and Lu₂O₃ as additives in this study. Specimens of Lu content 30% and higher exhibited lower activation energies for the α‐β phase transformation as compared with those of Lu content 20% and lower. In terms of the segregation behavior, La was preferably segregated at one site and Lu at the other site along β‐Si₃N₄/IGF interface in the specimens of Lu content 30% and higher. It is understood from these results that Lu segregation site should be more closely related with grain growth.     

Application of Poly(acetic Acid)–Based Graft Copolymer as a Compatibilizer for Poly(L-lactic Acid)/Poly(butylenesuccinate) Blend System

Poly(L-lactic acid) (PLLA) was blended with poly(butylenesuccinate) (PBS) using a single-screw extruder to modify the poor characteristics of these polymers. Furthermore, when both polymers were blended, the graft copolymer that was synthesized by partially saponified poly(vinyl alcohol) (PSPVA) and ?-caprolactone (?-CL) was used as a novel compatibilizer. The structure of the synthesized compatibilizer was determined by ¹H or ¹³C NMR. From this result, the ring-opening polymerization of the ?-CL occurred at the hydroxyl group of PSPVA. The structures of the PLLA/PBS solvent-cast blended films could be observed via an optical microscope. From the optical microscopic observation, the structures of the solvent-cast blended films with the synthesized compatibilizer were more homogeneous than those of the solvent-cast blended films without the compatibilizer. The mechanical properties of the PLLA/PBS extruded blended films were determined by a tensile test. The result showed the tensile strength of the blended films with the synthesized compatibilizer was greater than that of the blended films without the compatibilizer.     

Influence of diblock addition on tack in a polyacrylic triblock copolymer/tackifier system measured using a probe tack test

The influence of diblock copolymer addition on the tack properties of a polyacrylic triblock copolymer/tackifier system was investigated. For this purpose, poly(methyl methacrylate)‐block‐poly(n‐butyl acrylate)‐block‐poly(methyl methacrylate) triblock copolymer (MAM) and a 1/1 blend with a diblock copolymer consisting of the same components (MA) were used as base polymers, and a tackifier was added in amounts ranging from 10 to 30 wt %. The temperature dependence of tack was measured by a probe tack test. The tack of MAM/MA at room temperature was significantly higher than that of MAM, and the improvement of MAM/MA upon the addition of the tackifier was higher than that of MAM. The peeling process at the probe/adhesive interface during the probe tack test was observed using a high‐speed microscope. It was found that for MAM/MA, cavitation was caused in the entire adhesive layer, and peeling initiation was delayed by the absorption of strain energy due to deformation of the adhesive layer. In contrast, for MAM, peeling progressed linearly from the edge to the center of the probe. The greater flexibility of the soft block chain in the diblock copolymer resulted in improved interfacial adhesion. ¹H pulse nuclear magnetic resonance analysis showed that the addition of the tackifier improved the cohesive strength of the adhesive. Adhesion strength is affected by two factors: the development of interfacial adhesion and cohesive strength. In the MAM/MA/tackifier system, the presence of MA and the tackifier improved the interfacial adhesion and cohesive strength, respectively. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Grazing-incidence wide-angle X-ray diffraction study on molecular aggregation state of imprinted polyimide film before and after hard baking

Nanoimprint lithography (NIL) was carried out on precursor of polyimide (PI), poly(amic acid) film, and then hard baking to obtain imprinted PI film. The molecular aggregation states of imprinted PI films before and after hard baking were investigated by grazing-incidence wide-angle X-ray diffraction comparing with the one of flat PI film. It was found that NIL and hard baking can strongly affect the molecular aggregation states of PI film. Before hard baking, PI chain is aligned parallel to the line direction on the line. After hard baking, the alignment in ordered domain was changed to that the PI molecule of which chain axis is perpendicular to the line direction is significantly increased, while, PI molecule of which chain axis is parallel to the line direction is decreased after hard baking. Through comparing with the flat PI, crystallinity of imprinted PI film has been significantly enhanced.     

Porous cellulose acetate membrane prepared by thermally induced phase separation

Microporous cellulose acetate membranes were prepared by a thermally induced phase separation (TIPS) process. Two kinds of cellulose acetate with acetyl content of 51 and 55 mol % and two kinds of diluents, such as 2‐methyl‐2,4‐pentandiol and 2‐ethyl‐1,3‐hexanediol, were used. In all polymer‐diluent systems, cloud points were observed, which indicated that liquid–liquid phase separation occurred during the TIPS process. The growth of droplets formed after the phase separation was followed using three cooling conditions. The obtained pore structure was isotropic, that is, the pore size did not vary across the membrane. In addition, no macrovoids were formed. These pore structures were in contrast with those usually obtained by the immersion precipitation method. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 3951–3955, 2003     

Serial Changes of Serum Growth Factor Levels and Liver Regeneration after Partial Hepatectomy in Healthy Humans

This study aimed to investigate the associations of the serial changes of serum levels of various growth factors with liver regeneration after hepatectomy in healthy liver donors. Sixteen healthy liver donors who underwent conventional liver resection were included. Serum levels of various growth factors before hepatectomy and on postoperative day (POD) 1, 3, 5 and 7 were measured. Liver volume data calculated by multi-detector computed tomography using workstation. The ratio of remnant liver volume on POD 0 to liver volume before the operation was 51% ± 20%. The ratio of liver volume on POD 14 to liver volume on POD 0 were inversely correlated with remnant liver volume on POD 0 (r = −0.91). The ratio of liver volume on POD 14 to liver volume on POD 0 were significantly correlated with serum hepatocyte growth factor (HGF) levels on POD 1 (r = 0.54), serum leptin levels on POD 1 (r = 0.54), and serum macrophage colony-stimulating factor (M-CSF) levels on POD 5 (r = 0.76) and POD 7 (r = 0.80). These results suggest that early-phase elevation of serum levels of HGF, leptin and M-CSF may be associated with the acceleration of liver regeneration after hepatectomy in humans.     

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.