Fugitive Diffusion Barrier for Integration of Sol-Gel-Derived Lead Titanate with Oxidized Silicon Substrates

The crystalline phase development and microstructural changes with heating of sol-gel-derived lead titanate (PT) particles and films on silica with and without a fugitive (or removable) diffusion barrier layer were investigated. Amorphous gel-derived PT particles were deposited on SiO₂-coated TEM grids with and without polyimide (PI) or carbon barrier layers between SiO₂ and PT. TEM analysis showed that PI or carbon barriers prevented reaction between the gel-derived PT particles and SiO₂. PT particles crystallize and then the PI or carbon film decomposes. Sol-gel-derived PT films were deposited on oxidized Si substrates (Si/SiO₂) with and without a PI barrier layer. Perovskite PT films were prepared on Si/SiO₂ substrates with a PI barrier; however, some porosity remained in the films. Identically prepared films without the PI barrier formed a mixture of pyrochlore and perovskite. X-ray photoelectron spectroscopy results indicate that the PI film pre- vents the diffusion of Si into the PT film.     

Ammonia synthesis enhanced by magnesium chloride absorption

Conversion to ammonia with Haber–Bosch catalysts can be increased above 95% by selective absorption of ammonia by MgCl₂. The maximum conversion depends on reaction and absorption equilibria. At very short times, the measured conversion rate is the same with and without absorption by the MgCl₂ salt; the overall rate constants are comparable to those in the literature. At larger times, conversion to ammonia can be over seven times greater with MgCl₂ than without. However, the overall rate constants can be over 10 times slower because they are controlled by ammonia diffusion in the solid salt. An approximate, pseudosteady state theory consistent with these results provides a strategy for improving the overall rate while keeping the conversion over 90%. For example, the absorption rates might be increased using smaller particles of absorbent on a porous inert absorbent support. The results provide part of the basis for designing small scale ammonia plants. © 2015 American Institute of Chemical Engineers AIChE J, 61: 1364–1371, 2015     

Catalytic partial oxidation of ethane to ethylene and syngas over Rh and Pt coated monoliths: Spatial profiles of temperature and composition

The catalytic partial oxidation of C₂H₆ over Pt and Rh coated monolithic supports (4.7 wt% M/α-Al₂O₃ 45 PPI) was investigated with a capillary sampling technique for a range of C₂H₆/air ratios at constant inlet flow (～8 ms contact time), with and without H₂ addition. Effluent data clearly indicate the differences in product distribution between catalysts and equilibrium. Rh effectively converts the reactant mixtures to syngas with ～80% selectivity, whereas Pt produces C₂H₄ with ～55% C-atom selectivity, while neither produces thermodynamically favored C. Spatially resolved measurements provide direct evidence of the multi-zone nature of the reactors. With Rh, complete conversion of O₂ occurs to produce mostly CO, H₂ and H₂O within the first 3 mm of catalyst, followed by a reforming zone to produce additional syngas. Pt consumes O₂ more slowly, which results in a steady increase in temperature along the reactor. Ethylene formation correlates to reactor temperatures >750 °C, regardless of C/O, in line with the onset of homogeneous reactions. Hydrogen addition tests (C₂H₆/O₂/H₂=2/1/2) clearly exhibit preferential oxidation of H₂ with O₂ over Pt, which shifts the maximum in temperature upstream while preserving a portion of the C₂H₆ for C₂H₄ production. H₂ addition modifies the concentration and temperature profiles minimally on Rh. The main differences between catalysts are the high reforming and O₂ consumption activity with Rh compared to Pt, which are likely responsible for differences in C₂H₄ yields.     

Housing Affordability in Singapore: Can We Move from Public to Private Housing?

With 84 per cent of the Singapore resident population housed in public housing, the ultimate dream for many is to move into private housing, which is generally considered to offer better quality and more exclusive living. This article is concerned with the enabling factors of affordability in housing mobility. It examines the Singapore public housing homeowners' affordability of private housing, suggesting a measure of that affordability. The survey findings indicate that only a small percentage of public homeowners can afford to move to median-priced private apartments. The number is even smaller for the relatively more expensive landed housing with own garden. On a theoretical level, the study demonstrates that the use of multiple methods to measure housing affordability is beneficial as more affordability determinants are included in the measurement.     

美国棉花公司2011春夏流行色流行趋势

神圣的宗教感悟与现实的反置冲撞、纯真忆旧的年代与囊渺的未来意向盘根交错、交相辉映,将2011年春夏女装引入了前所未有的全盛时期。民族的特性、工艺的交叉、文化的融合、东西万审美的取向差异、简洁与繁复的抗衡、古典与现代的传承、奢华中带着浓重的古朴意蕴……这就是未来多元化并行带来的全新流行方向。     

Horizontal reactive distillation for multicomponent chiral resolution

A novel horizontal reactive distillation apparatus and a new overall process scheme are proposed for continuous multicomponent chiral resolution via reversible enantioselective acylation of a chiral (racemic) substrate by a chiral (racemic) acyl donor. The process enables simultaneous production of up to four enantiomers with enhanced chiral purity. Kinetic studies, miniplant experiments, and process simulation results are described for a model lipase‐catalyzed reaction: (R)‐enantioselective transesterification of (R,S)‐1‐n‐butoxy‐2‐propanol with (R,S)‐1‐methoxy‐2‐acetoxypropane to produce (R)‐1‐n‐butoxy‐2‐acetoxypropane, (R)‐1‐methoxy‐2‐propanol, and the two unreacted (S)‐enantiomers of the (R,S)‐reagents. A horizontal, compartmentalized reactive distillation vessel is specified instead of a conventional reactive distillation column to provide longer liquid‐phase residence time needed for adequate conversion. Low vapor‐traffic pressure drop allows operation under vacuum at reduced temperatures for good enzyme stability and enantioselectivity. The general technology has potential as a means to producing a wide range of chiral synthons used in asymmetric syntheses of chiral pharmaceuticals and other biologically active products. © 2013 American Institute of Chemical Engineers AIChE J, 59: 2603–2620, 2013     

Spatial and temporal profiles in millisecond partial oxidation processes

Methods are presented to measure axial species and temperature profiles within catalytic partial oxidation foam monoliths at atmospheric pressure with 0.3 mm spatial resolution using a capillary sampling technique with a quadrupole mass spectrometer. The system allows sampling within the catalyst with negligible interference in flow or temperature by using a 0.6 mm quartz capillary containing a thermocouple and possessing a 0.3 mm side orifice. The capillary tightly fills a concentric channel drilled within the 10 mm long ceramic foam minimizing gas bypass. This technique has been used to measure axial catalyst species profiles at temperatures up to 1300 °C for catalytic partial oxidation of methane and ethane to synthesis gas and ethylene, respectively. CH₄ and O₂ conversion are approximately twice as fast on Rh than on Pt. For C₂H₆ the reaction products at the catalyst entrance are H₂, H₂O, CO, and CO₂. Ethylene production begins only after ~4 mm into the catalyst after most of the O₂ has reacted. Transient operation where the feed composition is varied stepwise between different C/O ratios has also been used to characterize these systems. The capillary sampler has a time resolution of ~0.05 s, and C/O step changes within 0.5 s have been achieved using mass flow controllers. For switches from C/O = 0.6 to 1.4, sharp overshoots are observed for syngas (H₂ and CO) and similar undershoots for combustion products (H₂O and CO₂). By placing the sampling orifice at different positions and stepping the C/O ratio, spatio-temporal profiles can be obtained. Spatio-temporal profiles are extremely important in validating detailed reaction mechanisms because their information content is much higher compared to integral steady state measurements at the reactor outlet. The spatial profiles show where and how quickly different species are formed or consumed along the catalyst axis. Transient profiles provide additional diagnostics of mechanisms and surface coverages because they show how temperature and species concentrations follow a perturbation from steady state.