Stabilization of 6H-Hexagonal SrMnO3 Polymorph by Al2O3 insertion

We demonstrate the structural evolution of polymorphic phases in Al₂O₃-inserted SrMnO₃ ceramics synthesized by solid state reaction. While the 4H-hexagonal phase is predominant in pure SrMnO₃ ceramics, a small amount of 6H-hexagonal polymorph is identified in addition to the primary 4H-hexagonal SrMnO₃ and the secondary hexagonal SrAl₂O₄ phases in the as-sintered ceramics, evidenced by x-ray diffraction and subsequent Rietveld refinement analyses. The existence of the 6H-hexagonal SrMnO₃ phase is corroborated using Raman spectroscopy. The chemical compositions and electronic structures of the Al₂O₃-inserted SrMnO₃ compounds are also examined using energy dispersive spectroscopy and x-ray photoelectron spectroscopy, respectively. The first-principles calculations reveal that there is no clear difference between the total energies of 4H- and 6H-hexagonal polymorphs regardless of the presence/absence of Sr and oxygen vacancies. Possible origins are discussed with the estimation of actual strain based on the refined lattice parameter of 6H SrMnO₃.     

Electrocatalytic Reduction of CO2 to Ethylene by Molecular Cu‐Complex Immobilized on Graphitized Mesoporous Carbon

The electrochemical reduction of carbon dioxide (CO₂) to hydrocarbons is a challenging task because of the issues in controlling the efficiency and selectivity of the products. Among the various transition metals, copper has attracted attention as it yields more reduced and C2 products even while using mononuclear copper center as catalysts. In addition, it is found that reversible formation of copper nanoparticle acts as the real catalytically active site for the conversion of CO₂ to reduced products. Here, it is demonstrated that the dinuclear molecular copper complex immobilized over graphitized mesoporous carbon can act as catalysts for the conversion of CO₂ to hydrocarbons (methane and ethylene) up to 60%. Interestingly, high selectivity toward C2 product (40% faradaic efficiency) is achieved by a molecular complex based hybrid material from CO₂ in 0.1 m KCl. In addition, the role of local pH, porous structure, and carbon support in limiting the mass transport to achieve the highly reduced products is demonstrated. Although the spectroscopic analysis of the catalysts exhibits molecular nature of the complex after 2 h bulk electrolysis, morphological study reveals that the newly generated copper cluster is the real active site during the catalytic reactions.     

Frequency Insertion Strategy for Channel Assignment Problem

This paper presents a new heuristic method for quickly finding a good feasible solution to the channel assignment problem (CAP). Like many other greedy-type heuristics for CAP, the proposed method also assigns a frequency to a call, one at a time. Hence, the method requires computational time that increases only linear to the number of calls. However, what distinguishes the method from others is that it starts with a narrow enough frequency band so as to provoke violations of constraints that we need to comply with in order to avoid radio interference. Each violation is then resolved by inserting frequencies at the most appropriate positions so that the band of frequencies expands minimally. An extensive computational experiment using a set of randomly generated problems as well as the Philadelphia benchmark instances shows that the proposed method perform statistically better than existing methods of its kind and even yields optimum solutions to most of Philadelphia benchmark instances among which two cases are reported for the first time ever, in this paper. Won-Young Shin was born in Busan, Korea in 1978. He received B.S. in industrial engineering from Pohang University of Science and Technology (POSTECH) in 2001 and M.S in operation research and applied statistics from POSTECH in 2003. Since 2003 he has been a researcher of Agency for Defense Development (ADD) in Korea. He is interested in optimization of communication system and applied statistics. Soo Y. Chang is an associate professor in the Department of Industrial Engineering at Pohang University of Science and Technology (POSTECH), Pohang, Korea. He teaches linear programming, discrete optimization, network flows and operations research courses. His research interests include mathematical programming and scheduling. He has published in several journals including Discrete Applied Mathematics, Computers and Mathematics with Application, IIE Transactions, International Journal of Production Research, and so on. He is a member of Korean IIE, and ORMSS. Jaewook Lee is an assistant professor in the Department of Industrial Engineering at Pohang University of Science and Technology (POSTECH), Pohang, Korea. He received the B.S. degree in mathematics with honors from Seoul National University, and the Ph.D. degree from Cornell University in applied mathematics in 1993 and 1999, respectively. He is currently an assistant professor in the department of industrial engineering at the Pohang University of Science and Technology (POSTECH). His research interests include nonlinear systems, neural networks, nonlinear optimization, and their applications to data mining and financial engineering. Chi-Hyuck Jun was born in Seoul, Korea in 1954. He received B.S. in mineral and petroleum engineering from Seoul National University in 1977, M.S. in industrial engineering from Korea Advanced Institute of Science and Technology in 1979 and Ph.D. in operations research from University of California, Berkeley, in 1986. Since 1987 he has been with the department of industrial engineering, Pohang University of Science and Technology (POSTECH) and he is now a professor and the department head. He is interested in performance analysis of communication and production systems. He has published in several journals including IIE Transactions, IEEE Transactions, Queueing Systems and Chemometrics and Intelligent Laboratory Systems. He is a member of IEEE, INFORMS and ASQ.     

Ethylene polymerization over MgO‐supported zirconocene catalysts

Supported zirconcene catalysts on a new support, MgO, were prepared and tested in ethylene polymerization. Three types of impregnation methods were employed to find an optimum supporting method for MgO. The direct impregnation of Cp₂ZrCl₂ on MgO showed low metal loading and polymerization activity, while the catalyst had a higher metal loading and polymerization activity when MgO was treated with methylaluminoxane (MAO) before supporting. Treatment of MgO with MAO during the supporting step invoked two types of catalytic sites, which was evidenced by the bimodal molecular weight distribution of the polymer products. MgO is considered to have potential as a support for metallocenes.     

NO emission characteristics in counterflow diffusion flame of blended fuel of H2/CO2/Ar

Flame structure and NO emission characteristics in counterflow diffusion flame of blended fuel of H₂/CO₂/Ar have been numerically simulated with detailed chemistry. The combination of H₂, CO₂ and Ar as fuel is selected to clearly display the contribution of hydrocarbon products to flame structure and NO emission characteristics due to the breakdown of CO₂. A radiative heat loss term is involved to correctly describe the flame dynamics especially at low strain rates. The detailed chemistry adopts the reaction mechanism of GRI 2.11, which consists of 49 species and 279 elementary reactions. All mechanisms including thermal, NO₂, N₂O and Fenimore are taken into account to separately evaluate the effects of CO₂ addition on NO emission characteristics. The increase of added CO₂ quantity causes flame temperature to fall since at high strain rates a diluent effect is prevailing and at low strain rates the breakdown of CO₂ produces relatively populous hydrocarbon products and thus the existence of hydrocarbon products inhibits chain branching. It is also found that the contribution of NO production by N₂O and NO₂ mechanisms are negligible and that thermal mechanism is concentrated on only the reaction zone. As strain rate and CO₂ quantity increase, NO production is remarkably augmented. Copyright © 2002 John Wiley & Sons, Ltd.     

Poly(butylene terephthalate)–clay nanocomposites prepared by melt intercalation: morphology and thermomechanical properties

Nanocomposites based on poly(butylene terephthalate) (PBT) and an organoclay (Cloisite 30B) were prepared by melt blending using a twin‐screw extruder. Two kinds of PBTs, ie PBT‐A and PBT‐B, with different inherent viscosities (η_inh), were used for this study (η_inh of PBT‐A and PBT‐B were 0.74 and 1.48, respectively). Dispersion of the clay layers in the PBT nanocomposites was characterized by using X‐ray diffraction (XRD) and transmission electron microscopy (TEM). Tensile and dynamic mechanical properties and non‐isothermal crystallization temperatures of the nanocomposites were also examined. Nanocomposites based on the higher‐viscosity PBT (PBT‐B) showed a higher degree of exfoliation of the clay and a higher reinforcing effect when compared to the composites based on the lower‐viscosity PBT (PBT‐A). The clay nanolayers dispersed in PBT matrices lead to increases in the non‐isothermal crystallization temperatures of the PBTs, with such increases being more significant for the PBT‐B nanocomposites than for the PBT‐A nanoocomposites. Copyright © 2004 Society of Chemical Industry     

Protein binding study of isoflavone, perillyl alcohol and S-ibuprofen by high-performance frontal analysis

High-performance frontal analysis (HPFA) was used for a protein binding study of isoflavones (daidzein, genistin, and genistein), enantiomers of perillyl alcohol and S-ibuprofen to human serum albumin (HSA). The analyses were performed on a Develosil and Inertsil 100-Diol-5 column (10 cm×4.6mm). Sodium phosphate solution (pH 7.4, ionic strength 0.17) was used as the mobile phase at a flow rate of 1 ml/min. To ensure the drug to be eluted as a trapezoidal peak with a plateau, injection volumes were each fixed up the zonal profile with an evident plateau appears. The unbound drug concentration was determined from a plateau height of the plateau region after that experimental data were fitted by Scatchard equation. The binding constants (K) and total binding affinities (nK) of drugs to HSA were calculated, respectively.