Ultrasound‐activated Knoevenagel condensation of malononitrile with carbonylic compounds catalysed by alkaline‐doped saponites

α,β‐Unsaturated nitriles have been synthesized by Knoevenagel condensation of a carbonylic compound with malononitrile, assisted by sonochemical irradiation. Two alkaline‐promoted clays (Li⁺‐ and Cs⁺‐exchanged saponites) have been employed as catalysts. The influence of the carbonylic compound (benzaldehyde or cyclohexanone) and the use of a solvent on the catalytic activity have been studied. Remarkable increase in the conversion values has been found when the reaction is activated by ultrasound, as compared with the thermal activation. In this green, solvent‐free procedure, α,β‐unsaturated nitriles have been produced in very high yields (97%) when the Cs⁺‐saponite is used as catalyst. Copyright © 2004 Society of Chemical Industry     

Stabilization of bioethanol recovery with silicone rubber‐coated ethanol‐permselective silicalite membranes by controlling the pH of acidic feed solution

In order to produce highly concentrated bioethanol by pervaporation using an ethanol‐permselective silicalite membrane, techniques to suppress adsorption of succinic acid, which is a chief by‐product of ethanol fermentation and causes the deterioration in pervaporation performance, onto the silicalite crystals was investigated. The amount adsorbed increased as the pH of the aqueous succinic acid solution decreased. The pervaporation performance also decreased with decreasing pH when the ternary mixtures of ethanol/water/succinic acid were separated. Using silicalite membranes individually coated with two types of silicone rubber, pervaporation performance was significantly improved in the pH range of 5 to 7, when compared with that of non‐coated silicalite membranes in ternary mixtures of ethanol/water/succinic acid. Moreover, when using a silicalite membrane double‐coated with the two types of silicone rubber, pervaporation performance was stabilized at lower pH values. In the separation of bioethanol by pervaporation using the double‐coated silicalite membrane, removal of accumulated substances having an ultraviolet absorption maximum at approximately 260 nm from the fermentation broth proved to be vital for efficient pervaporation. Copyright © 2005 Society of Chemical Industry     

酸催化二甘醇脱水环化反应研究

以硫酸、磷钨酸、ZRP-5分子筛为催化剂,研究了二甘醇(DEG)脱水环化的反应规律。结果表明,DEG发生分子内脱水环化反应,生成1,4-二氧六环(DOX),DEG分子间脱水不仅可以生成四甘醇、六甘醇等,同时可生成三甘醇、五甘醇等一系列的多甘醇(PEG)。不仅DEG可以脱水环化生成DOX,在反应中生成的PEG也同样可以进行生成DOX的反应。对于二甘醇(DEG)脱水环化反应,硫酸是性能优良的催化剂,反应可以在较低的温度下进行,馏出产物中DOX选择性大于95％。     

Material state remapping in computational solid mechanics

A computational procedure for remapping material state information from one finite element mesh to another is described. The procedure is useful in connection with evolving meshes for inelastic problems, as for example occur in the context of fracture simulation and adaptive mesh refinement. The proposed method is based on weak enforcement of equality between corresponding fields on the two meshes, where piecewise‐constant fields on both meshes are generalized from the quadrature‐point values. The essential algorithmic problem is that of calculating the volume partition of an arbitrary convex region with respect to a covering set of disjoint convex regions. Instead of geometrically resolving the associated intersections, the problem is herein approximated by a constrained optimization problem, which may be readily and efficiently solved computationally. This formulation is a main contribution of the paper. Computational examples are given that illustrate the effectiveness of the proposed procedure. Copyright © 2002 John Wiley & Sons, Ltd.     

The radiation crosslinking and scission of ethylene-propylene copolymers studied by solid-state nuclear magnetic resonance

Methyl groups from chain scission and H-crosslinks have been identified by solid-state nuclear magnetic resonance in amorphous ethylene-propylene copolymers containing 23 and 36 mole % propylene after γ-irradiation to 10 MGy at 30°C. G (scission) and G (crosslink) values determined from the n.m.r. spectra and by extraction are in agreement, which suggests that the crosslinks are not clustered. This may differ from the situation in polyethylene where there is a substantial crystalline content. G(S). G(X) and the ratio G(S)/G(X) increase with increasing propylene content of the copolymers.     

A hybrid extended finite element/level set method for modeling phase transformations

A hybrid numerical method for modelling the evolution of sharp phase interfaces on fixed grids is presented. We focus attention on two‐dimensional solidification problems, where the temperature field evolves according to classical heat conduction in two subdomains separated by a moving freezing front. The enrichment strategies of the eXtended Finite Element Method (X‐FEM) are employed to represent the jump in the temperature gradient that governs the velocity of the phase boundary. A new approach with the X‐FEM is suggested for this class of problems whereby the partition of unity is constructed with C¹(Ω) polynomials and enriched with a C⁰(Ω) function. This approach leads to jumps in temperature gradient occurring only at the phase boundary, and is shown to significantly improve estimates for the front velocity. Temporal derivatives of the temperature field in the vicinity of the phase front are obtained with a projection that employs discontinuous enrichment. In conjunction with a finer finite difference grid, the Level Set method is used to represent the evolution of the phase interface. An iterative procedure is adopted to satisfy the constraints on the temperature field on the phase boundary. The robustness and utility of the method is demonstrated with several benchmark problems of phase transformation. Copyright © 2002 John Wiley & Sons, Ltd.     

A Composite Index of Compliance for Chronic In‐Center Hemodialysis Patients

We developed a composite compliance index as the sum of the compliance scores for interdialytic weight gain (IDWG), pre‐dialysis serum potassium and phosphorus concentrations (each scored from zero to 3, with 3 indicating the poorest compliance), and skipping hemodialysis sessions (scored from zero to 9, with 9 indicating the poorest compliance). We used this composite score to prospectively evaluate compliance in 25 prevalent hemodialysis patients over a period of 1 year. We then followed these patients for another 3.5 years. The patients studied were divided into two groups: group A (poor compliance) consisted of 9 subjects with composite score ≥ 9 (13.2 ± 3.2); group B (better compliance) consisted of 16 subjects with composite score < 9 (4.7 ± 1.8). Age, duration of hemodialysis, and frequency of diabetes mellitus did not differ between the groups. Group A contained higher fractions of subjects with history of alcoholism (66.7% vs 12.5%, p = 0.010), other substance addiction (44.4% vs 0%, p = 0.010), and severe psychosocial problems (88.9% vs 18.8%, p = 0.002). Mean survival from the beginning of observation, estimated by actuarial life‐table survival analysis, was 1.19 years in group A and 2.60 years in group B (p = 0.0265). A composite compliance index incorporating domains indicating adherence to diet, medications, and dialysis schedule identified other behavioral problems in poorly compliant patients. Hemodialysis patients characterized by this composite index as poorly compliant had shortened survival.     

Stable Oxygen and Carbon Isotopic Compositions of Lates stappersii Otoliths from Lake Tanganyika,East Africa

In this study, we measured growth trends in oxygen and carbon isotopic ratios in whole sagittal otoliths from three adult centropomid fish (Lates stappersii) from each of three sub-basins of Lake Tanganyika, East Africa. Sampling density was 20 to 50 samples per otolith. Both δ¹⁸O and δ¹³C values increase with age. The δ¹⁸O data suggest that otoliths were precipitated near the expected equilibrium with the ambient environment (ca. +3.5‰) and support a migration pattern from surface waters during larval stages to deeper waters (40 to 80 m) for mature fish. Relatively high δ¹⁸O values in the southern sub-basin are consistent with cooler temperatures in the region during seasonal upwelling. The δ13C increase from otolith core to edge is large (up to 4‰) and is interpreted as due to ontogenetic changes in diet and contributions from a decrease in the proportion of respired CO₂ incorporated into otolith carbonate as metabolic rates of the fish dropped with maturity. The data seem to successfully reveal life strategy and migration patterns of L. stappersii, document regional differences in lake conditions, and provide a record of temperature within the water column during which the fish lived. Higher resolution studies and analyses of historical samples could be used to constrain modern and past growth patterns, and to reconstruct past temperature gradients and productivity patterns in the lake.     

Temperature effects on the mass flow rate in the SBI and similar heat‐release rate test equipment

In various medium‐to‐large‐scale fire test equipments like the ISO room corner test (RC), and more recently, the single burning item test (SBI) the mass flow rate measurement of the combustion gases plays a key role in the determination of the heat‐release rate and smoke‐production rate. With the knowledge of the velocity profile and the temperature of the flow, the mass flow rate is obtained by measuring the velocity on the axis of the duct. This is done by means of a bi‐directional probe based on the pitot principle. However, due to the variation of the mean temperature and the temperature gradient in any cross section of the duct, introduced by ever changing combustion gas temperatures, the velocity nor the density profile are constant in time. This paper examines the resulting uncertainty on the mass flow rate. Copyright © 2006 John Wiley & Sons, Ltd.     

Improvement of levitation characteristics in a magnetic bearing system using HTSC‐permanent magnet hybrid structure

Magnetic bearing using pinning force of a permanent magnet and a high‐temperature superconductor has been developed. Additional permanent magnet is introduced to increase the levitation force of the magnetic bearing. In this hybrid magnetic bearing system, levitation force is mainly given by the repulsive force of the permanent magnets, and stability for the lateral direction is given by pinning force of the superconductor. The experimental device is developed. A ring‐type superconductor and a bulk one are examined. Levitation characteristics of the hybrid magnetic bearing are measured. The bulk superconductor shows better characteristics of both levitation and lateral stability than the ring one. Levitation force of the hybrid system becomes about twice as large as that of the nonhybrid one. Although, the repulsive force of the permanent magnet decreases the lateral stability of the system, its influence becomes small by choosing an adequate position of the permanent magnets and the superconductor. © 2004 Wiley Periodicals, Inc. Electr Eng Jpn, 150(1): 71–77, 2005; Published online in Wiley InterScience ( www.interscience.wiley.com ). DOI 10.1002/eej.10350