大型海湾水交换计算中随机游动方法的应用研究

水交换矩阵是反映大型海湾不同子区域之间水交换关系的有效工具,该文对随机游动方法在水交换矩阵计算中的应用进行了研究．通过与对流扩散模型的对比,指出用随机游动方法计算水交换矩阵比用对流扩散方程求解更快更灵活．同时,为了对不同区域之间的水交换特性进行长期快速预测,采用了Thompson提出的预测矩阵方法．通过理论分析得出,影响该矩阵预测效果的因素主要有:粒子数目、分区数和预测矩阵取值时间．以一个矩形海湾为例,将数值模拟结果和预测矩阵预测结果进行对比,分析了以上各因素对预测效果的影响．结果表明,粒子数目越多,预测矩阵取值时间越长,预测矩阵的预测效果越好．在粒子数目足够多的情形下,分区数越多,预测效果越好．相反,粒子数目如果较少,过多的分区数将可能导致预测矩阵效果太差而不可用．     

Linewidth Analysis of Spin Labels in Liquids: II. Experimental

This work demonstrates that homogeneous linewidths can be extracted from continuous wave electron paramagnetic resonance spectra and that they quantitatively agree with the predictions of existing relaxation theory. We suggest that relaxation theory can be used to predict experimental lineshapes provided that the simulations properly include sources of broadening. We have found that the rotational correlation times for spin labels in different percentages of glycerol/water mixtures are best modeled by a power law treatment for the viscosity, similar to that for translational diffusion. The translational diffusion coefficients themselves also have a power law dependence on the viscosity for glycerol/water mixtures. The linewidths were linearly dependent upon both the oxygen and the spin label concentration. The hyperfine splittings of all nuclei were observed to decrease linearly with increasing spin label concentration, completely at odds with existing theory which predicts a quadratic dependence upon concentration. The linear dependence was independent of hyperfine splitting until the magnitude of the hyperfine splitting was less than the homogeneous linewidth.     

Reversible Activation of Water by an Air- and Moisture-Stable Frustrated Rhodium Nitrogen Lewis Pair

[Cp*Rh(κ³N,N′,P- L )][SbF₆] (Cp*=C₅Me₅), bearing a guanidine-derived phosphano ligand L , behaves as a “dormant” frustrated Lewis pair and activates H₂ and H₂O in a reversible manner. When D₂O is employed, a facile H/D exchange at the Cp* ring takes place through sequential C(sp³)−H bond activation.     

Proton exchange membrane prepared by blending polybenzimidazole with poly (aminophosphonate ester)

In this article, we report a new amorphous-crystalline polymer blend system consisting of poly (4, 4′-diphenylether-5, 5′-bibenzimidazole) (OPBI) and poly (aminophosphonate ester) (PAPE) polymers, the membranes of which were fabricated using the solution blending route. A series of blend membranes at different ratios were prepared and systematically analysed for chemical interactions, morphological changes and their physico-chemical properties studied for use as proton exchange membrane. While FT-IR spectroscopy established the hydrogen bonding interactions between N–H of OPBI and phosphonate ester group of PAPE, X-ray diffraction studies revealed the development of crystallinity in the membrane matrix. Interestingly, the gradual induction of crystallinity in an amorphous OPBI matrix was found to influence the properties of the blend membranes favourably. For instance, the blend membrane containing 25 wt% PAPE in OPBI matrix displayed the maximum property enhancement in terms of storage modulus, glass transition temperature (T_g), phosphoric acid (PA) doping level (37 mol/OPBI repeat unit) and most importantly proton conductivity (0.135 S/cm at 180 °C) which is almost twice the value for pristine OPBI (0.05 S/cm at 180 °C) under identical conditions. Although improved properties were observed at other blend ratios as well, the studies ascertain that the membrane with 25 wt% PAPE was found to be the threshold ratio up to which properties increase and beyond which i.e. at >25 wt% PAPE, there is a decrement in properties like mechanical stability and proton conductivity. An important reason for this was attributed to the creation of a right balance of amorphous and crystalline domains and appropriate intra and inter-polymer hydrogen bonding interactions in the matrix of 75/25 (OPBI/PAPE) blend membrane.     

Operando Isotopic Exchange in Solid Oxide Fuel Cells: Oxygen-Transport Dependency on Applied Potential

The oxygen isotopic exchange technique is a powerful tool to investigate the oxygen transport kinetics in an oxide solid. In a solid oxide fuel cell, isotopic surface exchange and diffusion coefficients are classically determined by using the Isotopic Exchange Depth Profiling method followed by ex situ SIMS characterizations. Despite its relevance, the utilization of in situ or operando techniques to measure the isotopic exchange under an electrical bias remains marginal. We developed here a set-up which enables operando monitoring of oxygen exchange in SOFC type cells under polarization. The system has been used for studying the oxygen mobility dependency upon polarization on a symmetrical Pt/YSZ/Pt cell (YSZ: yttria-stabilized zirconia). Homomolecular and heterolytic exchange reactions were undertaken to investigate the oxygen activation step and discriminate the limiting step among the sequence of elementary steps which constitute the oxygen transport process in the SOFC system. Oxygen ions incorporation into the dense ionic conductor was identified to be the rate determining step, and its first order rate constant dependency on applied potential was established.     

Effect of deprotonation on the magnetic exchange coupling constant of fluorene‐based verdazyl diradical: A computational study

The magnetic behavior of the fluorene bridged verdazyl diradicals has been studied theoretically in their neutral and deprotonated states. The deprotonation of C9‐H site of the fluorene ring opens a new coupling pathway, which changes the nature of magnetic coupling. The transmission spectra analysis reveals that the transmission through fluorine has also increased due to the opening of a new coupling path after deprotonation.     

板翅式换热器物流分配研究综述

板翅式换热器由于具有紧凑高效等突出优点,在航空、化工、HVAC等领域具有重要地位。由多种因素引起换热器内部流动的不均匀分配,是造成换热效能的下降最主要原因之一。文中总结了国内外学者对于板翅式换热器物流分配不均匀的研究,详细阐述了各种流动分配模型及其对换热器效能的影响。     

混合法测量比热容的两个不可忽视的问题

文章论述了温度计浸在水中的体积和热交换时初始时温度是测量中不可忽视的问题     

Ultrasound assisted preparation of calcium alginate beads to improve absorption of Pb+2 from water

Calcium alginate (CaAlg) beads were prepared using ultrasound for use in the removal of lead from natural and wastewaters by ion exchange. Ultrasound was applied in a batch mode with an ultrasonic bath or in a flow mode using an ultrasonic clamp-on device. For comparison purposes the synthesis was performed in batch mode in the absence of the ultrasound. The beads prepared using ultrasound showed a greater ion exchange capability which could be ascribed to a larger specific surface area as a result of surface roughening induced by cavitation.Scanning Electron Microscopy (SEM) images revealed that the roughening was in the form of corrugation for the product with the best ion exchange capability obtained in the flow process where preformed CaAlg droplets were subjected to ultrasound during the setting process. These beads performed 11% better for lead removal than those synthesized in the absence of ultrasound.     

Experimental artefacts in 2D-MAS exchange experiments: non-uniform mixing time within a single 2D run

The practical realization of rotor-synchronized mixing-times in 2D-MAS exchange experiments without the need for a special hardware is reviewed; its consequence for the ‘true mixing time' of the experiment is discussed. We demonstrate influences on experimental rate constants derived from such experiments as well as on the appearance of the 2D-MAS spectra, taken at short mixing times.