中地壳的地球化学动力学和矿石成因

笔者重点进行了大于300℃——在近临界区至超临界区条件下的硅酸盐矿物与水反应动力学实验。矿物(钠长石Ab、透辉石Di、阳起石Act和磁铁矿Mt)的溶解反应动力学实验是使用流体通过叠层反应器的开放体系在25～400℃和22MPa下完成的。实验发现矿物在300℃至400℃范围,在跨越水临界点时出现反应速率的涨落。各种多金属氧化物硅酸盐与水反应时,各个元素溶解到溶液里的释放速率一般不一样,常称为一致溶解作用。但是,在近300℃变为一致溶解作用。实验发现在22MPa时硅酸盐矿物的最大溶解反应速率多是在300℃,如硅的最大释放速率是在300℃。其余元素如Na、K、Mg、Ca、Fe、Al等释放速率在<300℃22MPa时都高于硅的释放速率,在>300℃时硅的释放速率要高于其它元素的释放速率。确切地说,金属与氧之间的键的性质决定了它们(金属氧化物)与水之间反应速率。在一般情况下,Na-Obr,Ca-Obr,Mg-Obr,Al-Obr和Si-Obr的键桥(br),它们之间相对地由具有离子键性质逐步变为具有极性键的性质。由常温常压到亚临界区(300～374℃22MPa),再到大于临界点374℃、22MPa进入超临界区,水的性质随温度、压力变化。水由容易溶解离子键逐渐变为容易打破极性键。笔者还研究了黑钨矿、锡石(玄武岩、花岗闪长岩)与水在250～400℃条件下的反应动力学过程,得出了相同的结果。实验均发现在跨越水临界点时矿物(或岩石)与水反应的动力学涨落。这些实验结果可以用于说明中地壳上部的水/岩相互作用的特征。发生于中地壳的水、岩相互作用大多是在300～450℃和20～50MPa条件下进行的。各地区的地壳厚度不一,中地壳温度压力并不完全相同。模拟中地壳条件下水/岩相互作用实验,目的主要是研究矿物(或岩石)在300～450℃条件下反应动力学过程。已有热液矿床矿物流体包体数据表明:有一批矿床的主要矿石形成于300～500℃,低于NaCl H2O溶液临界线的条件。中地壳的流体处于由亚临界态跨越临界态,进入超临界流体太的演化过程。这种流体的性质变化会引起水/岩相互作用的反应动力学涨落和矿石大量沉淀。     

Predicting size effect on diffusion-limited current density of oxygen reduction by copper wire

The size effect of copper wire radius (0.04–0.82 mm) on the diffusion-limited current density of an oxygen reduction reaction in stagnant simulated seawater (naturally aerated 0.5 mol/L NaCl) is investigated by potentiodynamic polarization and electrochemical impedance spectroscopy (EIS) and compared with the results obtained in 0.5 mol/L H2SO4. In the oxygen diffusion-limited range, size effect is found to occur independent of electrolytes, which is attributed to non-linear diffusion. Additionally, to sati...     

Ultrasonic-assisted condensation of chitosan with salicylaldehyde

In order to synthesize an improved adsorbent for heavy metal ions, we studied the condensation reaction of chitosan with salicylaldehyde in ethanol to form a Schiff base. The effect irradiating the reaction using an ultrasonic liquid processor was contrasted with conventional methods. The IR spectra of condensed chitosan prepared by the two methods showed that their molecular structures were identical. The reaction conditions, including solvents, ultrasonic power density and irradiation time, pH, and reactant ratio, were optimized by orthogonal design. A shorter reaction time and a higher product yield were obtained using ultrasonic-assisted synthesis compared with the traditional method. A condensation degree of 89.63% was achieved using the optimized conditions: i.e. ultrasonic irradiation at 180 W for 60 min; 95% ethanol as the solvent, pH 4.0, and salicylaldehyde:chitosan ratio of 6:1.     

MCM-41/β介孔—微孔复合分子筛的合成、表征及催化性能

以β分子筛为前驱体,水玻璃和硫酸铝为外加硅铝源,采用二元混合表面活性剂为结构导向剂,水热晶化合成MCM-41/β介孔—微孔复合分子筛,并利用XRD、SEM、TEM、N2吸附—脱附和Py-IR等对复合分子筛进行表征,以十氢萘为模型化合物考察复合样品的催化裂解反应性能.结果表明:MCM-41/β介孔—微孔复合分子筛中存在MCM-41分子筛六方介孔结构和β分子筛微孔结构,对十氢萘具有较强的催化反应活性,催化裂解转化率为93.16%.     

Nonlinear analysis of laterally loaded rigid piles in cohesive soil

This article presents a method for the nonlinear analysis of laterally loaded rigid piles in cohesive soil. The method considers the force and the moment equilibrium to derive the system equations for a rigid pile under a lateral eccentric load. The system equations are then solved using an iteration scheme to obtain the response of the pile. The method considers the nonlinear variation of the ultimate lateral soil resistance with depth and uses a new closed‐form expression proposed in this article to determine the lateral bearing factor. The method also considers the horizontal shear resistance at the pile base, and a bilinear relationship between the shear resistance and the displacement is used. For simplicity, the modulus of horizontal subgrade reaction is assumed to be constant with depth, which is applicable to piles in overconsolidated clay. The nonlinearity of the modulus of horizontal subgrade reaction with pile displacement at ground surface is also considered. The validity of the developed method is demonstrated by comparing its results with those of 3D finite element analysis. The applications of the developed method to analyze five field test piles also show good agreement between the predictions and the experimental results. The developed method offers an alternative approach for simple and effective analysis of laterally loaded rigid piles in cohesive soil. Copyright © 2011 John Wiley & Sons, Ltd.     

基于梯度分析法的长江上游水库群供水-发电-环境互馈关系解析

长江上游水资源耦合系统优化调控涉及供水、发电和生态需水等相互竞争、不可公度的调控目标。其供水-发电-环境互馈协变机制难以数学解析和刻画，多维目标效益均衡优化调控难以实施。为此，以多目标优化、运筹学理论及方法为基础，提出了基于梯度分析法的供水-发电-环境两两互馈关系研究方法。通过多目标约束优化方法求解长江上游水库群联合优化调度在供水-发电-环境目标空间的最优解集，并进行插值构造了供水-发电-环境互馈关系多维空间曲面，以此为基础，采用一阶差分近似求解供水对环境和发电对环境偏导函数值，以量化环境对供水变化和发电变化响应的梯度，进而解析环境-供水和环境-发电间互馈协变关系。该方法为水库群优化调度多目标互馈关系研究提供了一种新的思路。     

A garnet population in Yellowknife schist, Canada

Abstract Data are presented on a garnet population in a specimen of garnet-biotite-plagioclase-quartz schist from the cordierite zone of an Archaean thermal dome in the Southern Slave Province of the Canadian Shield. Garnet crystals are bounded by planar dodecahedral faces and by trapezohedral faces which on the 10-μm scale are corrugated. Crystal distribution, as revealed by dissection of a small cubic volume of rock, is random. The size distribution is normal, with a mean diameter of 0.81 mm and a standard deviation of 0.32 mm. In the largest crystal of the population (mean radius 0.83 mm), [Mn] = 100 Mn/(Fe + Mg + Mn + Ca) decreases from 14.5 at the centre to 7.5 and then increases in the outer margin to 8.5; [Fe] increases continuously from 67 at the centre to 77 at the surface; [Mg] increases from 12.5 to 13.5 and then falls sharply to 11; [Ca] remains unchanged at 4.0 and then drops to 3.3. Progressively smaller crystals have progressively lower [Mn] and higher [Fe] concentrations at their centres, while all crystals have the same margin composition. Growth vectors extending from given concentration contours to crystal surfaces are of equal length regardless of the size of the crystal in which the vector is located. A garnet-forming model is presented in which reaction was initiated by a rise in temperature. Nucleation sites were randomly selected. The nucleation rate increased with time and then declined. Crystal faces advanced at a constant linear rate, which implies an increase in volume proportional to surface area. Initially, the composition of garnet deposited on crystal surfaces was determined by van Laar equations of equilibrium, which demanded the withdrawal of Mn and Fe from within chlorite crystals. This transfer reaction was then accompanied by an ion exchange reaction which moved Mn and Fe to garnet surfaces from biotite, in exchange for Mg. The exchange reaction provides an explanation for the high overall concentration of Mn and Fe in garnet and for the observed Mn and Mg reversals in the margins of crystals. The increase of garnet volume in the garnet population is found to be parabolic, i.e. Vαα⁵.