Evolution of Localized Damage Zone in Heterogeneous Media

Evolution of localized damage zone is a key to catastrophic rupture in heterogeneous materials. In the present article, the evolutions of strain fields of rock specimens are investigated experimentally. The observed evolution of fluctuations and autocorrelations of strain fields under uniaxial compression demonstrates that the localization of deformation always appears ahead of catastrophic rupture. In particular, the localization evolves pronouncedly with increasing deformation in the rock experiments. By means of the definition of the zone with high strain rate and likely damage localization, it is found that the size of the localized zone decreases from the sample size at peak load to an eventual value. Actually, the deformation field beyond peak load is bound to suffer bifurcation, namely an elastic unloading part and a continuing but localized damage part will co-exist in series in a specimen. To describe this continuous bifurcation and localization process observed in experiments, a model on continuum mechanics is developed. The model can explain why the decreasing width of localized zone can lead stable deformation to unstable, but it still has not provided the complete equations governing the evolution of the localized zone.

Catastrophic rupture of heterogeneous brittle materials under impact loading

The catastrophic failure of heterogeneous brittle materials under impact loading is not fully understood. To describe the catastrophic failure behavior of heterogeneous brittle materials under impact loading, an elasto-statistical-brittle (ESB) model is proposed in this paper. The ESB model characterizes the disordered inhomogeneity of material at mesoscopic scale with the statistical description of the shear strength of mesoscopic units. If the applied shear stress reaches the strength, the mesoscopic unit fails, which causes degradation in the shear modulus of the material. With a simplified ESB model, the failure wave in brittle material under uni-axial compression is analyzed. It is shown that the failure wave is a wave of strain or particle velocity resulted from the catastrophic fracture in an elastically stressed brittle media when the impact velocity reaches a critical value. In addition, the failure wave causes an increase in the rear surface velocity, which agrees well with experimental observations. The critical condition to generate failure wave and the speed of failure wave are also obtained.

氮杂环化合物的绿色合成研究

氮杂环化合物大多数都是具有生理活性的物质，例如喹喔啉化合物与苯二氮卓类化合物，因此研究氮杂环化合物骨架的构建方法具有一定意义。绿色化学的迅速发展迫切要求化学家发展清洁、经济和环境较友好条件下的有机合成方法。其中，水相反应与绿色固体酸催化剂的使用都是实现绿色有机合成的重要途径，它们非常具有潜力，近些年受到了广泛关注。本论文的主要工作是围绕水相及固体酸催化条件下两类具有生物活性的含氮杂环小分子的合成方法而开展的，具体包括以下内容： 1. 研究和探索出了两类绿色固体酸催化剂蒙脱土（Mont. K-10）和杂多酸(H4SiW12O40), 在水相条件下成功合成出喹喔啉化合物的有效方法。两个催化体系都以无毒无公害的水作反应溶剂，实验条件温和，操作安全简便，反应速度快，底物普适性强，产率高，且产物易分离收集。两类固体酸催化剂，对设备腐蚀性小，可回收循环使用，对环境无公害; 蒙脱土催化大部分底物能得到当量产率的产物，硅钨酸催化催化剂负载量小。 2. 实现了无溶剂条件下，以杂多酸（H3PW12O40）作催化剂，高效合成1,5-苯二氮卓衍生物的合成方法。该催化体系具有以下一些优势：实验条件温和，反应速度较快，底物普适性良好，产物易分离收集，反应过程中没有加入其它有机溶剂，绿色环保。 ‘Green Chemistry’ is currently a major issue of modern chemistry. It is widely acknowledged that there is a growing need for more environmentally acceptable processes in the chemical industry. New green catalysts and green reaction media are the important and efficient strategies in green chemistry. New green catalysts include solid acid catalysts, solid base catalysts, metal catalysts not only possess higher activity and selectivity, but also are easily separated from reaction system. Green reaction media include water, supercritical fluids and ionic liquids can not only substitute traditional toxic and harmed organic solvents, but also improve reaction activity and selectivity. Meanwhile water is a promising green reaction medium for use in modern chemistry because it has a number of advantages such as the cheapest solvent available on earth, being non-hazardous and non-toxic to the environment. Solid acids had also attracted much attention for realizing green chemistry due to their unique acidity, high activity and efficiency as organic catalysts. Nitrogen-containing heterocyclic compounds of different ring sizes such as quinoxaline and benzodiazepine are the important pharmacologically active compounds. Due to the wide biological significance of these compounds, the synthesis of these types of compounds have received a great deal of attention. Despite the large availability of methods to construct nitrogen-containing heterocyclic compounds, there is still a strong need to further explore green methods to efficiently and safely synthesize these compounds. Thus, we aim at developing efficient and green methodology for the synthesis of quinoxaline and benzodiazepine carried out under water condition with solid acid catalysts. The contents of this dissertation are listed as the following: 1. We have developed two catalytic systems for the synthesis quinoxaline via the condensation of an aryl 1,2-diamine with a 1,2-diketone compound in the presence of Mont. K-10 or H4SiW12O40 as a catalyst in water solvent. Both of these two methods can be applied to wide range of substrates, tolerating aryl 1,2-diamine/1,2-diketone with the electron donating/drawing substituent. Operational simplicity, the ambient conditions, use of an economically convenient catalyst, use of water as a desirable solvent, high yields and short reaction times are the key features of these two protocols. 2. We developed a convenient and efficient protocol for the synthesis of a variety of 1,5-benzodiazepines in high yields via condensation of aryl o-phenylenediamine derivatives with a variety of ketones using H3PW12O40 as a green recyclable and heterogeneous catalyst under solvent-free condition. The simple experiment procedure combined with ease of recovery and reuse of this catalyst make this procedure quite simple, more convenient and environmentally benign.

Performance comparison of low-temperature direct alcohol fuel cells with different anode catalysts

Low-temperature polymer electrolyte membrane fuel cells directly fed by methanol and ethanol were investigated employing carbon supported Pt, PtSn and PtRu as anode catalysts, respectively. Employing Pt/C as anode catalyst, both direct methanol fuel cell (DMFC) and direct ethanol fuel cell (DEFC) showed poor performances even in presence of high Pt loading on anode. It was found that the addition of Ru or Sn to the Pt dramatically enhances the electro-oxidation of both methanol and ethanol. It was also found that the single cell adopting PtRu/C as anode shows better DMFC performance, while PtSn/C catalyst shows better DEFC performance. The single fuel cell using PtSn/C as anode catalyst at 90degreesC shows similar power densities whenever fueled by methanol or ethanol. The cyclic voltammetry (CV) and single fuel cell tests indicated that PtRu is more suitable for DMFC while PtSn is more suitable for DEFC. (C) 2003 Elsevier B.V. All rights reserved.

NOx storage-reduction over Pt/Mg-Al-O catalysts with different Mg/Al atomic ratios

A series of Pt/Mg-Al-O catalysts with different Mg/Al atomic ratios were prepared. The NOx storage capacities of these catalysts were measured by isothermal storage at 350 degreesC. It was found that the NOx storage capacity increased with increasing Mg/Al atomic ratios. The catalytic behaviors of Pt/Mg-Al-O and Pt/MgO were studied with storage-reduction cycles at 400 degreesC. Under oxidizing conditions, NOx concentration in the outlet gas gradually increased with time, which indicated the catalysts could store NOx effectively. After a switch from oxidizing conditions to reducing conditions, NOx desorption peak emerged immediately due to the incomplete reduction of stored NOx, which lowered the total NOx conversion. With increasing Mg/Al atomic ratio in the catalysts, NOx conversion increases. Pt/MgO has the highest NOx conversion because of its best activity in the reduction of NOx by C3H6. It seems that with an increasing amount of MgO in the catalysts, the self-poisoning of Pt-sites by adsorbed species during the reaction of NOx with C3H6 may be inhibited effectively.