土体耗散势的存在性

从热力学出发,基于不可逆热力学土体损伤理论所存在的基本问题:耗散势函数可否分解为塑性势函数和损伤势函数,即塑性、损伤两种耗散机制可否解耦,给出了全量型耗散势函数存在的充分必要条件并加以严格证明。结合土体的基本变形性质,证明了土体不存在耗散势函数。     

东南极中山站附近湖冰与固定冰热力学过程比较

2006年对东南极中山站附近湖冰和固定冰的热力学过程进行了系统观测.基于观测数据比较湖冰和固定冰热力学生消过程;分析湖冰和固定冰温度对气温变化的响应规律;计算不同深度层湖冰和固定冰的垂向热传导通量.结果表明:观测的湖泊和海岸区均在2月底至3月初形成连续冰层;湖冰9月底至10月初达到最大冰厚,早于固定冰1-2个月,湖冰最...     

A coupled damage–plasticity model for concrete based on thermodynamic principles: Part I: model formulation and parameter identification

The development of a coupled damage‐plasticity constitutive model for concrete is presented. Emphasis is put on thermodynamic admissibility, rigour and consistency both in the formulation of the model, and in the identification of model parameters based on experimental tests. The key feature of the thermodynamic framework used in this study is that all behaviour of the model can be derived from two specified energy potentials, following procedures established beforehand. Based on this framework, a constitutive model featuring full coupling between damage and plasticity in both tension and compression is developed. Tensile and compressive responses of the material are captured using two separate damage criteria, and a yield criterion with a multiple hardening rule. A crucial part of this study is the identification of model parameters, with these all being shown to be identifiable and computable based on standard tests on concrete. Behaviour of the model is assessed against experimental data on concrete. Copyright © 2007 John Wiley & Sons, Ltd.     

水溶液中各化学组分可能存在式形分配及Eh值的计算方法

本文在参阅Crerar D.A.等人的资料的基础上,比较系统地论述了水溶液中各种化学组分可能存在形式分配及Eh值的计算方法。文章从对施实计算所需的原始数据的说明开始,主要从以下几个方面说明了计算方法:1.热力学问题的数学描述;2.问题的数值解;3.活度系数的校正;4.迭代步骤;5.Eh值的计算。文中以华清池温泉水化学分析资料为例,分别给出了此资料在12℃和42℃时的计算结果。由于分析技术和计算方法的误差,Eh值的计算结果存在一定的偏离,这也可能是由于给定温度下水中某些组分间存在着非平衡而引起的。     

The effects of stress on reactions in the Earth: Sometimes rather mean,usually normal,always important

Stress affects chemical processes on all scales in the Earth but the magnitude of its effect is debated. Here, I give a new synthesis of the theory that describes the effects of stress on chemistry, elaborating upon work in Materials Science which is built from fundamental thermodynamic laws, and show its significance in Earth Science. There are separate but compatible relationships describing what happens (1) at interfaces and (2) within grains. (1) The main chemical effects of stress in the Earth are due to variations in normal stress along grain interfaces and between interfaces with different orientations. For reactions involving diffusion these variations give effects on mineral stability broadly equivalent to pressure changes of (molar volume)/(molar volume change during reaction) × (stress variation). The volume ratio is generally large and so the effects of normal stress variations are always important since all stressed rocks have interfaces supporting different normal stresses. There is no global chemical equilibrium in a stressed system, so reaction kinetics contribute to ongoing evolution until stresses relax: this evolution can include deformation by diffusion creep and pressure solution, possibly with new mineral growth. These effects are relevant for predicting the conditions for reactions involving fluids, such as serpentinite formation and breakdown (relevant for the Earth's volatile cycles) and for other reactions such as ringwoodite breakdown (relevant for understanding the 660 km mantle discontinuity). (2) Within stressed solid solution grains it is not possible to define chemical potentials of all chemical components since one has to be specified as “immobile.” The chemical potential of a “mobile” component such as an exchange vector can be defined. It depends on the “partial molar strain,” a second rank tensor defining the variation in unit cell geometry with composition. In cubic crystals the partial molar strain is isotropic and the chemical potential of a mobile component depends on mean stress. In other crystal systems the partial molar strain is anisotropic and the chemical potential depends on a “weighted” mean stress; orientation as well as magnitude of stress has an influence. I propose “chemical palaeopiezometry”—the possibility of measuring past stress levels via chemistry. Examples show that stress variations in hundreds of MPa to GPa are required to produce 2% variations in composition but high stresses and/or precise chemical analyses will allow this proposal to be tested. High stresses around inclusions and dislocations could be targeted. So, the weighted mean stress inside grains has an effect which is relatively minor although potentially valuable in explaining chemical variations; the normal stress at interfaces plays the main role in chemical processes and its effects are of significant magnitude.     

热带气旋边界层关键结构研究进展

边界层的动热力结构在很大程度上决定了热带气旋(TC)的发生发展,首先,TC边界层是触发TC对流的源地,并作为海-陆-气能量交换的主要中介,提供TC发生发展的重要能源;其次,边界层是TC对流发展所需水汽的主要输送通道;第三,TC登陆时,陆地下垫面摩擦直接作用于边界层,加强辐合、对流和湍流输送.对这些特征的了解有利于从根本上掌握TC发展变化的规律,为提高登陆TC分析和预报水平奠定基础,具有重要的科学价值和实际意义.本文在前期TC边界层研究工作的基础上,从热力学和动力学的角度,介绍了近年来国际上关于TC边界层风场、湍流交换、卷涡、能量和水汽输送等关键结构特征研究的主要进展.阐述了边界层入流对于TC能量平衡、水汽输送的重要作用,揭示了边界层超梯度风现象存在的机制和成因,以及边界层卷涡与边界层动量输送和TC强度发展的关系.这些认识有助于加强TC边界层关键结构对TC发展作用的理论认识.在此基础上,指出了目前TC边界层研究中存在的核心难点问题,并建议将TC边界层研究与数值预报方法相结合:除了将边界层观测通过资料同化应用于TC数值模式初始化,还可研究优化与TC涡旋结构相关的边界层参数化方法,实现TC数值模式初始化与边界层物理过程的衔接,探索可切实改进TC预报的有效途径.     

Unsaturated hydro-mechanical-chemo coupled constitutive model with consideration of osmotic flow

Since low permeability rock has the potential to behave as an actual semi-permeable osmotic membrane, chemical osmosis may have an effect on water flow and needs to be accounted for in analysis. Hence, an advanced fully coupled formulation for modelling unsaturated hydro, chemical and mechanical effects is here presented based on modified mixture theory. Firstly, the classical Darcy’s law has been modified to include the chemical potential. Secondly, the mechanical deformation, which affects the permeability, has been coupled with the water and chemical flows by using Helmholtz free energy and the Gibbs–Duhem equation. Finally, an illustrative numerical example with relevance to radioactive waste disposal has been analysed to investigate the performance of the coupled formulation and the relative influence of parameters.     

针铁矿和蒙脱石对菲的吸附解吸行为与热力学研究

采用批量振荡吸附平衡法设计针铁矿和蒙脱石对菲的吸附解吸试验,对比研究了针铁矿和蒙脱石对菲的吸附解吸行为,并考察了不同K+浓度的溶液对蒙脱石吸附菲的影响,比较分析了线性吸附模型和Freundlich吸附模型描述矿物吸附等温线的准确性,并从吸附热力学角度探讨了矿物的吸附机理。结果表明:针铁矿和蒙脱石对菲的吸附解吸均表现出明显的非线性和解吸滞后现象;相对于线性吸附模型来说,针铁矿和蒙脱石对菲的吸附解吸更符合Freundlich吸附模型;与蒙脱石相比,针铁矿对菲的吸附更为显著,且具有更好的稳定性;溶液中软阳离子K+的存在使蒙脱石对菲的吸附能力得到显著提高;菲在蒙脱石和针铁矿上的吸附过程是一个自发放热,同时伴随着熵值减小的过程;随着温度的升高,蒙脱石和针铁矿对菲的吸附能力均减弱。     

边界热质传递过程的主动传递过程分析及应用

边界热质传递过程的主动传递(Active Transport)为由"低势"向"高势"的物量(包括质量、能量和信息等)传递,传递动力由边界内的其他能量(如化学反应等)或耦合作用提供,主动传递过程已经超越经典传热学和热力学的范围.基于Kedem分析方法,采用传热学和不可逆热力学理论相结合的方法研究边界热质传递过程的主动传递机理,提出耦合流、正耦合、负耦合和耦合程度等概念,并以两组分膜分离系统为例进行分析.     

磷酸根对水稻土中重金属镉汞铅吸附特性的影响研究

以合肥市郊的大兴镇和义城镇地区水稻土为主要研究对象,利用批量平衡法初步研究了重金属在两种土壤中的吸附热力学,据此分析研究水稻土对重金属的吸附性能及机理。在施磷情况下两种水稻土对三种重金属Cd,Hg,Pb吸附自由能均为负值,是常温常压下可以自发进行的过程,是物理和化学吸附并存的过程。两种水稻土对三种重金属Cd,Hg,Pb吸附过程均是熵增过程。