Chloride transfer in cement‐based materials. Part 1. Theoretical basis and modelling

In this first part of the work, we develop macroscopic models for migration and diffusion–migration of ionic species in saturated porous media, based on periodic homogenization. The prior application is chloride transport in cementitious materials. The dimensional analysis of Nernst–Planck equation lets appear to dimensionless numbers characterizing the ionic transfer in the porous medium. Using experimental data obtained from electrodiffusion tests on cement‐based materials (Part II), these dimensionless numbers are linked to the perturbation parameter ?. For a strong imposed electrical field, the asymptotic expansion of Nernst–Planck equation leads to a macroscopic model where the migration is predominant. For a weak imposed electrical field or in natural diffusion, we obtain a macroscopic model coupling diffusion and migration at the same order. In both models, the expression of the homogenized diffusion tensor is identical and only involves the geometric properties of the material microstructure. Copyright © 2012 John Wiley & Sons, Ltd.     

基于混合物理论的水力-化学-力学污染物输运模型研究

由于废弃物的堆积以及填埋场上覆盖层的重量,衬垫因此承受一定的压力,发生力学固结;由于黏土本身的结构特性,当污染物通过黏土垫层时可能会发生化学固结,而固结作用可直接对污染物的对流输运产生影响,也会引起土层体积和结构的变化,从而改变其固有的输运性质。从混合物理论出发,建立了水力-化学-力学作用下的溶质输运理论框架,统一地描述了水力-化学-力学作用下变形、水的吸附或解吸附、对流和扩散现象。将输运系数考虑为有效孔隙率的函数,由此反映固结对输运参数的影响。对所建立的数学模型进行无量纲化处理,并使用有限元软件COMSOL Multiphysics进行求解,最后进行了参数分析。研究结果表明,垫层土体中吸附水和自由水之间的化学势差异越大,层间吸附水的解吸附量越大;当土体的软硬性质不同时,当层间吸附水解吸附后,土体固结程度不同,从而对污染物输运过程的影响不同。而当垫层上覆荷载增大时,土体宏观孔隙的扩张的限制作用增强,从而对土体产生一种修复作用,抑制污染物在土体中的输运。     

Upwind‐mixed methods for transport equations

In this paper, we continue our analysis of upwind‐mixed methods for advection–diffusion equations, which have been developed and analyzed by the first author over the past several years. In previous work, our analysis has been limited to low order approximating spaces, positive definite diffusion coefficients and Dirichlet boundary conditions. In this paper, we extend our results to higher order approximating spaces, possibly zero diffusion, and more physically realistic boundary conditions. Moreover, unlike previous papers, we avoid the use of Gronwall's Inequality, which can result in extremely large constants in the stability and error bounds. Numerical results are presented for constant, linear and quadratic approximating spaces. This revised version was published online in July 2006 with corrections to the Cover Date.     

湍流混合动力学机理研究

在分析传统混合动力学机理基础上,通过宏观混合与微观混合时间量级的对比,提出了湍流条件下,涡流扩散主导宏观混合,分子扩散主导微观混合,而混合过程由宏观混合主导,欧拉数Eu可作为混合效果的控制指标,并通过3种不同容积反应器的混合搅拌试验,进一步证实了该指标的实用性。     

A reactive transport simulator for variable porosity problems

ReactMiCP, a new reactive transport simulator was developed based on the semismooth speciation solver SpecMiCP. Its main feature is a sequential iterative operator splitting algorithm where macroscopic model parameters are explicitly included in the formulation. Its correctness, robustness, and efficiency are tested against the MoMaS benchmark and two sets of cement paste lab experiments. We show that a robust speciation solver is a key requirement for good performance of the reactive transport simulator. We also demonstrate that a sequential iterative solver should be preferred over non-iterative solvers when using operator splitting. The flexibility and the speed of the simulator are used to test the influence of the database, the initial condition, and the diffusion coefficient model for the cement paste simulations.     

考虑非等温环境下污染物在黏土中的运移解析模型

利用广义积分变换法推导了非等温条件下污染物在压实黏土衬垫中的运移解析解。所提出的解析解考虑了分子扩散、对流、吸附和热扩散的耦合效应,并考虑了压实黏土的渗透系数、分布系数和有效扩散系数3个参数随温度的变化。通过与热扩散试验结果、已有的解析解和基于COMSOL软件的数值模型的对比,验证了所提出的解析解。利用经过验证的解析解,研究了非等温环境以及压实黏土的渗透系数、有效扩散系数和分布系数3个参数随温度的变化对甲苯在压实黏土衬垫系统中迁移的影响。结果表明,非等温环境以及压实黏土的渗透系数、有效扩散系数和分布系数随温度的变化均对甲苯在压实黏土衬垫中迁移有着显著的影响。不考虑非等温环境的影响将极大低估污染物的溢出量和污染物的击穿时间。既有解析解忽略压实黏土的渗透系数和有效扩散系数随温度的变化会极大低估甲苯的流出速率,而忽略压实黏土分布系数随温度的变化会极大高估甲苯击穿衬垫系统的时间和达到稳态的时间。所提出的解析解能够考虑热扩散作用,同时考虑了压实黏土的渗透系数、分布系数和有效扩散系数3个参数随温度的变化,较既有解析解更贴近工程实际,能够为压实黏土衬垫系统的设计和服役性能评价提供指导和借鉴。     

颗粒煤甲烷吸附过程扩散特征

为了研究甲烷在颗粒煤中扩散、吸附至平衡过程的扩散特性,基于颗粒煤吸附甲烷幂函数扩散模型,利用磁悬浮天平高压等温吸附仪,测定不同压力下颗粒煤甲烷吸附过程中扩散量随时间变化值,研究颗粒煤甲烷吸附达到平衡前的扩散特征。实验结果表明:平衡压力对颗粒煤甲烷吸附和扩散特性影响显著;吸附量和平均扩散系数随着压力增大而增大;颗粒煤甲烷吸附过程扩散系数随时间呈幂函数衰减,前500 s衰减幅度较大,平均扩散系数与时间呈负相关关系。研究认为颗粒煤吸附甲烷幂函数扩散模型对于描述颗粒煤甲烷吸附扩散过程具有较高准确性,有助于分析煤层气排采过程煤层气吸附量的动态变化,提高煤层气采收率。      

高塌落度防渗墙填料扩散系数快速测定的透析试验

扩散是低渗透系数情况下溶质迁移的主要方式,目前尚没有测定高塌落度防渗墙填料扩散系数的试验方法。根据沥出试验原理,将处于流动状态的填料用半透膜包裹进行透析试验,通过有限圆柱中溶质迁移解析解对溶质迁移过程进行拟合求其扩散系数,探讨了试验和数据处理的相关问题,研究了膨润土含量和盐浴浓度对扩散系数的影响规律。结果表明,随拟合天数增加,填料中NaCl有效扩散系数减小,而误差增大;高塌落度填料中溶质迁移明显比压实土样中快,按拟合误差小于0.5%作为试验数据取舍依据,这一误差要求实际上是对溶质迁移以扩散为主导这一条件的量化,保证了采用纯扩散解析解进行数据拟合的合理性;扩散系数随填料中膨润土含量增加而减小,随盐浴浓度增加而减小,但在试验范围内数值变化不大,透析试验是快速测定防渗墙填料中溶质有效扩散系数的可行方法。     

结晶岩石分子扩散系数薄片渗透测试方法

结晶岩石分子扩散系数是影响岩石内部物质运移的重要水文地质参数。由于结晶岩石结构致密,渗透性差,以通常的松散岩石分子扩散系数测试方法无法测得该参数。为此,本文提出薄片渗透测试方法,能够有效地观测出结晶岩石分子扩散现象,计算出分子扩散系数。实验证明,这是结晶岩石分子扩散系数测定的有效方法。     

粘土衬垫中渗透系数与扩散系数的关系

扩散系数和渗透系数是设计与评价垃圾填埋场衬垫等环境工程研究时需要确定的重要参数。通过分析粘土衬垫材料中渗透系数和扩散系数的物理意义和确定方法,在土多孔介质微观结构分析的基础上得到渗透系数和扩散系数的关系表达式,并基于蒙脱石层间Poiseuille定律得到膨润土有效扩散系数的计算公式。验证表明,在一定精度范围内文中表达式是有效的。得出的渗透系数和扩散系数的关系表达式,对于根据已有渗透系数的研究成果来预测和分析扩散系数是有意义的。      

Numerical estimation of effective diffusion coefficients for charged porous materials based on micro-scale analyses

In order to describe diffusive transport of solutes through a porous material, estimation of effective diffusion coefficients is required. It has been shown theoretically that in the case of uncharged porous materials the effective diffusion coefficient of solutes is a function of the pore morphology of the material and can be described by the tortuosity (tensor) (Bear, 1988 [1]). Given detailed information of the pore geometry at the micro-scale the tortuosity of different materials can be accurately estimated using homogenization procedures. However, many engineering materials (e.g., clays and shales) are characterized by electrical surface charges on particles of the porous material which strongly affect the (diffusive) transport properties of ions. For these type of materials, estimation of effective diffusion coefficients have been mostly based on phenomenological equations with no link to underlying micro-scale properties of these charged materials although a few recent studies have used alternative methods to obtain the diffusion parameters (Jougnot et al., 2009; Pivonka et al., 2009; Revil and Linde, 2006 2, 3 and 4). In this paper we employ a recently proposed up-scaled Poisson–Nernst–Planck type of equation (PNP) and its micro-scale counterpart to estimate effective ion diffusion coefficients in thin charged membranes. We investigate a variety of different pore geometries together with different surface charges on particles. Here, we show that independent of the charges on particles, a (generalized) tortuosity factor can be identified as function of the pore morphology only using the new PNP model. On the other hand, all electro-static interactions of ions and charges on particles can consistently be captured by the ratio of average concentration to effective intrinsic concentration in the macroscopic PNP equations. Using this formulation allows to consistently take into account electrochemical interactions of ions and charges on particles and so excludes any ambiguity generally encountered in phenomenological equations.     

Effect of particle friction and polydispersity on the macroscopic stress–strain relations of granular materials

The macroscopic mechanical behavior of granular materials inherently depends on the properties of particles that compose them. Using the discrete element method, the effect of particle contact friction and polydispersity on the macroscopic stress response of 3D sphere packings is studied. The analytical expressions for the pressure, coordination number and fraction of rattlers proposed for isotropically deformed frictionless systems also hold when the interparticle coefficient of friction is finite; however, the numerical values of the parameters such as the jamming volume fraction change with varying microscopic contact and particle properties. The macroscopic response under deviatoric loading is studied with triaxial test simulations. Concerning the shear strength, our results agree with previous studies showing that the deviatoric stress ratio increases with particle coefficient of friction μ starting from a nonzero value for μ = 0 and saturating for large μ. On the other hand, the volumetric strain does not have a monotonic dependence on the particle contact friction. Most notably, maximum compaction is reached at an intermediate value of the coefficient of friction μ ≈ 0.3. The effect of polydispersity on the macroscopic stress–strain relationship cannot be studied independent of initial packing conditions. The shear strength increases with polydispersity when the initial volume fraction is fixed, but the effect of polydispersity is much less pronounced when the initial pressure of the packings is fixed. Finally, a simple hypoplastic constitutive model is calibrated with numerical test results following an established procedure to ascertain the relation between particle properties and material coefficients of the macroscopic model. The calibrated model is in good qualitative agreement with simulation results.     

铅污染对黄土宏观持水性能和微观结构演化的影响研究

垃圾填埋场渗滤液中的重金属与土体发生物理化学反应,可能导致土体微观结构的改变,重金属等有毒物质得以扩散、运移,威胁人体健康和周边环境。为探究重金属污染对黄土宏观持水性及微观结构的影响,采用轴平移技术测得铅污染黄土的土-水特征曲线。通过扫描电子显微镜（SEM）、压汞（MIP）、X射线衍射（XRD）和Zeta电位试验,阐明细观结构变化特征。结果表明：铅污染黄土的进气值随铅离子浓度的增加而减小,当铅污染浓度由0 mg/kg增加至2 000 mg/kg时,进气值从19.18 kPa下降至12.12 kPa;铅污染导致持水性能降低,渗透系数随铅离子浓度的增加而增加,饱和渗透系数从7.92×10–8 m/s增加到3.73×10–7 m/s;铅污染引起的物理化学反应及Zeta电位的降低导致絮凝结构形成,小孔隙占比减小,中孔隙占比增加;铅污染引起的微观结构演化与宏观持水性和渗透性具有良好的对应关系。该研究结果可为重金属污染场地非饱和渗流及溶质运移等问题的研究提供重要参数。     

构造煤与原生结构煤中甲烷扩散性能差异性分析

原生结构煤受构造应力破坏后形成不同类型煤体结构煤,其孔隙结构、吸附/解吸、扩散和渗透能力等将发生变化,从而影响煤层气的赋存与产出.通过对沁水盆地赵庄井田3号煤层原生结构煤与构造煤样品进行甲烷等温吸附实验、低温液氮和二氧化碳吸附实验,分析了构造煤与原生结构煤的吸附?解吸性能及孔隙结构特征;应用单孔和双孔非稳态扩散模型,揭...     

川南煤层甲烷解吸动力学影响因素实验研究

为了系统研究煤层气（甲烷）解吸动力学的影响因素,选用川南地区的无烟煤,设计了不同压力、温度、粒度和湿度下的煤层气解吸动力学实验。采用高温高压煤层气吸附/解吸测试系统进行实验,并拟合实验结果获得了不同条件下的扩散系数。研究表明:压力和温度越高,甲烷解吸量和解吸速率越大;粒度越大,甲烷解吸量和解吸速率越小;低于平衡水含量时,湿度增大,甲烷解吸量和解吸速率降低;甲烷扩散系数拟合结果揭示,扩散系数随压力增高而减小,随温度升高而增大,随湿度增大而减小。      

A new interpretation of measured ionic diffusion coefficient in compacted bentonite-based materials

Previous model based on free-water properties to interpret the measured diffusion coefficient in compacted bentonite-based materials is demonstrated to be inadequate. A model considering ionic diffusion in clay surface (bound) and interstitial (free) water is presented to interpret the measured diffusion coefficients and to explain the possible reasons for the discrepancies in the data. The measured diffusion coefficient is determined by the predominant diffusion pathway, which depends on the charge of diffusing species, soil fabric, diffusion time and by the starting concentration condition of the method used.     

应用土柱试验求解地下含水介质弥散系数

污染物质在地下含水介质中的运移,除受渗透系数等水文地质条件的制约外,还受到含水介质弥散系数的控制。污染物的扩散,首先是从包气带开始进行的,浑河冲洪积扇地包气带主要岩性是亚粘土及亚砂土,因此,计算出浑河冲洪积扇包气带的弥散系数,对于认识污染物的运移能力是一项必要的工作。本文利用室内动态土柱装置,模拟包气带岩性环境,以0.05 mol/L的NaCl溶液作为示踪剂,经长时间监测,运用弥散系数计算公式进行求参。计算结果是包气带以亚粘土为主要岩性的弥散系数为0.005 71 m2/d,亚砂土的弥散系数为0.012 47 m2/d。     

Quantification of electrical resistance to estimate NaCl behavior in a column under controlled conditions

Accurate prediction of solute transport processes in surface water and its underlying bed is an important task not only for proper management of the surface water but also for pollution control in these water bodies. Key issue in this task is an estimation of parameters as diffusion coefficient and velocity for solute transport both in water body and in the underlying bed. This estimation would greatly help us to understand the deposition and release mechanism of solute across the water-bed interface. In this study, a column experiment was conducted in laboratory to estimate the velocity and diffusion coefficient of sodium chloride (NaCl) in water body and underlying sand layer (bed). The column used with a diameter of 30 cm and a height of 100 cm, was filled with sand at the lower half part and water at the upper half part. Total 64 stainless steel electrodes were installed on its surface around. The sodium chloride solution was injected from the top of the column, and electrical resistance between electrodes was monitored for 71 h. Then the dimensionless resistance breakthrough curve was fitted with one dimensional analytic solution for solute transport and the related diffusion coefficient and velocity parameters were estimated. The results show that the NaCl transport velocity was high in the water body but extremely low in the underlying sand layer (bed). The diffusion coefficient estimated in sand layer coincides with those reported well. This indicates that the electrical resistance based solute transport parameter estimation method is not only effective but also has an advantage of multipoints monitoring. This is useful both in mapping solute transport parameter for solute transport process analysis and in providing parameter input for solute transport numerical modeling.     

煤基质中甲烷扩散特征及其对气井产能的影响

扩散是煤层甲烷运移的关键环节之一,而目前有关煤层中甲烷扩散特征的认识并不充分.以沁水盆地南部高煤阶煤层气藏为例,应用微纳渗流力学理论分析了煤基质中气体扩散模式及定量表征参数;应用Simed软件开展了扩散性能对不同煤体结构煤层气排采规律的影响数值研究.结果表明:煤层甲烷的扩散受化学势梯度的驱动,产气过程中体相扩散、努森扩散和构型扩散模式并存且呈动态变化;甲烷扩散性能受气体温度、压力、气体种类、水分以及基质孔隙结构共同影响,基质孔隙吸附甲烷会改变微孔孔径并影响扩散路径的空间形态;煤基质中甲烷的扩散是非热力平衡过程,扩散系数是吸附量的函数.基于拟稳态扩散的数值研究表明,扩散性能强弱对于长期累计产气量几乎没有影响,而对短期产气速率具有较大的影响;扩散性能弱的,产气速率峰值较低,但峰值之后的一段时间内产气速率相对较高;与高渗煤层相比,低渗构造煤层的产气速率对吸附时间常数更敏感.