A new procedure to measure effective molecular diffusion coefficients of salts solutions in building materials

The aim of this work is to present a mathematical and experimental formulation of a new simple procedure for the measurement of effective molecular diffusion coefficients of a salt solution in a water-saturated building material. This innovate experimental procedure and mathematical formulation is presented in detail and experimental values of “effective” molecular diffusion coefficient of sodium chloride in a concrete sample (w/c = 0.45), at five different temperatures (between 10 and 30 °C) and four different initial NaCl concentrations (between 0.1 and 0.5 M), are reported. The experimental results obtained are in good agreement with the theoretical and experimental values of molecular diffusion coefficient presented in literature. An empirical correlation is presented for the prediction of “effective” molecular diffusion coefficient over the entire range of temperatures and initial salt concentrations studied.     

Modeling the Chlorides Transport in Cementitious Materials By Periodic Homogenization

In this work, we develop a macroscopic model for 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 dimensionless numbers characterizing the ionic transfer in porous media. Using experimental data, these dimensionless numbers are linked to the perturbation parameter ${\varepsilon}$ . For a weak-imposed electrical field, or in natural diffusion, the asymptotic expansion of Nernst–Planck equation leads to a macroscopic model coupling diffusion and migration at the same order. The expression of the homogenized diffusion coefficient only involves the geometrical properties of the material microstructure. Then, parametric simulations are performed to compute the chloride diffusion coefficient through different complexity of the elementary cell to go on as close as possible to experimental diffusion coefficient of the two cement pastes tested.     

Equivalent Diffusion in a Thin Film Flow with a Non-One-Dimensional Velocity Field and Anisotropic Diffusion Tensor

For describing the mass transfer processes in channels, Taylor's dispersion theory is widely used. This theory makes it possible, with asymptotic rigor, to replace the complete diffusion (heat conduction) equation with a convective term that depends on the coordinate transverse to the flow by an effective diffusion (dispersion) equation with constant coefficients, averaged over the channel cross-section. In numerous subsequent studies, Taylor's theory was generalized to include more complex situations, and novel algorithms for constructing the dispersion equations were proposed. For thin film flows a theory similar to Taylor's leads to a matrix of dispersion coefficients.In this study, Taylor's theory is extended to film flows with a non-one-dimensional velocity field and anisotropic diffusion tensor. These characteristics also depend to a considerable extent on the spatial coordinates and time. The dispersion equations obtained can be simplified in regions in which the effective diffusion coefficient tensor changes sharply.     

均匀化方法在粘弹性多层复合材料中的应用

主要研究了由各向同性线弹性加强体和各向同性线粘弹性基体组成的多层复合材料的问题,在已有的线弹性多层材料的均匀化方法的基础上,应用弹性一粘弹性对应原理,在Carson域中求解粘弹性多层材料的问题。通过Burgers模型表示线粘弹性基体材料,反演得到了多层材料的有效松弛模量和有效泊松比在时间域中的表达式,并且与实验结果和其他结果进行了比较。     

Transport of reactive solutes in unsteady annular flow subject to wall reactions

The present paper concerns with the dispersion process in steady and oscillatory flows through an annular pipe in presence of reversible and irreversible reactions at the wall. Method of homogenization, a multiple-scale method of averaging, is adopted for deriving the effective transport equations. The main objective is to look into the effect of aspect ratio of the annular pipe on the dispersion coefficient due to the combined effect of axial convection and radial diffusion in steady and oscillatory flows along the annulus, subject to the kinetic reversible phase exchange and irreversible absorption at the outer wall. Results demonstrate that upto a certain critical value of aspect ratio, dispersion coefficient increases with increase of aspect ratio when the wall is retentive, though the wall inertness may lead to decrease of dispersion coefficient with increase of aspect ratio. The results would be useful to the medical practitioners working in the domain of catheterized artery.     

Asymptotic form of the admixture transport equation for a channel flow with an anisotropic diffusion tensor

The problem of the asymptotically correct reduction of a 3-D mass (heat) transfer equation to a 1-D equation in a flow with anisotropic diffusion properties is considered. The convective mass (heat) transfer domain is a cylindrical channel of arbitrary cross section. The diffusion coefficient matrix is assumed to be independent of the spatial coordinates. In the equivalent diffusion equation constructed, a certain effective diffusion (dispersion [1]) coefficient is introduced. Formulas for this coefficient are obtained. A relation between the effective diffusion coefficient calculations and the problem of minimization of a certain functional is established, i. e. the possibility of calculations based on variational methods is noted. An example of an exact calculation of the effective diffusion coefficient is considered. The possibility of a generalization of the problem, in which the effective diffusion (heat conduction) equation is essentially a nonlinear equation of general form for the one-dimensional case, is indicated. Sankt-Peterburg. Translated from Izvestiya Rossiiskoi Akademii Nauk, Mekhanika Zhidkosti i Gaza, No. 2, pp. 110–123, March–April, 2000.     

基于均匀化理论的页岩微观多孔黏土强度特性

页岩强度是页岩油气开发所必需的基础技术参数之一,对页岩强度的研究贯穿于钻完井、压裂工艺施工的全过程.常规宏观室内实验存在试样获取困难、耗时较长,受井下工矿制约,地球物理方法获取资料品质欠佳且增加了井下设备卡、埋风险.因此,提出基于均匀化理论评价页岩微观多孔黏土强度的方法,进行多孔黏土组成与力学分析.基于耗散能原理和Drucker-Prager准则,开展了微观多孔黏土的强度与$\pi$函数的应变求解分析;讨论黏土颗粒与粒间孔隙的力学特性,建立多孔黏土的均匀化应变能;采用强度均匀化理论构建微观非线性函数模型,建立与多孔黏土组成、摩擦系数、内聚系数等参数相关的均匀化函数模型;基于纳米力学实验、量纲分析和有限元模拟,分析多孔黏土硬度、强度与组成的内在关系.研究结果表明,页岩微观多孔黏土的弹性模量和硬度与黏土堆积密度正相关,当黏土堆积密度一定时,硬度与内聚系数的比值受摩擦系数影响较大,为非线性递增;通过量纲分析和有限元模拟,求解页岩微观多孔黏土关于硬度--强度--堆积密度的$\pi$函数,揭示页岩微观黏土矿物的组成与力学性质的关系,为进一步深入研究页岩细观强度参数和宏观强度预测奠定基础.      

Monitoring of Pollutant Diffusion into Clay Liners by Electrical Methods

A non-destructive test was carried out on a liner material—sand bentonite mixture (SB) with a continuous concentration diffusion of NaCl electrolyte. The work reported studied the spacio-temporal variation of the electrical conductivity $\sigma ^{*}_{\mathrm{s}}$ (z, t) in a diffusion soil column with different heights. A relationship between the interstitial pore fluid concentration of SB and the electrical conductivity of the solution has been established by mixing and compacting samples of sand bentonite with NaCl electrolytes at different concentrations. Electrical conductivity of compacted specimens was measured with a two-electrode cell. The conductivity measurements were used to quantify the pore fluid concentration and effective diffusion coefficient of SB liners. It is concluded here that the electrical conductivity of compacted specimens depends mainly on the salt concentration in the pore fluid and it could be used to measure ionic movement through liners during diffusion. The experimental diffusion coefficient reached theoretical diffusion coefficient when sample height is equal to 40 cm.     

Modeling of Nuclear Species Diffusion Through Cement-Based Materials

The use of cement-based materials for radioactive waste confinement and storage must rest on precise measurements of their physical and chemical properties. An important property is the diffusivity of tritium in its liquid form (tritiated water) through a sample considered as representative. Here, we report quantitatively the effect of radioactive decay compared to the effective diffusion coefficient on tritium diffusion. The numerical model was validated by comparing it to experimental data. We found that, in the worst case scenario, the calculated effective diffusion coefficient of tritiated water based on the classical analytical solution to Fick’s law is underestimated by more than 20 %, compared with the results provided by the numerical model, which accounts for the radioactive decay within the material.     

Application of the asymptotic homogenization method to find the expansion coefficient of a water-saturated porous medium during freezing processes

An approach is proposed to determine the effective relative expansion coefficient of a porous medium filled with water during its freezing. This approach is based on an asymptotic homogenization method. An explicit formula is derived to find the expansion coefficient in the case of open pores. In the case of closed pores, the expansion coefficient is a second-rank tensor. Its determination requires to solve the so-called local problems in a representative volume element. The proposed approach can be used to determine the effective expansion coefficient during the freezing of water in the soil. Its efficiency is confirmed for model and realistic geological structures.     

Computation of Saturation Dependence of Effective Diffusion Coefficient in Unsaturated Argillite Micro-fracture by Lattice Boltzmann Method

Getting access to the effective diffusion coefficient is a key point to provide realistic predictions of migration of radionuclides from radioactive waste repository in deep argillaceous geological formations. In the present work, the effective diffusion coefficient was computed inside an argillite micro-fracture as a function of its saturation level. The micrometric fracture geometry was extracted from the X-ray \(\mu \)-tomography image (\(0.7\,\upmu \mathrm{m}\) voxel resolution) of an Opalinus clay sample. It was collected in the host rock excavated damaged zone surrounding a borehole in the Mont Terri laboratory. The computations were performed using two two-relaxation-time lattice Boltzmann models. The first one, a phase separation model, was used to extract the connected liquid phase inside the fracture for given saturations. The second, a diffusion model, was used to compute non-reactive tracer diffusion in the connected liquid phase of the fracture and to calculate the effective diffusion coefficient for the associated saturations. The dependence of the effective diffusion coefficient on saturation was found to be quasi-linear and to qualitatively match the Maxwell expression for saturations lower than 0.8.     

Diffusion of Randon in Porous Media Saturated with Gels and Emulsions

The effective diffusion coefficient of radon was determined in polymer/silicate gels and clay suspension used as sealing materials in environmental protection. On the basis of the experimental findings, it was concluded that both materials drastically decrease the convective mass transport in porous media. Simultaneously, the effective diffusion coefficient was reduced significantly. Thus, the radon flux might be decreased by 5 to 6 orders of magnitude in porous systems originally having gas or low water saturation by injection of gel-forming materials or placement of clay suspensions. At high water saturation, however, the diffusion transport of radon can be slightly restricted in consolidated and unconsolidated porous media. The laboratory studies may firmly allow us to conclude that hydrogels and clay suspensions are prospective candidates in an integrated environmental technology to be used for restriction of radon migration in subsurface regions.     

Measurement of the concentration diffusion coefficient for He-Ar and Ne-Kr by a two bulb method

Summary A two bulb glass apparatus was used to measure the concentration diffusion coefficient of the binary gas systems He-Ar and Ne-Kr. The coefficients were determined for equimolar mixtures at temperatures between 0°C and 70°C. The diffusion was followed as a function of time by withdrawing samples and analyzing them in a specially designed thermal conductivity analyzer with high accuracy. The diffusion coefficients agree with earlier reported experimental values and with those obtained on the basis of the Chapman-Enskog theory in conjunction with the modified Buckingham exp-six and Lennard-Jones (12-6) intermolecular potentials. The smoothed values were used to predict viscosity and thermal conductivity of these mixtures as a function of composition and temperature.     

Analytic Model for DBF Under Multiple Particle Retention Mechanisms

Discrepancies between classical model (CM) predictions and experimental data for deep bed filtration (DBF) have been reported by various authors. In order to understand these discrepancies, an analytic continuum model for DBF is proposed. In this model, a filter coefficient is attributed to each distinct retention mechanism (straining, diffusion, gravity interception, etc.). It was shown that these coefficients generally cannot be merged into an effective filter coefficient, as considered in the CM. Furthermore, the derived analytic solutions for the proposed model (PM) were applied for fitting experimental data, and a very good agreement between experimental data and PM predictions were obtained. Comparison of the obtained results with empirical correlations allowed identifying the dominant retention mechanisms. In addition, it was shown that the larger the ratio of particle to pore sizes, the more intensive the straining mechanism and the larger the discrepancies between experimental data and CM predictions. Finally, the CM and PM were compared via statistical analysis. The obtained $p$ values allow concluding that the PM should be preferred especially when straining plays an important role.     

A brief note on upwind collocation

Upwind collocation on Hermite cubics is compared to orthogonal collocation with respect to effective diffusion. The one-dimensional constant coefficient advection-diffusion equation is employed to this end. The effective diffusion coefficient is determined exactly and is found to be dependent on the nodal solution values. The effective diffusion coefficients of three other upwinding schemes are also presented. Upwind collocation is found to have an effective diffusion coefficient like other upwinding schemes plus an extra term which may enhance or reduce the non-advective flux, depending on the problem solution and point location within the domain.     

Computation of the Longitudinal and Transverse Dispersion Coefficient in an Adsorbing Porous Medium Using Homogenization

This article compares for the first time, local longitudinal and transverse dispersion coefficients obtained by homogenization with experimental data of dispersion coefficients in porous media, using the correct porosity dependence. It is shown that the longitudinal dispersion coefficient can be reasonably represented by a simple periodic unit cell (PUC), which consists of a single sphere in a cube. We present a slightly modified and simplified approach to derive the homogenized equations, which emphasizes physical aspects of homogenization. Subsequently, we give full dimensional expressions for the dispersion tensor based on a comparison with the convective dispersion equation used for contaminant transport, inclusive the correct dependence on porosity. For the PUC of choice, the dispersion relations are identical to the relations obtained for periodic media. We show that commercial finite element software can be readily used to compute longitudinal and transverse dispersion coefficients in 2D and 3D. The 3D results are for the first time obtained at relevant Peclet numbers. There is good agreement for longitudinal dispersion. The computed transverse dispersion coefficients for a single sphere in a cube are much too low. The effect of adsorption on the dispersion coefficient is also studied. Adsorption does not affect the transverse dispersion coefficient. However, adsorption enhances the longitudinal dispersion coefficient in agreement with an analysis of homogenization applied to Taylor dispersion discussed in the literature.     

Asymptotic homogenization of three-dimensional thermoelectric composites

Thermoelectric composites are promising for high efficiency energy conversion between thermal flows and electric conduction, though their effective behaviors remain poorly understood due to nonlinear thermoelectric coupling. In this paper, we develop an asymptotic homogenization theory to analyze the effective behavior of three-dimensional (3D) thermoelectric composites, built on the observation that the equations governing microscopic field fluctuations in the composite are actually linear instead of nonlinear after separation of length scales. A set of solutions similar to Green's function method are used to construct the unit cell problem, and appropriate interfacial continuity conditions and boundary conditions are derived. The homogenized governing equations are then developed for thermoelectric composites, and they are further reduced for a special case wherein the heat flow and electric conduction in the composite remains one-dimensional (1D) at macroscopic scale, even though the composite itself is 3D in general. The general homogenization theory is implemented using finite element method, and a key constant in the constructed solutions is determined using the reformulated eigenvalue problem. The algorithm is validated, and is applied for a number of case studies for the effective behavior of thermoelectric composites.