Characterizing the Gas Permeability of Natural and Synthetic Materials

The objective of this article is to propose an experimental method to compare the gas permeability of all the different materials used as gas barrier, such as compacted clay liners or geomembranes. This method is based on the falling pressure experiment, allowing the determination of a single coefficient whatever the material tested. This coefficient is the time constant τ, which is obtained by analytical solutions of the simplified equations describing the transport of gas through the material. The domain of validity is specified for porous media, thanks to a numerical solution of the complete equations system. Two applications are presented, showing the applicability of the method on compacted clay liners and on high density polyethylene geomembranes.     

A Two-Scale Model for Coupled Electro-Chemo-Mechanical Phenomena and Onsager’s Reciprocity Relations in Expansive Clays: II Computational Validation

In Part I Moyne and Murad [Transport in Porous Media 62, (2006), 333–380] a two-scale model of coupled electro-chemo-mechanical phenomena in swelling porous media was derived by a formal asymptotic homogenization analysis. The microscopic portrait of the model consists of a two-phase system composed of an electrolyte solution and colloidal clay particles. The movement of the liquid at the microscale is ruled by the modified Stokes problem; the advection, diffusion and electro-migration of monovalent ions Na⁺ and Cl⁻ are governed by the Nernst–Planck equations and the local electric potential distribution is dictated by the Poisson problem. The microscopic governing equations in the fluid domain are coupled with the elasticity problem for the clay particles through boundary conditions on the solid–fluid interface. The up-scaling procedure led to a macroscopic model based on Onsager’s reciprocity relations coupled with a modified form of Terzaghi’s effective stress principle including an additional swelling stress component. A notable consequence of the two-scale framework are the new closure problems derived for the macroscopic electro-chemo-mechanical parameters. Such local representation bridge the gap between the macroscopic Thermodynamics of Irreversible Processes and microscopic Electro-Hydrodynamics by establishing a direct correlation between the magnitude of the effective properties and the electrical double layer potential, whose local distribution is governed by a microscale Poisson–Boltzmann equation. The purpose of this paper is to validate computationally the two-scale model and to introduce new concepts inherent to the problem considering a particular form of microstructure wherein the clay fabric is composed of parallel particles of face-to-face contact. By discretizing the local Poisson–Boltzmann equation and solving numerically the closure problems, the constitutive behavior of the diffusion coefficients of cations and anions, chemico-osmotic and electro-osmotic conductivities in Darcy’s law, Onsager’s parameters, swelling pressure, electro-chemical compressibility, surface tension, primary/secondary electroviscous effects and the reflection coefficient are computed for a range particle distances and sat concentrations.     

Water Vapor Diffusion Through Soil as Affected by Temperature and Aggregate Size

Water vapor diffusion through the soil is an important part in the total water flux in the unsaturated zone of arid or semiarid regions and has several significant agricultural and engineering applications because soil moisture contents near the surface are relatively low. Water vapor diffusing through dry soil is absorbed for both long and short terms. Long-term absorption allows more water to enter than exit the soil, as reflected in the concentration gradient. Short-term absorption leads to an apparent reduction in the diffusion rate, as reflected in the diffusion coefficient. This investigation studied the effects of soil temperature and porosity on the isothermal diffusion of water vapor through soil. The diffusion model consisted of 25.4 cm × 8.9 cm × 20.3 cm Plexiglas box divided into two compartments by a partition holding a soil reservoir. Water vapor moved from a container suspended by a spring in one compartment, through the porous medium in the center of the model, to calcium chloride in a container suspended by a spring in the other compartment. The porous materials consisted of aggregates of varying size (2–2.8, 1–2, and 0.5–1 mm) of a Fayatte silty clay loam (a fine-silty, mixed mesic Typic Hapludalf). The flow rates of water vapor were measured at temperatures of 10, 20, 30, and 40°C. Warmer temperatures increased the rate of diffusion through dry soil while reduced the amount of water absorbed by that soil. Reducing porosity slowed the rate of diffusion and increased the amount of water absorbed. The dry soil in this study absorbed from 1/8 to 2/3 of the diffusing water. Maximum absorption rates occurred with the most compact soil samples at the highest temperature, though the maximum absorption as a percentage of the diffusing water was in the compact samples at the lowest temperature. The diffusivity equation D/D ₀ = [(S – 0.1)/0.9]² fit the D/D ₀ values obtained from these data if a coefficient of 1/3 or 1/3.5 is added to correct for the time delays caused by temporary sorption of the diffusing water vapor. The data, influenced by the interaction of water vapor and soil materials, represent a diffusion rate lower than the diffusion rate that would have resulted without this interaction. Mention of trade names, proprietary products, or specific equipment is intended for reader information only and does not constitute a guarantee or warranty by the USDA-ARS nor does it imply approval of the product named to the exclusion of other products. An erratum to this article can be found at     

Effective hydraulic conductivities in unsaturated heterogeneous media by Monte Carlo simulation

When modeling flow and transport through unsaturated heterogeneous geological deposits, it may be neither computationally nor technically feasible to account for the actual heterogeneity in the simulations. One would fall short in terms of technical feasibility because there is simply no way that the entire spatial domain could be characterized (e.g., you cannot measure hydraulic conductivity at every location at a site). With respect to computational feasibility, the non-linear nature of the Richards equation (which is used to model the flow process) makes simulation of most sites extremely computationally intensive. The computational roadblock is being dismantled as computer hardware advances, but our inability to precisely characterize geological heterogeneity is expected to remain with us for a very long time. To address this problem, the analyst typically uses average or effective properties to model flow and transport behavior through heterogeneous media. In this paper, a variety of approaches for developing effective unsaturated flow properties are assessed. Computational results have been obtained which give the hydraulic conductivity ratios (K _parallel/K _nomal) for highly nonisotropic layered materials. These results are compared with analytical models. Good agreement was obtained for all soil saturation levels except for extremely dry conditions.This work was performed at Sandia National Laboratories, which is operated for the U.S. Department of Energy under contract number DE-AC04-76DP00789.     

The Role of Tortuosity in Upscaling

The concept of tortuosity is an integral part of models that describe transport in multiscale systems. Traditionally, tortuosity is defined as the ratio of an effective path length to the shortest path length in the microstructure. While the shortest path length can be unambiguously specified, the same is not true for the effective path length, since it changes from one type of transport to another. Consequently, it is possible to have different values of tortuosity for different transport processes taking place in the same system. This is convenient since, under this approach, different transport processes can involve the same type of filters of the microscale information, but the nature of such information is what characterizes each type of transport process. In order to avoid running into unclear interpretations, a set of tortuosity rules are proposed, which relate this concept only to the microscale geometry. On the basis of these rules, we examine the pertinence of introducing the tortuosity concept in mass transport. In particular, we study mass diffusion with and without chemical reaction and convection in porous media. Of all these cases, our analysis indicates that the concept of tortuosity is only adequate for passive diffusion, since in the other cases there is an unavoidable coupling of the transport phenomena that determine the effective path of the solute.     

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.     

Fractal and superdiffusive transport and hydrodynamic dispersion in heterogeneous porous media

We review and discuss diffusion and hydrodynamic dispersion in a heterogeneous porous medium. Two types of heterogeneities are considered. One is percolation disorder in which a fraction of the pores do not allow transport to take place at all. In the other type, the permeabilities of various regions of the pore space are fractally distributed with long-range correlations. Both systems give rise to unusual transport in which the mean square displacement <r ²(t)> of a particle grows nonlinearly with time. Depending on the heterogeneities and the mechanism of diffusion and disperison, we may havefractal transport in which <r ²> growsslower than linearly with time, orsuperdiffusive transport in which <r ²> growsfaster than linearly with time. We show that percolation models can give rise to both types of transport with scale-dependent transport coefficients such as diffusivity and dispersion coefficients, which are consistent with many experimental observations.     

Effects of Evaporation and Different Flow Regimes on Solute Distribution in Soil

Water evaporation and solute transport processes were studied in large soil columns filled with a sandy clay loam (SCL) and a clay loam (CL) soils. To create different water flow velocity through the soil column, the 3 cm (Treatment I) and 6 cm (Treatment II) depths of water were ponded at the soil surface during leaching. After leaching, soils were left for evaporation for 10 days. Some salinity parameters were monitored during three leaching and evaporation periods. To achieve the same degree of leaching more water was needed in Treatment II than in Treatment I for both soils. The electrical conductivity (EC) at the soil surface after evaporation increased, to 41–46% of the pre-drying level for the SCL and 28–31% for the CL. Although very low concentrations of Cl^– were detected at the soil surface after the first leaching in both soils, high increase was monitored after the evaporation period, due to the high mobility of this anion. The fluctuation of exchangeable sodium percentage (ESP) during the leaching and evaporation periods was attributed to the different transportation rates of Na⁺, Ca²⁺ and Mg²⁺. The boron leaching in Treatment I was more effective than that in Treatment II for both soils.     

3D contaminant migration model with consolidation dependent transport coefficients

Soil consolidation would induce variations of its transport coefficients such as hydraulic conductivity and diffusion coefficient. This paper presents a study of the influence of barrier consolidation on transport coefficients, and a 3D transport model based on mixture theory is proposed for describing the liners that involve circular defects in the geomembrane. The elastoplastic ALPHA model is revised by using the spatially mobilized plane (SMP) criterion for simulating the deformation of the soils. Then, the 3D model coupling the nonlinear consolidation and contaminant advection-diffusion is solved using the finite element software ABAQUS. The results show that the importance of reducing the defect size in the geomembrane and the liner porosity to control the contaminant concentration increase.     

Evidence for a Second Transport Porosity for the Diffusion of Tritiated Water (HTO) in a Sedimentary Rock (Opalinus Clay - OPA): Application of Through- and Out-Diffusion Techniques

The diffusion of tritiated water (HTO) in Opalinus clay (OPA) samples from bore cores from the Benken area (Northern Switzerland) was studied using the radial through- and out-diffusion technique. Results from inverse modelling of out-diffusion data for HTO indicated the presence of two preferential diffusion pathways: a fast and a slow one. Analysing through-diffusion data, however, provides hardly any information concerning a second transport-relevant porosity. Only by also analysing the out-diffusion phase can finer details of the diffusion process and information on sample heterogeneity be recognised. The extracted values for the effective diffusion coefficient are in the order of 3 × 10^–11 m² s^–1 for the faster transport porosity and roughly an order of magnitude smaller for the slower type of porosity. We had to account for tritium sorption on the clay minerals by a small but non-zero K_d-value in the order of 10^–5 m³ kg^–1 in order to reproduce the data with acceptable precision. In the model applied both porosities are considered as being independent from each other. Roughly 30% of the tracer diffused through the second, slower porosity; such a fact might be interesting for future performance assessments for radioactive waste repositories hosted by clay formations. Based on our present picture from water-saturated OPA, on a microscopic scale three different kind of waters can be discriminated: free water, double layer water and interlayer water. However, using HTO as tracer only, it could not be deduced which type of water-filled pores finally account for the transport-relevant porosity.Author for correspondence: Tel.: +41-56-3102257; Fax: +41-56-3104438; E-mail: luc.vanloon@psi.ch     

Investigation of Donnan equilibrium in charged porous materials—a scale transition analysis

We propose a new theory describing how the macroscopic Donnan equilibrium potential can be derived from the microscale by a scale transition analysis. Knowledge of the location and magnitude of the charge density, together with the morphology of the pore space allows one to calculate the Donnan potential, characterizing ion exclusion in charged porous materials. Use of the electrochemical potential together with Gauss’ electrostatic theorem allows the computation of the ion and voltage distribution at the microscale. On the other hand, commonly used macroscopic counterparts of these equations allow the estimation of the Donnan potential and ion concentration on the macroscale. However, the classical macroscopic equations describing phase equilibrium do not account for the non-homogeneous distribution of ions and voltage at the microscale, leading to inconsistencies in determining the Donnan potential (at the macroscale). A new generalized macroscopic equilibrium equation is derived by means of volume averaging of the microscale electrochemical potential. These equations show that the macroscopic voltage is linked to so-called “effective ion concentrations”, which for ideal solutions are related to logarithmic volume averages of the ion concentration at the microscale. The effective ion concentrations must be linked to an effective fixed charge concentration by means of a generalized Poisson equation in order to deliver the correct Donnan potential. The theory is verified analytically and numerically for the case of two monovalent electrolytic solutions separated by a charged porous material. For the numerical analysis a hierarchical modeling approach is employed using a one-dimensional (1D)macroscale model and a two-dimensional (2D)microscale model. The influence of various parameters such as surface charge density and ion concentration on the Donnan potential are investigated.     

Application of a n-Phase Model to the Diffusion Coefficient of Chloride in Mortar

The determination of the chloride diffusion coefficient of a concrete is needed to help the prediction of the service life of concrete structure. In this paper, we propose first a critical review of models for chloride diffusion coefficients already used in literature at different scales and then we develop an analytical model, which takes into account the characteristics of the different phases of concrete. These materials are treated as a three-phase composite, consisting of a cement continuous phase, of an aggregates dispersed phase and of an interface transition zone. Chloride diffusion coefficient using an n-layered inclusion-based micromechanical modeling is predicted. The details of calculations are summarized hereafter and experimental measurements obtained on mortars are compared with predicted results.     

Heat,Water, and Solution Transfer in Unsaturated Porous Media: I -- Theory Development and Transport Coefficient Evaluation

A detailed theory describing the simultaneous transfer of heat, water, and solute in unsaturated porous mediais developed. The theory includes three fully-coupledpartial differential equations. Heat, water, andsolute move in the presence of temperature, T; matricpressure head, _m ; solution osmotic pressure head _o ; and solute concentration C gradients. Thetheory can be applied to describe the mass and energyin radioactive waste repositories, food processing,underground energy storage sites, buried electriccables positions, waste disposal sites, and inagricultural soil. Several transport coefficients forheat, water, and solute are included in the theory. The coefficients are evaluated for a silty clay loamsoil to clarify their dependence on water content (),T, and C. The thermal vapor diffusivity D _Tv first increased as increased to0.22 m³/m³ then decreased with furtherincreases in . D _Tv was 3 orders of magnitudegreater than either isothermal vapor D _mv orosmotic vapor D _ov , diffusivities at of0.20~m³/m³, T of 50°C, and C of 0.001mol/kg. All of the liquid and vapor water transport coefficients increased with increasing T. D _Tv decreased with increasing C to a greater extent thanD _mv and D _ov . The effective thermalconductivity decreased slightly with increasing C. Thesolute diffusion coefficient D _d was 6 to 7orders of magnitude greater than the thermal soluteand salt sieving diffusion coefficients at of0.20~m³/m³, T of 50°C, and C of 0.001 mol/kg.     

Solute diffusion in fractured porous media with memory effects due to adsorption

Modelling of solute transport in fractured porous media is a subject of intensive research in many engineering disciplines, such as petroleum engineering, water resources management, civil engineering. Recent field and laboratory experiments show that, in presence of strong adsorption, the behaviour of solute penetrating into the fractured porous medium diverges from classical hypotheses, rendering impossible the adjustment of classical transport models. The aim of this paper is to develop a mathematical continuous model of solute transport, when strong adsorption of solute occurs on the grains of the porous matrix. The macroscopic model is obtained by upscaling the pore and the fracture behaviours, by using the multiple scale expansion method. We obtain a non-standard diffusion behaviour of solute which shows local non-equilibrium between transport in the fractures and in the porous matrix, as well as memory effects. To cite this article: J. Lewandowska et al., C. R. Mecanique 330 (2002) 879–884.     

Jump Condition for Diffusive and Convective Mass Transfer Between a Porous Medium and a Fluid Involving Adsorption and Chemical Reaction

In this paper, mass transfer at the fluid–porous medium boundaries is studied. The problem considers both diffusive and convective transport, along with adsorption and reaction effects in the porous medium. The result is a mass flux jump condition that is expressed in terms of effective transport coefficients. Such coefficients (a total dispersion tensor and effective reaction and adsorption coefficients) may be computed from the solution of the corresponding closure problem here stated and solved as a function of the Péclet number (Pe), the porosity and a local Thiele modulus. For the case of negligible convective transport (i.e., ), the closure problem reduces to the one recently solved by the authors for diffusion and reaction between a fluid and a microporous medium.     

Age dependence of the drag force in an aqueous foam

The drag force on a sphere moving through an aqueous foam is measured as the foam ages. After an initial period, the steady-state drag decreases with age T as T ^{−0.54±0.14}. As the mean bubble size R in the foam coarsens as T ^0.5, this implies that the drag force scales as The transient buildup of the force when the sphere starts to move is described by a single exponential approach to the steady-state drag while its relaxation when the motion stops is described by the sum of three exponential relaxations. This is as for fresh foam, but the coefficients and time constants vary systematically with age. For the most part, these quantities also show a power law scaling with T. The age dependence of the quantities determined in this study is discussed in terms of the mean bubble size.     

A generalization of the Chapman-Enskog and Grad methods

By using the method of Chapman-Enskog as a base, we have determined successive approximations of any order to the transport coefficients of shear viscosity and thermal conductivity for a monatomic ideal gas. The expressions for the transport coefficients involve only integrals which can be evaluated once the law of interaction between the spherically symmetrical particles is known. Moreover, we have developed a (13 + 9N)-field theory based on the method of Grad and showed that the transition from this theory to a five-field theory leads to the same results as those obtained through the method of Chapman-Enskog.     

A Three-Scale Model of pH-Dependent Flows and Ion Transport with Equilibrium Adsorption in Kaolinite Clays: II Effective-Medium Behavior

In part I (Lima et al., Transp Porous Media, 2009), a three-scale model governing the movement of an aqueous saline solution containing four monovalent species (Na⁺, H⁺, Cl^?, OH^?) in kaolinite clays was derived. Unlike purely macroscopic approaches, the novelty of the formulation relied on the double averaging of the nanoscopic electro- chemistry of particle/electrolyte solution interface ruled by the electrical double layer coupled with protonation/deprotonation reactions. The passage from the nano to the micro (pore)-scale gave rise to ion-sorbed concentrations and slip velocity at the solid/fluid interface which are coupled with the microscopic Stokes problem and Nernst–Planck equations governing the hydrodynamics and ion transport in the micropores. Application of a formal homogenization procedure led to macroscopic governing equations with effective electro-chemical parameters, such as retardation coefficients, electro-osmotic permeability, and electric conductivity. In this study, we reconstruct the constitutive laws of the macroscopic coefficients by solving the nano and microscopic closure problems. New generalized isotherms for Na⁺ and H⁺ ? OH^? sorption are build-up based on a perturbation approach and the limitations of classical Freundlich isotherm for modeling ion sorption at the solid/fluid interface are discussed. The macroscopic governing equations are discretized by the finite volume method and numerical simulations of a transient electroosmosis experiment for desalination of a clay sample by electrokinetics are presented.     

Translational diffusion of rubrene and tetracene in polyisobutylene

The translational diffusion coefficients of rubrene and tetracene in amorphous polyisobutylene (PIB) were measured using the holographic fluorescence recovery after photobleaching technique. Over the temperature range from 400 to 235 K (T _g =205 K), tracer diffusion coefficients from 10^–7 to 10^–14 cm²/s were observed. These diffusion coefficients have essentially the same temperature dependence as the rotational correlation times for these two probes in PIB. Both of these observables have a slightly stronger temperature dependence than does the viscosity. These results contrast strongly with the results of similar experiments on polystyrene and polysulfone. These results are consistent with the hypothesis that local segmental dynamics are more spatially homogeneous in PIB than in polystyrene and polysulfone.Dedicated to Prof. John D. Ferry on the occasion of his 85th birthday.