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The current literature on ionic diffusion through porous media teaches that the diffusion coefficient is a complicated function depending on concentration, concentration gradient, and electrical potential gradient. This paper documents how natural diffusion tests and migration tests (electrically enhanced transport) lead to the measurement of a unique diffusion coefficient for a given ionic species and a given material. Natural diffusion tests for chloride and a ceramic of TiO2 were implemented at two different concentration levels. The experiments were designed to emphasize the impact of the membrane potential in the pore solution on the chloride flux. By accounting for the membrane potential it is shown that the chloride diffusion coefficient is unique for a given material. An iterative method based on a numerical model solving the continuity equations and the current law is proposed to determine the diffusion coefficient. The approach is applied with success to published results on a cement-based material. Migration tests were also performed with chloride in a cementitious material, where the chloride transport is enhanced by an external electrical field. The experimental results reveal the competition between diffusion and electrical effects in the case of noncontaminated porous materials. By varying the electrical potential difference it is shown that the flux of chloride varies linearly with the electrical field, meaning that the chloride diffusion coefficient does not depend on the electrical field. The main conclusion is that there is only one chloride diffusion coefficient for a given porous material. [ABSTRACT FROM AUTHOR]

This paper documents the measurement of the chloride diffusion coefficient through partially saturated porous materials. The method was electrochemical impedance spectroscopy, and it was validated by comparison to migration tests in fully saturated samples. A microstructure-based electrical equivalent circuit was developed to obtain the main features of the sample including the material electrical resistance for any water saturation degree. It is shown that the chloride diffusion coefficient varies over four orders of magnitude when the material is almost dry to fully saturated. [ABSTRACT FROM AUTHOR]

Highlights: [•] The chloride diffusion coefficient is measured as a function of the saturation level by impedance spectroscopy. [•] 4 Types of materials made of Portland cement and blended cement are tested in a saturation level ranging from 0.2–1. [•] The evolution of the diffusion coefficient with the saturation level is closely related to the pore size distribution. [Copyright &y& Elsevier]

Abstract: This paper proposes to compare several experimental ways of obtaining the chloride diffusion coefficient through saturated porous materials. The first method is based on the application of the Nernst–Einstein equation for which the conductivity of the saturated sample is measured by impedance spectroscopy for two kinds of materials: inert samples of TiO2, and concretes based on type I and type V cements. The second method is a migration test in which the flux of chloride measured upstream allows calculating the diffusion coefficient by means of the Nernst–Planck equation. In the third case, the diffusion coefficient is calculated by current measurements in an equivalent configuration as the second method. It is shown that the formation factor does not vary neither with the ionic strength of the saturation solution, nor with the change in the pore solution constituents when the material is without mineral additions. The CEM-V concrete exhibits a specific behavior with a strong influence of the addition of chloride in its pore solution on the formation factor. The diffusion coefficients calculated with the three methods are in good agreement provided the metrology of the experiments is carefully controlled. [Copyright &y& Elsevier]

Abstract: Relative permeabilities and water vapor diffusion reduction factor coefficients are essential data regarding the modeling of moisture transport and hence the prediction of structure lifetimes. The dependency of these parameters on the humidity history and the chemical evolutions of the material limits their experimental measurement since tests are long to carry out. For cement-based materials, the most usual approach for the calculation of relative permeabilities is the one developed for soils by Van Genuchten, requiring calibration on experimental water retention curves. Moreover, the model involves a pore network connectivity factor, the value of which varies from one author to another. The water vapor diffusion reduction factor is often calculated via Millington's semi-empirical model. This paper presents new methods for calculating transport factors based on physical and statistical considerations associated with a pore network model developed for the prediction of water sorption isotherms. [Copyright &y& Elsevier]

The influence of atmospheric carbonation on gas diffusion was investigated using four hardened cement pastes (CEM I, CEM III/A, CEM V/A, and a low-alkalinity binder) with common water-to-binder ratio (0.4). The diffusivity of the non‑carbonated and carbonated pastes with respect to helium and nitrogen was measured at different relative humidities. Carbonation decreased the diffusivity of the CEM I paste, whereas that of the other binders significantly increased after carbonation. These results show the competition between porosity clogging and cracking induced by carbonation. The consequences of carbonation are therefore believed to depend on the considered binder. Clogging dominates in ordinary Portland cement (OPC), leading to a decrease in its transport properties after carbonation; cracking dominates in blended cements, leading to a significant increase in its transport properties after carbonation. [ABSTRACT FROM AUTHOR]