Simultaneous Transport of Chloride and Calcium Ions in Hydrated Cement Systems

Abstract

This paper presents a new method for numerically calculating the concentration profiles of both solid calcium and total chloride ions (Cl⁻) in concrete in contact with 3% (0.5 mol/l) sodium chloride (NaCl) solution. Since the diffusion of ions present in the pore solution is a primary controlling factor, the application of mutual diffusion coefficients of corresponding ions that are influenced by the concentration of other coexisting ions is proposed. The method of calculation is based on the generalized form of Fick's First Law suggested by Onsager, which is composed of the Onsager phenomenological coefficient and the thermodynamic force between ions, which occurs according to the gradient of electrochemical potential in a multicomponent concentrated solution for the pore solution. In addition, the chemical equilibrium for Ca(OH)₂ dissolution and C-S-H decalcification are also modeled and coupled with diffusion. Increased porosity due to dissolved Ca²⁺ and a chloride binding isotherm are taken into consideration. The concentration profiles of solid calcium and the presence of Friedel's salt in mortar specimens are experimentally identified by the X-ray diffraction method (XRD) and the thermal analysis (TG/DTA) as well as the total chloride profile using an acid extraction method after three years of exposure to 0.5 mol/l NaCl solution. This experimental result verifies the calculation result.