Electromigration of Chloride Ions in Cementitious Material: Extension of Nernst–Planck Theory

The transport of chloride ions in concrete is often affected by electric fields, and its concentration distribution is generally evaluated using the Nernst–Planck equation. The Nernst–Planck theory can only effectively predict the mass electromigration in ideal porous media. However, under an electric field, cementitious materials still have a certain binding ability to chloride ions. This causes the transport model to have significant prediction errors, and the specific value of the electromigration coefficient cannot be accurately measured. This article systematically investigated the transfer rate of chloride ions in cementitious material under different current densities. An analytical solution of the Nernst–Planck equation containing an independent electromigration coefficient was presented, and its value was quantitatively measured and discussed. The results indicated that the relationship between the electromigration and the apparent diffusion coefficient of chloride ions needs to be fitted in segments corresponding to various electric voltage intensities; but the electromigration coefficient shows a highly linear relationship with the pure effective diffusion coefficient. This work can provide assistance and valuable data support for the evaluation of mass transport in non-ideal porous media, such as cementitious materials, using the Nernst–Planck theory.