Investigation of Carbonation Kinetics in Carbonated Cementitious Materials by Reactive Molecular Dynamics Simulations.

Calcium carbonate (CaCO3) precipitation plays a significant role during the carbon capture process; however, the mechanism is still only partially understood. Understanding the atomic-level carbonation mechanism of cementitious materials can promote the mineralization capture, immobilization, and utilization of carbon dioxide, as well as the improvement of carbonated cementitious materials' performance. Therefore, based on molecular dynamics simulations, this paper investigates the effect of Si/Al concentrations in cementitious materials on carbonation kinetics. We first verify the force field used in this paper. Then, we analyze the network connectivity evolution, the number and size of the carbonate cluster during gelation, the polymerization rate, and the activation energy. Finally, in order to reveal the reasons that caused the evolution of polymerization rate and activation energy, we analyze the local stress and charge of atoms. Results show that the Ca-Oc bond number and carbonate cluster size increase with the decrease of the Si/Al concentration and the increase of temperature, leading to the higher amorphous calcium carbonate gel polymerization degree. The local stress of each atom in the system is the driving force of the gelation transition. The presence of Si and Al components increases the atom's local stress and average charge, thus causing the increase of the energy barrier of CaCO3 polymerization and the activation energy of carbonation.

Effects of temperature and CO2 concentration on the early stage nucleation of calcium carbonate by reactive molecular dynamics simulations.

It is significant to investigate the calcium carbonate (CaCO3) precipitation mechanism during the carbon capture process; nevertheless, CaCO3 precipitation is not clearly understood yet. Understanding the carbonation mechanism at the atomic level can contribute to the mineralization capture and utilization of carbon dioxide, as well as the development of new cementitious materials with high-performance. There are many factors, such as temperature and CO2 concentration, that can influence the carbonation reaction. In order to achieve better carbonation efficiency, the reaction conditions of carbonation should be fully verified. Therefore, based on molecular dynamics simulations, this paper investigates the atomic-scale mechanism of carbonation. We investigate the effect of carbonation factors, including temperature and concentration, on the kinetics of carbonation (polymerization rate and activation energy), the early nucleation of calcium carbonate, etc. Then, we analyze the local stresses of atoms to reveal the driving force of early stage carbonate nucleation and the reasons for the evolution of polymerization rate and activation energy. Results show that the higher the calcium concentration or temperature, the higher the polymerization rate of calcium carbonate. In addition, the activation energies of the carbonation reaction increase with the decrease in calcium concentrations.