Nanoscale Insights into the Protection of Calcium Silicate Hydrate by Polydimethylsiloxane Coatings in Sulfate Environments: Different Degrees of Polymerization

Calcium silicate hydrate (CSH) plays a crucial role in concrete by controlling its properties and durability. The degradation of CSH often signifies concrete damage. Polydimethylsiloxane (PDMS) is commonly used to protect concrete from sulfate corrosion; however, the comprehensive mechanistic understanding of its protective effects against CSH remains limited. Here, molecular dynamics (MD) simulations were employed to explore atomic-scale interactions between PDMS coatings and CSH in a sulfate-rich environment. Our results reveal that PDMS mitigates sulfate-induced CSH decalcification by forming a positively charged layer, ultimately reducing sulfate bonding by 83.3% compared to the blank group. Molecular structure analysis highlights key hydrogen bonding and calcium-oxygen bonding interactions that are critical for this protection. Higher polymerization stabilizes substrate adsorption, reducing surface diffusion to 33.3% of low-polymerization PDMS, thereby enhancing protection. Additionally, water molecule interactions with the CSH matrix are negatively correlated with the amount of adsorbed sulfate. Simulation results offer valuable insights into the molecular-level dynamic response of the material, contributing to a deeper understanding of the protective mechanisms of PDMS against sulfate-induced CSH degradation in concrete. These findings can guide experimenters and engineers in designing more effective protective coatings for concrete exposed to sulfate-rich environments, thereby laying a foundation for further experimental research and the development of concrete materials with enhanced durability under challenging environmental conditions.