Atomic Origins of the Self-Healing Function in Cement–Polymer Composites

Motivated by recent advances in self-healing cement and epoxy polymer composites, we present a combined ab initio molecular dynamics and sum frequency generation (SFG) vibrational spectroscopy study of a calcium–silicate–hydrate/polymer interface. On stable, low-defect surfaces, the polymer only weakly adheres through coordination and hydrogen bonding interactions and can be easily mobilized toward defected surfaces. Conversely, on fractured surfaces, the polymer strongly anchors through ionic Ca–O bonds resulting from the deprotonation of polymer hydroxyl groups. In addition, polymer S–S groups are turned away from the cement–polymer interface, allowing for the self-healing function within the polymer. The overall elasticity and healing properties of these composites stem from a flexible hydrogen bonding network that can readily adapt to surface morphology. The theoretical vibrational signals associated with the proposed cement–polymer interfacial chemistry were confirmed experimentally by SFG vibrational spectroscopy.