This study examines the effects of three polymer binders—polyvinyl alcohol (PVA), polyethylene glycol (PEG), and polyacrylic acid (PAA) on the mechanical properties and dry–wet cycle corrosion resistance of cement mortar at different dosages (1–4%). Mechanical testing combined with scanning electron microscopy (SEM) and molecular dynamics (MD) simulations was conducted to validate the experimental findings and reveal the underlying mechanisms. Results show that polymers reduce early-age strength but improve flexural performance, and at low dosage, enhance compressive strength. PVA and PAA exhibited a pronounced improvement in mechanical strength while PVA and PEG showed a significant improvement in wet cycle corrosion resistance. SEM observations indicated that polymers encapsulate cement particles, enhancing interfacial bonding while partially inhibiting hydration. MD simulations revealed that PVA and PAA interact with Ca²⁺ via Ca-O coordination, while PEG primarily forms hydrogen bonds, resulting in distinct water-binding capacities (PEG > PVA > PAA). These interactions explain the enhanced mechanism of mechanical and dry–wet cycle resistance properties. This work combined experimental and molecular-level validation to clarify how polymer–matrix and polymer–water interactions govern mechanical and durability, respectively. The findings provide theoretical and practical guidance for designing advanced polymer binders with tailored interfacial adhesion and water absorption properties to improve cementitious materials.

In this study, cellulose nanocrystals (CNs) were utilized to enhance the mechanical properties and sulfate corrosion resistance of engineered cementitious composites (ECCs). The results of compressive strength and uniaxial tensile tests demonstrated that the incorporation of CNs significantly improved the compressive strength, strain rate, tensile strength, and sulfate corrosion resistance of ECC specimens. Scanning electron microscopy (SEM) observations revealed that the addition of CNs facilitated the formation of increased amounts of ettringite and calcium silicate hydrate (C-S-H) in the matrix, enhancing the hydration degree of the cementitious system and increasing the overall density of the ECC structure. Molecular dynamics simulations were employed to investigate the interactions between CN, C-S-H, water molecules, and sulfate ions (SO₄²⁻) while also calculating the kinetic parameters of atoms at the interface. These simulations provided insights into the microstructural strengthening mechanism of CNs in improving the sulfate corrosion resistance of ECCs. The results indicated that CNs adsorb onto C-S-H via Ca-O and H-O coordination, forming a protective layer that inhibits the penetration of SO₄²⁻ and water molecules into the C-S-H structure. Additionally, CNs form hydrogen bonds with SO₄²⁻ and water molecules, which restricts their diffusion and reduces their coordination with the C-S-H interface and the dissolution of SO₄²⁻ and water to the hydration product, thereby enhancing the sulfate corrosion resistance of ECCs.