Durability of epoxy and vinyl ester polymers in wet, seawater, and seawater sea sand concrete environments: Molecular dynamics simulations

Epoxy and vinyl ester (VE) deteriorate under harsh environmental conditions typical of marine and offshore applications. Enhancing their performance requires a deeper understanding of their molecular-level interactions with these environments. This study uses molecular dynamics simulations to investigate the behavior of epoxy and VE under dry, wet, Na2SO4, NaCl, NaOH, KOH, and simulated seawater sea sand concrete (SWSSC) pore solution environments. The effect of temperatures ranging from 300 K to 368 K was also explored. Key parameters, such as radial distribution function, hydrogen bond dynamics, diffusion coefficients of water molecules and ions, swelling ratio, and glass transition temperature (Tg), were analyzed. Results show that epoxy is more sensitive to environmental effects than VE. In the dry state, three types of hydrogen bonds (H-bonds) were identified, with 64 % of the hydroxyl (OH) group involved in epoxy and 34 % in VE. As temperature increases, polymer chain interactions weaken, leading to a decrease in H-bonds, with epoxy showing a faster decline. Absorbed water molecules accumulate near the polymer polar sites, particularly at the OH groups, breaking some polymer-polymer H-bonds and forming new ones with the polymer polar sites. The hydrogen atoms of most absorbed water molecules orient away from the OH group, creating binding sites for water clustering through water-water H-bonds, leading to plasticization and potential hydrolytic degradation. Ions increase the number of polymer-water H-bonds, significantly decreasing polymer-polymer H-bonds (by 59.22% for epoxy and 51.52% for VE in SWSSC), thus accelerating material deterioration. Free volume distribution and dynamics, the transition between bound and free water, hydrogen bond dynamics, as well as ion hydration and dehydration collectively influence the water diffusion process in the polymer networks. Ion species diffuse much slower than water molecules, with epoxy showing higher permeability to Cl- and OH-compared to VE. Glass transition temperature (Tg) of both polymers is sensitive to environmental exposure, with epoxy being more affected. The detrimental effect on Tg is ranked as SWSSC > KOH > NaOH > NaCl > Na2SO4 > Wet. These findings provide new nanoscale insights into the interactions between polymers and SWSSC environments, offering a foundation for accurately predicting the durability of polymer-reinforced SWSSC.