Multiscale Investigation on the Mechanical Enhancement Mechanisms of In Situ Polymerization Modified Cementitious Materials

The low flexural strength and high brittleness of cement-based materials greatly compromise their safety, durability, and service life. In situ polymerization is a promising strategy for enhancing the toughness of cement-based materials. However, the underlying mechanisms responsible for this mechanical improvement remain insufficiently understood. This study introduces acrylamide (AM) monomer into a cement matrix, where in situ polymerization forms a strong polymer–cement network, demonstrably enhancing mechanical performance. The factors influencing this mechanical enhancement were investigated across multiple scales using techniques including nanoindentation, crack width measurement, solid-state silicon nuclear magnetic resonance (29Si NMR), thermogravimetric analysis (TGA), and so on. This research confirms that in situ polymerization influences silicate chain length (from 3.405 to 3.714) and pore structure at the nanoscale, modifies the morphology of hydration products, enhances the hardness of the interfacial transition zone (0.025 ± 0.002 to 0.055 ± 0.004 GPa) at the microscale, and reveals that at monomer concentrations below 1 wt%, both the compressive and flexural strengths of the cement-based material are improved, with 28d compressive and flexural strength increasing by 23.86% and 26.58%, respectively. Conversely, higher monomer dosages lead to a simultaneous reduction in both compressive and flexural strengths. Consequently, through tracking the hydration process on the mechanical properties of cement-based materials across multiple scales, this study provides deeper insights into the in situ polymerization system and offers an effective strategy for the design and preparation of high-performance concrete.