High-throughput atomistic modeling of nanocrystalline structure and mechanics of calcium aluminate silicate hydrate

Although aluminum-containing cements have gained attention as environmentally friendly construction materials, the nanocrystalline structure and mechanical behavior of their primary hydration product, calcium aluminate silicate hydrate (C-A-S-H), remain poorly understood due to its complex chemical composition and structural disorder. Here, we present a high-throughput atomistic modeling framework to systematically investigate the structural and mechanical properties of C-A-S-H across a broad range of Ca/Si (1.3-1.9) and Al/Si (0-0.15) ratios. The compositional, structural, and mechanical features of C-A-S-H are accurately captured by molecular dynamics simulations of 1600 distinct C-A-S-H structures constructed using our in-house automatic structure generation program, CASHgen. Our findings highlight the influence of Ca/Si and Al/Si ratios on key C-A-S-H characteristics, including the mean chain length (MCL), interlayer spacing, coordination number and elastic moduli. Specifically, C-A-S-H exhibits optimal mechanical performance at a Ca/Si ratio of approximately 1.5, while further increases in Ca/Si introduce disorder and reduce stiffness. In contrast, increasing the Al/Si ratio promotes chain polymerization, leading to longer MCLs and improved mechanical performance. These results provide atomic-scale insights into the structure-property relationships in C-A-S-H and offer design guidelines for high-performance, low-carbon cementitious materials.