A Review of Carbonation of C-S-H: From Atomic Structure to Macroscopic Behavior

Calcium–silicate–hydrate (C-S-H), the primary binding phase governing cement paste cohesion, undergoes progressive physicochemical transformation upon carbonation—a process that critically dictates concrete durability in atmospheric environments. When CO2 penetrates the porous cement matrix, it triggers a cascade of degradation mechanisms: calcium leaching decalcifies the C-S-H structure, inducing polymerization of silicate chains from dimeric to longer-chain configurations, while concurrent precipitation of calcium carbonate and amorphous silica gel fundamentally reconstitutes the nanoscale architecture. These nanoscale alterations propagate to macroscopic property evolution, manifesting as initial strength and stiffness gains due to pore-filling carbonation products followed by eventual deterioration as the cohesive binding network deteriorates. This review synthesizes current understanding of carbonation-induced structural evolution, examining the coupled influences of environmental parameters—CO2 concentration, relative humidity, and temperature—alongside C-S-H intrinsic chemistry (Ca/Si ratio, aluminum substitution, and alkali content) on reaction kinetics and material performance. However, significant knowledge gaps persist: predictive models for in-service carbonation rates remain elusive due to the disconnect between idealized laboratory conditions and the heterogeneous, cracked reality of field concrete; the causal linkage between nanoscale C-S-H alteration and macroscale cracking patterns along with physical performance is poorly resolved, and most mechanistic studies rely on synthetic C-S-H, neglecting the compositional complexity of real Portland cement systems. We further propose emerging protection strategies, including surface barrier coatings and low-carbon alternative binders (geopolymers, calcium sulfoaluminate cements, carbon-negative materials such as recycled cement), which demonstrate enhanced carbonation resistance. Future research priorities include developing effective coating barriers for carbonation protection, developing operando characterization techniques for real-time reaction monitoring, deploying machine learning algorithms to bridge atomistic simulations with structural-scale predictions, and establishing long-term field performance databases to validate laboratory-derived degradation models.