Exploring the Potential of Nonclassical Crystallization Pathways to Advance Cementitious Materials.

Understanding the crystallization of cement-binding phases, from basic units to macroscopic structures, can enhance cement performance, reduce clinker use, and lower CO 2 emissions in the construction sector. This review examines the crystallization pathways of C-S-H (the main phase in PC cement) and other alternative binding phases, particularly as cement formulations evolve toward increasing SCMs and alternative binders as clinker replacements. We adopt a nonclassical crystallization perspective, which recognizes the existence of critical intermediate steps between ions in solution and the final crystalline phases, such as solute ion associates, dense liquid phases, amorphous intermediates, and nanoparticles. These multistep pathways uncover innovative strategies for controlling the crystallization of binding phases through additive use, potentially leading to highly optimized cement matrices. An outstanding example of additive-controlled crystallization in cementitious materials is the synthetically produced mesocrystalline C-S-H, renowned for its remarkable flexural strength. This highly ordered microstructure, which intercalates soft matter between inorganic and brittle C-S-H, was obtained by controlling the assembly of individual C-S-H subunits. While large-scale production of cementitious materials by a bottom-up self-assembly method is not yet feasible, the fundamental insights into the crystallization mechanism of cement binding phases presented here provide a foundation for developing advanced cement-based materials.