Time-Space-Resolved Chemical Deconvolution of Cementitious Colloidal Systems Using Raman Spectroscopy

Concrete is one of the most used materials in the world, second only to water. One of the key advantages of this versatile material is its workability in the early stages before setting. Here, we use in situ underwater Raman microspectroscopy to investigate and visualize the early hydration kinetics of ordinary Portland cement (OPC) with submicron spatial and high temporal resolution. First, the spectral features of the C-S-H gel were analyzed in the hydroxyl stretching region to confirm the coexistence of Ca-OH and Si-OH bonds in a highly disordered C-S-H gel. Second, the disordered calcium hydroxide (Ca(OH)₂) is experimentally identified for the first time in the mixture before setting, suggesting that Ca(OH)₂ crystallization and growth are essential in the setting of cement paste. Finally, the phase transformations of clinker, C-S-H, and Ca(OH)₂ are spatially and temporally resolved, and the hydration kinetics are studied by analyzing the spatial relationships of these phases using two-point correlation functions. The results quantitatively validate that the setting occurs as a percolation process, wherein the hydration products intersect and form an interconnected network. This time-space-resolved characterization method can map and quantitatively analyze the heterogeneous reaction of the cementitious colloidal system and thus provide potential application value in the field of cement chemistry and materials design more broadly.