Nano and Sub-nano multiscale porosity formation and other features revealed by 1H NMR relaxometry during cement hydration

Cement hydration occurs when water is added to cement powder, leading to the formation of crystalline products like Portlandite and the quasi-amorphous, poorly crystalline, calcium silicate hydrate (C-S-H) gel. Despite its importance in determining the final properties of the cement, many models exist for the nano and sub-nano level organization of this liquid stone. H-1 NMR relaxometry in White Portland Cement paste during hydration allowed us to monitor the formation and evolution of the multiscale porosity of the cement, with the formation of structures at nano and sub-nano levels of C-S-H gel (calcium silicate interlayer water, water in small and large gel pores) along with three low-mobility H-1 pools, identified as H-1 nuclei in C-S-H layers, likely belonging to OH groups, with H-1 nuclei in Portlandite, and in crystal water of Ettringite. By assuming these assignments, our data allowed us to compute the distances of pairs of H-1 nuclei in Portlandite and in crystal water ((1.9 +/- 0.2) angstrom and (1.6 +/- 0.1)angstrom, respectively), consistent with the known values of these distances. The picture of the porous structure at nano and sub-nano levels emerging from our results is consistent with the Jennings colloidal model for C-S-H gel. Moreover, the constant values observed during hydration of parameters extracted from our data analysis strongly support that model, being compatible with the picture of C-S-H gel developing in comparable-sized clumps of the same composition, but not easily interpretable by models proposing quasi continuous sheets of C-S-H layers.