Structure of nanocrystalline calcium silicate hydrates: insights from X-ray diffraction, synchrotron X-ray absorption and nuclear magnetic resonance

The structure of nanocrystalline calcium silicate hydrates (C–S–H) having Ca/Si ratios ranging between 0.57 ± 0.05 and 1.47 ± 0.04 was studied using an electron probe micro‐analyser, powder X‐ray diffraction, 29Si magic angle spinning NMR, and Fourier‐transform infrared and synchrotron X‐ray absorption spectroscopies. All samples can be described as nanocrystalline and defective tobermorite. At low Ca/Si ratio, the Si chains are defect free and the Si Q3 and Q2 environments account, respectively, for up to 40.2 ± 1.5% and 55.6 ± 3.0% of the total Si, with part of the Q3 Si being attributable to remnants of the synthesis reactant. As the Ca/Si ratio increases up to 0.87 ± 0.02, the Si Q3 environment decreases down to 0 and is preferentially replaced by the Q2 environment, which reaches 87.9 ± 2.0%. At higher ratios, Q2 decreases down to 32.0 ± 7.6% for Ca/Si = 1.38 ± 0.03 and is replaced by the Q1 environment, which peaks at 68.1 ± 3.8%. The combination of X‐ray diffraction and NMR allowed capturing the depolymerization of Si chains as well as a two‐step variation in the layer‐to‐layer distance. This latter first increases from ∼11.3 Å (for samples having a Ca/Si ratio