Smectite illitization is a common mineralogical reaction occurring during the burial diagenesis of clay-rich sediments and shales, and has thus attracted sustained interest over the last fifty years. Prior studies have concluded that smectite illitization proceeds through a steady set of homogeneous reactions involving intermediate mixed layers of varying compositions. In these intermediate structures, illite and smectite or, more generally, expandable layers (I and Exp layers, respectively) coexist among the same crystallites giving rise to non-periodic structures (I-Exp) characterized by specific diffraction effects. Consistent with this model, reaction progress was characterized by the simultaneous increase in the illite content in I-Exp and in their stacking order leading to the following mineralogical sequence: smectite → randomly interstratified I-Exp with high smectite contents (> 50% Exp layers) → ordered I-Exp with high illite contents (> 50% I layers) → illite. Although reaction mechanisms have been extensively debated, this structural characterization has not been challenged, possibly due to a methodological bias. In the present study, X-ray diffraction patterns typical of the diagenetic illitization of smectite are interpreted using modern approaches involving profile fitting (multi-specimen method). Novel insights into the structure of intermediate reaction products are thus obtained. In particular, original clay parageneses are described that include the systematic presence of illite, kaolinite, chlorite and a mixed layer containing kaolinite and expandable layers (K-Exp).

X-ray diffraction (XRD) patterns were calculated and compared to literature data with the aim of investigating the crystal structure of nanocrystalline calcium silicate hydrates (C-S-H), the main binding phase in hydrated Portland cement pastes. Published XRD patterns from C-S-H of Ca/Si ratios ranging from ~ 0.6 to ~ 1.7 are fully compatible with nanocrystalline and turbostratic tobermorite. Even at a ratio close or slightly higher than that of jennite (Ca/Si = 1.5) this latter mineral, which is required in some models to describe the structure of C-S-H, is not detected in the experimental XRD patterns. The 001 basal reflection from C-S-H, positioned at ~ 13.5 Å when the C-S-H structural Ca/Si ratio is low (< 0.9), shifts towards smaller d values and sharpens with increasing Ca/Si ratio, to reach ~ 11.2 Å when the Ca/Si ratio is higher than 1.5. Calculations indicate that the sharpening of the 001 reflection may be related to a crystallite size along c* (i.e. a mean number of stacked layers) increasing with the C-S-H Ca/Si ratio. Such an increase would contribute to the observed shift of the 001 reflection, but fails to quantitatively explain it. It is proposed that the observed shift could result from interstratification of at least two tobermorite-like layers, one having a high and the other a low Ca/Si ratio with a basal spacing of 11.3 and 14 Å, respectively.

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 SiQ³andQ²environments account, respectively, for up to 40.2 ± 1.5% and 55.6 ± 3.0% of the total Si, with part of theQ³Si being attributable to remnants of the synthesis reactant. As the Ca/Si ratio increases up to 0.87 ± 0.02, the SiQ³environment decreases down to 0 and is preferentially replaced by theQ²environment, which reaches 87.9 ± 2.0%. At higher ratios,Q²decreases down to 32.0 ± 7.6% for Ca/Si = 1.38 ± 0.03 and is replaced by theQ¹environment, 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 <∼0.6) up to 12.25 Å at Ca/Si = 0.87 ± 0.02, probably as a result of a weaker layer-to-layer connectivity, and then decreases down to 11 Å when the Ca/Si ratio reaches 1.38 ± 0.03. The decrease in layer-to-layer distance results from the incorporation of interlayer Ca that may form a Ca(OH)₂-like structure, nanocrystalline and intermixed with C–S–H layers, at high Ca/Si ratios.