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International audienceInteractions between cementitious materials and claystone are driven by chemical gradients in pore water and might lead to mineralogical modifications in both materials. In the context of a radioactive waste repository, this alteration might influence safety-relevant clay properties like swelling pressure, permeability, or specific retention. In this study, interfaces of Opalinus Clay, a potential host-rock in Switzerland, and three concrete formulations emplaced in the Cement-Clay Interaction (CI) Experiment at the Mont Terri Underground Laboratory (St. Ursanne, Switzerland) were analysed after 2.2 years of interaction. Sampling techniques with interface stabilisation followed by inclined intersection drilling were developed. Element distribution maps of the concrete-clay interfaces show complex zonations like sulphur enrichment, zones depleted in Ca but enriched in Mg, strong Mg enrichment adjacent to the interface, or carbonation. Consistently, the carbonated zone shows a reduced porosity. Properties of the complex zonation strongly depend on cement properties like water content and pH (ordinary Portland cement vs. low-pH cement). An increased Ca or Mg content in the first 100 lm next to the interface is observed in Opalinus Clay. The cation occupancy of clay exchanger phases next to the ordinary Portland cement interface is depleted in Mg, but enriched in Na, whereas porosity shows no changes at all. The current data suggests migration of CO2=HCO 3 , SO2 4 , and Mg species from clay into cement. pH decrease in the cement next to the interface leads to instability of ettringite, and the sulphate liberated diffuses towards higher pH regions (away from the interface), where additional ettringite can form

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Quantitative analysis of the X-ray pair distribution function collected on calcium silicate hydrates having Ca/Si ratios ranging between 0.57 and 1.47 was applied. With increasing Ca/Si ratio, Si bridging tetrahedra are omitted and Ca(OH)2 is detected at the highest ratios.

Understanding calcium silicate hydrates (CSHs) is of paramount importance for understanding the behavior of cement materials because they control most of the properties of these man-made materials. The atomic scale water content and structure have a major influence on their properties, as is analogous with clay minerals, and we should assess these. Here, we used a multiple analytical approach to quantify water distribution in CSH samples and to determine the relative proportions of water sorbed on external and internal (interlayer) surfaces. Water vapor isotherms were used to explain the water distribution in the CSH microstructure. As with many layered compounds, CSHs have external and internal (interlayer) surfaces displaying multilayer adsorption of water molecules on external surfaces owing to the hydrophilic surfaces. Interlayer water was also quantified from water vapor isotherm, X-ray diffraction (XRD), and thermal gravimetric analyses (TGA) data, displaying nonreversible swelling/shrinkage behavior in response to drying/rewetting cycles. From this quantification and balance of water distribution, we were able to explain most of the widely dispersed data already published according to the various relative humidity (RH) conditions and measurement techniques. Stoichiometric formulas were proposed for the different CSH samples analyzed (0.6 < Ca/Si < 1.6), considering the interlayer water contribution.