Distribution of Water in Synthetic Calcium Silicate Hydrates.

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.

Sorption of beryllium in cementitious systems relevant for nuclear waste disposal: Quantitative description and mechanistic understanding.

Beryllium has applications in fission and fusion reactors, and it is present in specific streams of radioactive waste. Accordingly, the environmental mobility of beryllium needs to be assessed in the context of repositories for nuclear waste. Although cement is widely used in these facilities, Be(II) uptake by cementitious materials was not previously investigated and was hence assumed negligible. Sorption experiments were performed under Ar-atmosphere. Ordinary Portland cement, low pH cement, calcium silicate hydrated (C-S-H) phases and the model system TiO2 were investigated. Sorption kinetics, sorption isotherms and distribution ratios (Rd, in kg⋅L-1) were determined for these systems. Molecular dynamics were used to characterize the surface processes driving Be(II) uptake. A strong uptake (5 ≤ log Rd ≤ 7) is quantified for all investigated cementitious systems. Linear sorption isotherms are observed over three orders of magnitude in [Be(II)]aq, confirming that the uptake is controlled by sorption processes and that solubility phenomena is not relevant within the investigated conditions. The analogous behaviour observed for cement and C-S-H support that the latter are the main sink of beryllium. The two step sorption kinetics is explained by a fast surface complexation process, followed by the slow incorporation of Be(II) in C-S-H. Molecular dynamics indicate that Be(OH)3- and Be(OH)42- are sorbed to the C-S-H surface through Ca-bridges. This work provides a comprehensive quantitative and mechanistic description of Be(II) uptake by cementitious materials, whose retention properties can be now reliably assessed for a wide range of boundary conditions of relevance in nuclear waste disposal.