Stéphane Gaboreau

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.

Simulation of Cement/Clay Interactions: Feedback on the Increasing Complexity of Modelling Strategies

During the last decade, numerous studies have focused on long-term predictive reactive transport modelling of cement/clay interactions. These simulations have been performed using modelling strategies of growing complexity, e.g. (i) taking more minerals into account, (ii) considering the effect of dissolution/precipitation kinetics versus thermodynamic equilibrium, (iii) refining the spatial discretisation of the models, etc. The present study reviews these simulations in order to identify the main factors affecting numerical results (e.g. mass transport, mesh, selected phases). Simulations are reproduced here with a consistent set of data and input parameters arranged with increasing order of complexity. Only such a standardised approach can allow a proper comparison of numerical results. Modelled reaction pathways (i.e. mineralogical transformations) appear to be independent from the chosen modelling assumptions. Irrespective of the simulated case or the underlying hypotheses, the geochemical transformations remain located very close to the cement/clay interface.

A generalized model for predicting the thermodynamic properties of clay minerals

A set of models for estimating the enthalpy of formation, the entropy, the heat capacity and the volume of dehydrated phyllosilicates is presented. The model for entropy and heat capacity estimation is essentially based on a method of decomposition into polyhedral units, similar to that published by Holland (1989). The model for predicting the enthalpy of formation is based on the electronegativity scale, as previously developed by Vieillard (1994a, 1994b). For the sake of consistency, the models are parameterized using the same critical selection of thermodynamic properties from the literature. This includes a set of direct measurements especially dedicated to clay minerals that had not been taken into account in previous calculation methods. The accuracy of the predictions is tested for each property. The verification tests are also carried out for minerals that include different chemical elements than the phases used to derive the model constants, especially lithium-bearing micas. Verification tests also concern the Gibbs energy function that combines contributions from both models. Finally, the models are used in order to propose a complete thermodynamic database for clay mineral end-members. The consistency of the stability domains calculated on the basis of these thermodynamic properties is investigated by drawing relevant predominance diagrams for some chemical systems of interest. The models proposed represent a significant improvement with respect to previous works as regards the global accuracy of the estimates and because the developments were realized and tested using the same set of minerals, whose properties had been collected through a critical selection of the literature.

Impact of microstructure on anion exclusion in compacted clay media

The sensitivity of ion concentration distribution models to three key model assumptions, the pore-size distribution of clay media, the distance of closest approach of ions to the clay surface, and the accessibility of sub-nanometer-wide clay mineral interlayer spaces to anions, was explored by solving the Poisson-Boltzmann equation for swelling and non-swelling clay materials. Our calculations show that all three model assumptions significantly impact values predicted for the anion accessible porosity. As a consequence, macroscopic measurements of anion exclusion in clay media cannot be used to test any of the three model assumptions independently of the two others. Information gained at the nanoscale,in particular, a detailed characterization of pore size distribution, is necessary to develop accurate predictive models of the anion accessible porosity of clay media.