6533b822fe1ef96bd127d45c

RESEARCH PRODUCT

Etude de l'influence de l'hydratation des laitiers sur les propriétés de transfert gazeux dans les matériaux cimentaires

subject

description

Cements with high slag content are currently studied as possible candidate for nuclear waste containment materials. In this context it is important to know their microstructure and the transport properties (permeability and diffusion) of the gases that are formed by the radiolysis of the water present in this material. According to literature, these properties are strongly impacted by the addition of blast furnace slag. The aim of this work is to correlate the hydration processes of slag blended cements with their transport properties. In the first part of this work, the hydration of the slag blended cements, for which only few results have been reported to date, has been studied. Silicon-29 and aluminium-27 Magic-Angle Spinning Nuclear Magnetic Resonance (MAS NMR) were used to follow the variations of anhydrous phases of clinker (C3S, C2S, C3A and C4AF) and of the main oxides of the slag (SiO2, Al2O3, CaO, MgO and SO3). The quantity of calcium dissolved from slag was deduced by fitting the quantity of portlandite [Ca(OH)2] calculated by a geochemical software (PHREEQC - coupled to a thermodynamic database) with TGA measurements. Our approach enabled the evolution of the hydration degree (percentage of reacted material) of various oxides of slag to be determined. A progressive and an incongruent dissolution (the rate of dissolution of the oxides is different) of the slag is observed. The low reactivity of slag could be linked, at a hydration time, to a lower content of bound water, chemical shrinkage and heat of hydration. Quantitatively accounting for the dissolution of clinker and oxide of slag yields a more accurate description of the hydration process. The second part of this work is focused on the microstructure evolution and its influence on the transport properties (diffusion and permeability). Time-evolution of the diffusion coefficients and the intrinsic permeability could be monitored and were then compared to that of the microstructure (global porosity, pore entry size distribution, specific surface area and the degree of connectivity). The results showed a decrease in the diffusion coefficient and permeability over time which is due to the progressive filling of the porosity. A decrease of these parameters with the slag content increasing was also observed. This is a consequence of the diminution of the capillary porosity and augmentation of the nanoporosity resulting from changes in the microstructure of C-S-H. The last part concerns the relation between the hydration processes, the microstructure and the transport properties. To this aim, volumetric balances of reactions involved in the hydration processes were made by considering globally or specifically the hydration of the different phases. Accounting for the hydration of each phase of the cement allowed us to determine the global porosity, the bound water content and the chemical shrinkage with accuracy of the order of 10 %. This description allows the understanding of the transport properties variations in time for a same material To establish this time evolutions for all the cements, the apparent volume of C-S-H was recalculated to account for the microstructure of these hydrates