Development of calcium aluminate based systems for sludge cementation from radwaste decontamination

Nuclear industry generated waste including radioactive wastes, which have different forms and origins. The wastes produced by reprocessing of nuclear fuel are characterized by important water content, by high pH and temperature sensitivity. The cementation in ettringite systems might be a promising solution to solidify radioactive wastes. Mixtures of Calcium Aluminate Cement (CAC) and calcium sulfate are planned to be used, instead of Ordinary Portland Cement (OPC), to form a significant amount of ettringite able to catch water molecules when forming. Moreover, due to the low pH of CAC-based matrices, the latter have a good compatibility with the compounds used to stabilize active elements. Initially, the stability of the sorbent of cesium used in this study was tested in different pH environments (2 to 14) and temperature. Chemical analysis and different microstructural characterizations like X-ray diffraction, FTIR and SEM-EDS have allowed to set stability limits of ettringite systems. Then microstructural study on binary systems composed by mixture of CAC/calcium sulfate (hemihydrate and/or anhydrite) was realized to characterize ettringite stability during the time of hydration. Low pH properties were checked by chemical pore solutions analysis. However, the heat generated by hydration and the possible formation of expansive systems require an increase of e/s ratio and additional components like Ground Granulated Furnace Slag (GGBS). These two parameters were studied subsequently. Microstructural study of GGBS reactivity and the modification of ettringite assemblage were showed that GGBS act as filler at early time of hydration. To promote the GGBS reactivity at long term of hydration by alkaline and sulfate activation, different nature of calcium sulfate was used. Then the microstructural characteristic of this ternary system in presence of different e/s ratio was studied. Finally, different information on the effect of formulation parameters obtained led to the development of tests on formulations containing an inert simulated waste and enriched in chlorides. Systematic tests of fluidity, mechanical strength and for some expansion and heat generation should identify a series of mixtures adapted to test prototype to industrial scale for cementing wastes. (author)