Stability of phyllosilicates in Ca(OH)2 solution: Influence of layer nature, octahedral occupation, presence of tetrahedral Al and degree of crystallinity

This paper presents the results of a comprehensive investigation of the interaction of layered silicates with Ca(OH)2 in hydrothermal conditions. The study is intended to evaluate the stability of the clay buffer in radioactive waste repositories, at the intermediate stages of concrete leaching, when the pH is controlled by the dissolution of portlandite. The influence of layer nature, octahedral occupation, presence of tetrahedral Al and degree of crystallinity will be assessed by analysing the behaviour of a set of well-selected phyllosilicates and using the combined capabilities of 29Si and 27Al MAS-NMR spectroscopy, powder X-ray diffraction and SEM/EDX. The results show that the main factor affecting the stability of the clay is the octahedral occupation, so that trioctahedral phyllosilicates are much more stable than dioctahedral ones. The nature and expandability of the layer does not seem to much influence the stability of the clay, so that a 2:1 expandable phyllosilicate shows the same stability as a chemically analogous 1:1 non-expandable phyllosilicate. However other factors like the poor crystallinity of the starting material or the presence of Al in the tetrahedral sheet of trioctahedral phyllosilicates weaken the clay structure in alkaline conditions and favour the transformation towards other phases.