Influence of anionic silica forms in clear sodium silicate precursors on metakaolin geopolymerisation via 29Si and 27Al MAS-NMR and microstructural studies

Abstract

A number of synthesis parameters directly influence the degree of reticulation/geopolymerisation of metakaolin exposed to alkaline solutions of sodium hydroxide and/or sodium silicate. In the latter case, a sodium silicate solution can be depolymerised by the introduction of an appropriate amount of NaOH. The effects of the ageing of the activator solution on the reticulation of metakaolin-based geopolymers are quantified for the first time in this work. We studied the anionic species of the sodium silicate solution with the addition of NaOH made just before the preparation of the paste, 24 h or 7 days before. These three ageing periods cause a significant difference in the Si-bearing species in solution, as demonstrated by nuclear magnetic resonance on 29Si. The effect of these anionic species on the reticulation/polymerisation of metakaolin at room temperature was demonstrated by solid-state 27Al and 29Si MAS-NMR, the chemical stability in various solutions (deionised water, HCl, HNO3, H2SO4), and X-ray diffraction on geopolymer powders before and after immersion in acids. Compressive strength before and after the immersion in acidic media was an additional measurement to assess the overall structural stability of the 3D polymerised network of the final dense ceramic-like product. Ageing of the activator solution affected the chemical stability of the hardened geopolymers accompanied by a slight to severe reduction in strength after leaching in HNO3 or HCl and in H2SO4, respectively. The quantitative MAS-NMR description of the Si and Al coordination in the geopolymers was correlated with the chemical stability where the formulations with the higher number of Q4(0Al) and Q4(1Al) for the silicon species were more resistant (lower number of Na+ compensating for Al+3 to be exchanged with H+). The formulations with higher Al content in the structure, i.e. higher number of Q4(3Al) silicon species showed higher mechanical stability. These results show that the timing of the preparation of the alkaline activator is essential for a correct mix design.