Aluminosilicate network formation during geopolymerization followed by in-situ 27Al nutation NMR
May 27-June 1, 2018
In classical cement systems, hydration reactions can typically be stopped by a solvent exchange (such as isopropanol) or by drying1. Subsequently, the chemical reactions are studied by separating and characterizing independently the solid and the liquid phases at different times, to follow their respective compositions and to establish a reaction process by finding chemical intermediates and products. As for geopolymers, they are formed by a dissolution-condensation mechanism resulting from the mixing a solid aluminosilicate source (for example metakaolin) with a highly concentrated alkali-silicate solution. The properties of the suspension do not allow to employ phase separation. This is the reason why the reaction mechanism leading to geopolymers is still said to be unclear, because it has only been studied by indirect methods so far, such as calorimetry, time-resolved rheology or small-angle scattering2 for instance.
In-situ static 27Al NMR has already been used as a direct method to probe and quantify the aluminate species in the liquid phase during geopolymerization, using the quadrupolar nature of 27Al nuclei. Aluminum is not present in the liquid state at the very beginning of the process but goes to the initial aluminosilicate powder to the final solid product, naturally making it the nucleus of interest for an NMR study. While dissolved species are mobile enough for the quadrupolar interaction to be averaged, the quadrupolar coupling persists in less mobile species or in solids, leading to different nutation behaviors.
In the present study, it will be demonstrated that a nutation experiment, which simply consists in varying the pulse length and measuring the resulting signal, allows filtering out the reactant aluminosilicate source from the 27Al NMR signal to detect reaction intermediates, and apparently also products. The evolution of the 27Al NMR signal was followed over longer periods of time up to several days during the geopolymerization process of metakaolin-based systems. It was shown that more than two steps can be identified in the geopolymerization process, depending on the frequency of the radiofrequency field applied during the experiment. Simulation of nutation curves at different times of the reactions allowed to follow the evolution of the quadrupolar coupling constant, and gave insight on the aluminate intermediates. Finally, the NMR results were confronted to time-resolved rheology and isothermal calorimetry in order to understand processes occurring on different time scales.
1- Collier et al. The influence of water removal techniques on the composition and microstructure of hardened cement pastes, Cement and Concrete Research, 38(6) (2008) pp. 737-744.
2- Steins et al. Structural Evolution during Geopolymerization from an Early Age to Consolidated Material, Langmuir, 28 (2012) pp. 8502-8510.
3- Favier et al., Mechanical properties and compositional heterogeneities of fresh geopolymer pastes, Cement and Concrete Research, 48 (2013) pp. 9-16.
Virginie Benavent, Jean-Baptiste d’Espinose de Lacaillerie, Guylaine Ducouret, Jan-Philip Merkl, Maxim Pulkin, and Karsten Seidel, "Aluminosilicate network formation during geopolymerization followed by in-situ 27Al nutation NMR" in "International Conference on Alkali Activated Materials and Geopolymers: Versatile Materials Offering High Performance and Low Emissions", J. Provis, University of Sheffield C. Leonelli, Univ. of Modena and Reggio Emilia W. Kriven, Univ. of Illinois at Urbana-Champaign A. Boccaccini, Univ. of Erlangen-Nuremberg A. Van Riessen, Curtin University, Australia Eds, ECI Symposium Series, (2018). http://dc.engconfintl.org/geopolymers/96