Different route of hydroxide incorporation and thermal stability of new type of water clathrate: X-ray single crystal and Raman investigation

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Abstract

Chlormayenite Ca12Al14O32[♦4Cl2] (♦-vacancy) is partially hydrated micro porouss mineral with hydroxide groups situated at various crystallographic sites. There are few mechanisms describing its hydration. The first one assumes Cl- substitution by OH- at the center of the structural cages (W-site). The second one determines the converting a T1O4 tetrahedron to a T1O3(OH)3 octahedron due to the replacement of oxygen at the O2 site by three OH-groups according to the scheme: (O2O2- + W Cl-) → 3 × O2aOH. The third mechanism, not considered so far in the case of zeolite-like minerals, includes the hydroxide incorporation in form of hydrogarnet defect due to the arrangement of tetrahedral (OH)4 in vacant cages. This yields a strong hydrated phase containing even up to 35% of water more than in any currently known mineral applicable to Portland cement. Moreover, water molecules present in different structural cages are stable up to 355 K while dehydroxylation linked to the gradual loss of only 8% of OH- groups according to 3 O2aOH- → O2O2- + W OH- + gH2O occurs at temperature range from 355 K to 598 K.

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Dulski, M., Marzec, K. M., Kusz, J., Galuskina, I., Majzner, K., & Galuskin, E. (2017). Different route of hydroxide incorporation and thermal stability of new type of water clathrate: X-ray single crystal and Raman investigation. Scientific Reports, 7(1). https://doi.org/10.1038/s41598-017-08152-1

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