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

Chlormayenite Ca(12)Al(14)O(32)[♦(4)Cl(2)] (♦-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 T1O(4) tetrahedron to a T1O(3)(OH)(3) octahedron due to the replacement of oxygen at the O2 site by three OH-groups according to the scheme: ((O2)O(2−) + (W)Cl(−)) → 3 × (O2a)OH. 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(O2a)OH(−) → (O2)O(2−) +(W)OH(−) + (g)H(2)O occurs at temperature range from 355 K to 598 K.