Peralkalinity, Al{rightleftharpoons}Si Substitution, and Solubility Mechanisms of H2O in Aluminosilicate Melts

The solubility mechanisms of H₂O in peralkaline sodium aluminosilicatequenched melts (anhydrous NBO/T = 0.5) have been studied withRaman spectroscopy as a function of Al/(Al + Si) (0–0–3)and H²O content (0–7.5 wt.%). The coexisting structuralunits in the anhydrous quenched melts are TO2 (Q4), T2O5(Q3),and TO3 (Q2). In Al-free Na₂Si₄O₉ (NS4) melt, H₂O forms complexes with Na⁺(Na–OH bonds) and with Si⁴⁺ (Si–OH bonds). MolecularH₂O is also detected. TO3 structural units are not detectedin this composition. In the H₂O concentration range between0 and 4 wt.%, there is an approximately 20% increase in NBO/Tresulting from the increased abundance ratio, T₂O₅/TO2. Withfurther increments in water activity, the NBO/T of hydrous NS4melt is reduced. The depolymerization results from hydroxylationof the silica tetrahedra, whereas polymerization is due to formationof complexes with Na–OH bonding. In Al-bearing compositions on the Na₂Si₄O₉–Na₂(NaAl)₄O₉–join, there is evidence for Al–OH bonding in additionto Na–OH and Si–OH bonds. Among these complexes,the relative abundance of those with Si–OH bonds diminisheswith increasing Al/(A1 + Si), whereas complexes with Al–OHand Na–OH bonds become more important. Complexes withNa–OH bonds dominate for H₂O4 wt.%, whereas complexeswith Al–OH dominate at higher water content. The threestructural units, TO₃, T₂O₅, and TO², were observed in bothanhydrous and hydrous peralkaline sodium aluminosilicate melts.Their abundance varies, however, with the H₂O concentrationin the melts. The NBO/T decreases to a minimum (a 30–50%lowering of NBO/T relative to anhydrous materials) for low H₂Ocontents (3–4 wt.% H₂O), and increases as the H₂O contentis increased further.