In the experiment, the aluminosilicate glasses with aluminum saturation index (ASI), defined as the Al2O3/(Na2O+K2O+2CaO), equal to 0.74, 1.72. 2.52, or 4.05 were synthesized. The spectroscopy tests (MIR and Al-27 MAS-NMR) confirm that in glass with ASI < 1, the aluminum ions occur in the [AlO4](5-) only. In glasses with ASI > 1, the aluminum ions create mainly [AlO4](5-), but part of them occurs in the form of [AlO6](9-). The content of [AlO6](9-) octahedrons increases successively for ASI from 1.72 to 4.05. Glass with ASI equal to 4.05 demonstrates the highest content of pozzolanic active Al2O3. Model ashes were prepared by mixing 70 wt.% of glass, 20 wt.% of synthetic mullite and 10 wt.% of SiO2 as an equivalent of quartz. Then Portland cement CEM I 42.5R was milled together with 20 wt.% of each of model ashes to Blaine's specific surface area of 4,200 +/- 50 cm(2) g(-1). It was found that the addition of ash with higher content of [AlO6](9-) octahedrons in the structure of glass accelerates the hydration process of cement blend, which, in turn, positively affects its usable features (heat of hydration, initial setting time and compressive strength). According to the requirements of PN-EN 197-1:2012 standard, the introduction of ash with ASI coefficient equal to 4.05 gives cement blend of strength class of 52.5N. Cement blends with the ash of ASI value equal to 1.72 and 2.52 correspond to strength class of 32.5R, whereas the cement blend with the ash of ASI value equal to 0.74 does not achieve the minimum value of strength for any cement strength class. Results show that the change in chemical composition of fly ash glass and resulting from this diversified structure are essential from the point of view of hydration and properties of cement containing fly ashes in its composition.
