Transformations to the aluminum coordination environment and network polymerization in amorphous aluminosilicates under pressure

The structure of calcium aluminosilicate glasses (CaO)x(Al2O3)y(SiO2)1−x−y with the near tectosilicate compositions x ≃ 0.19 and 1 − x − y ≃ 0.61 or x ≃ 0.26 and 1 − x − y ≃ 0.49 was investigated by in situ high-pressure neutron diffraction and 27Al nuclear magnetic resonance (NMR) spectroscopy. The results show three distinct pressure regimes for the transformation of the aluminum coordination environment from tetrahedral to octahedral, which map onto the deformations observed in the production of permanently densified materials. The oxygen packing fraction serves as a marker for signaling a change to the coordination number of the network forming motifs. For a wide variety of permanently densified aluminosilicates, the aluminum speciation shares a common dependence on the reduced density ρ′ = ρ/ρ0, where ρ is the density and ρ0 is its value for the uncompressed material. The observed increase in the Al–O coordination number with ρ′ originates primarily from the formation of six-coordinated aluminum Al(VI) species, the fraction of which increases rapidly beyond a threshold ρthr′∼ 1.1. The findings are combined to produce a self-consistent model for pressure-induced structural change. Provided the glass network is depolymerized, one-coordinated non-bridging oxygen atoms are consumed to produce two-coordinated bridging oxygen atoms, thus increasing the network connectivity in accordance with the results from 17O NMR experiments. Otherwise, three-coordinated oxygen atoms or triclusters appear, and their fraction is quantified by reference to the mean coordination number of the silicon plus aluminum species. The impact of treating Al(VI) as a network modifier is discussed.