Densification of sodium and magnesium aluminosilicate glasses at ambient temperature: structural investigations by solid-state nuclear magnetic resonance and molecular dynamics simulations

Abstract

Sodium and magnesium aluminosilicate glasses with compositions 20Na₂O–20Al₂O₃–60SiO₂ (NAS) and 20MgO–20Al₂O₃–60SiO₂ (MAS) were subjected to a 12 and 25 GPa compression and decompression at room temperature, resulting in density increases from 3.7% to 5.3% (NAS) and from 8.2 to 8.4% (MAS), respectively. The pressurization at 25 GPa was done on ¹⁷O-enriched glasses, to facilitate characterization by ¹⁷O NMR. The structural changes associated with this process have been investigated by solid state ²⁹Si, ²⁷Al, ²³Na, ²⁵Mg, and ¹⁷O magic-angle spinning NMR and compared with the situation in thermally relaxed glasses and/or glasses prepared at ambient pressure. While in the Na aluminosilicate glass only subtle structural changes were observed in a sample densified at 12 GPa, the average coordination number of Al 〈CN(Al)〉 increases moderately from 4.00 to 4.26 by pressurization at 25 GPa. In the Mg-based system, 〈CN(Al)〉 increases from 4.34 to 4.57 to 4.83 in the sequence 10⁻⁴ GPa → 12 GPa → 25 GPa. The experimental result at 25 GPa was qualitatively confirmed by molecular dynamics (MD) simulations. Overall, pressurization results in more positive ²⁹Si and ¹⁷O chemical shifts, most likely reflecting a reduction in the Si–O–Si and Si–O–Al bonding angles in the pressurized glasses. Furthermore, the results are also consistent with either an increased number of non-bridging O-atoms upon pressurization, or a larger number of Si–O–Al or Al–O–Al linkages. The significantly higher sensitivity of MAS, compared to NAS glass, to an increase in 〈CN(Al)〉 upon pressurization, provides a good structural rationale for its significantly higher crack initiation resistance.