Structural Aspects of Ambient-Temperature Densification of Highly Crack-Resistant Borosilicate and Aluminoborosilicate Glasses: Two Case Studies Examined by Solid-State NMR.

The structural aspects of ambient-temperature densification via pressurization at 25 GPa were studied by solid-state NMR for two case studies: An alkaline earth boroaluminosilicate glass with the composition 6CaO-3SrO-1BaO-10Al2O3-10B2O3-70SiO2 (labeled SAB) and a sodium magnesium borosilicate glass with the composition 10Na2O-10MgO-20B2O3-60SiO2 (labeled MNBS). For SAB glass, cold pressurization results in significant increases in the average coordination numbers of both boron and aluminum, in line with previous results found in hot-compressed alkali aluminoborosilicate glasses. In addition, 27Al/11B dipolar recoupling experiments reveal a significant decrease in the 11B/27Al dipolar interaction strength upon pressurization, suggesting that the higher-coordinated boron and aluminum species experience weaker magnetic interactions. While this is an expected consequence of the longer internuclear distances involving higher coordination states, the magnitude of the effect also is consistent with a decrease of average B-O-Al internuclear connectivity. By conjecture, a decreased B-O-Al connectivity may present a mechanism of plastic flow inhibiting crack initiation in aluminoborosilicate glasses. In the case of the MNBS glass, no change in the average boron coordination number was observed within experimental error; however, densification increases the extent of B-O-Si connectivity at the expense of small ring structures with dominant B-O-B connectivity. With regard to boron coordination, the data obtained for both case studies differ from those previously found in a series of alkali borosilicate glasses, which had shown an unexpected decrease in N4 upon increased pressure. The results of the present study highlight the importance of changes of medium-range order regarding densification.