The evolution of the network connectivity
of borosilicate glasses
with the progressive addition of aluminum is analyzed using solid-state
multinuclear magnetic resonance (NMR) spectroscopy to better understand
the structural mechanism by which boron inhibits nepheline crystallization
in nuclear-waste glasses. The [4]Al units exert a stronger
influence on Na+ than do the [4]B units, resulting
in the reorganization of tetrahedral to trigonal-planar boron ([4]B → [3]B) with increasing Al. The [3]B units preferably bond to [4]Al and interfere
with the Si–Al ordering critical to nepheline formation, thereby
inhibiting nucleation. Moreover, as Na+ charge compensates
both [4]B and [4]Al units, the presence of anionic
borate units confers a heterogeneous chemical environment about Na+ and prevents its transformation into a nepheline-like crystalline
environment. The NMR results for aluminoborosilicate glasses are compared
with those of their gallium analogues to assess the structural similarities
of Al and Ga in silicate-based glasses. Gallium integrates into the
borosilicate network as tetrahedral units similar to Al but is less
effective in competing with [4]B for Na+, leading
to higher [4]B ratios. The relative fractions of silicate
Q3 and Q4 species are determined semiquantitatively
using charge-balance constraints on 29Si NMR results, showing
that the silicate speciation in high-Ga glasses is restricted to Q4 units, which may affect the properties relevant to nuclear-waste
immobilization.