Local structures and Al/Si ordering in lanthanum aluminosilicate glasses explored by advanced 27Al NMR experiments...

The structures of 15 La-Al-Si-O glasses, whose compositions span 11-28 mol% La(2)O(3), 11-30 mol% Al(2)O(3), and 45-78 mol% SiO(2), are explored over both short and intermediate length-scales by using a combination of solid-state (27)Al magic-angle spinning (MAS) nuclear magnetic resonance (NMR) spectroscopy and molecular dynamics (MD) simulations. MAS NMR reveals Al speciations dominated by AlO(4) groups, with minor but significant fractions of AlO(5) (5-10%) and AlO(6) (≲3%) polyhedra present in all La(2)O(3)-Al(2)O(3)-SiO(2) glasses; the amounts of Al([5]) and Al([6]) coordinations increase for decreasing molar fraction of Si. The MD simulations reproduce this compositional trend, with the fractional populations of AlO(p) groups (p = 4, 5, 6) according well with the experimental results. The modeled La speciations mainly involve LaO(6) and LaO(7) polyhedra, giving a range of average La(3+) coordination numbers between 6.0 and 6.6; the latter increases slightly for decreasing Si content of the sample. Besides the expected bridging and non-bridging O species, minor contributions of oxygen triclusters (≤9%) and free O(2-) ions (≤4%) are observed in all MD data. The glass structures exhibit a pronounced Al/Si disorder; the MD simulations reveal essentially random SiO(4)-SiO(4), SiO(4)-AlO(p) and AlO(p)-AlO(q) (p, q = 4, 5, 6) associations, including significant amounts of AlO(4)-AlO(4) contacts, regardless of the n(Al)/n(Si) molar ratio of the glass. The strong violation of Al([4])-Al([4]) avoidance is verified by 2D (27)Al NMR experimentation that correlates double-quantum and single-quantum coherences, here applied for the first time to aluminosilicate glasses, and evidencing AlO(p)-AlO(q) connectivities dominated by AlO(4)-AlO(4) and AlO(4)-AlO(5) pairs. The potential bearings from distinct fictive temperatures of the experimental and modeled glass structures are discussed.