Intermediate Role of Gallium in Oxidic Glasses: Solid State NMR Structural Studies of the Ga2O3–NaPO3 System

A series of (NaPO3)1–x(Ga2O3)x glasses (0 ≤ x ≤ 0.35) prepared by conventional melt-quenching methods has been structurally characterized by various complementary high resolution one-dimensional and two-dimensional (2D) solid state magic angle spinning nuclear magnetic resonance (MAS NMR) techniques, which were validated by corresponding experiments on the crystalline model compounds GaPO4 (quartz) and Ga(PO3)3. Alloying NaPO3 glass by Ga2O3 results in a marked increase in the glass transition temperature, similar to the effect observed with Al2O3. At the atomic level, multiple phosphate species QnmGa (n = 0, 1, and 2; m = 0, 1, 2, and 3) can be observed. Here n denotes the number of P–O–P and m the number of P–O–Ga linkages, and (m + n ≤ 4). For resolved resonances, the value of n can be quantified by 2D J-resolved spectroscopy, refocused INADEQUATE, and a recently developed homonuclear dipolar recoupling method termed DQ-DRENAR (double-quantum based dipolar recoupling effects nuclear alignment reduction...

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