NaPON Doping of Na4P2S7 Glass and Its Effects on the Structure and Properties of Mixed Oxy-Sulfide-Nitride Phosphate Glass

The preparation, properties, and short-range order (SRO) structures of glasses in the series (1-x)[2/3Na2S + 1/3P2S5] + x[1/3Na2S + 2/3NaPO2.31N0.46] = Na4P2S7-6xO4.62xN0.92x, where 0 ≤ x ≤ 0.5 (NaPSON), are reported on. In this study, these mixed oxy-sulfide-nitride (MOSN) glasses were prepared by adding the nitrided material NaPO3-(3/2)yNy; y = 0.46 = NaPO2.31N0.46 (NaPON) to the base sulfide glass Na4P2S7. For comparison purposes, additions of the unitrided material, y = 0, NaPO3, were also studied (NaPSO). Accordingly, large batches of bubble-free glass could be prepared making this route of nitrogen doping amendable toward scaling-up the glass melting process; though, only small amounts of nitrogen could be incorporated in this manner. Nitrogen and sulfur compositional analysis were combined with XPS, Raman, FT-IR, and 31P MAS NMR spectroscopies to determine the amount of retained nitrogen in the glass after melting and quenching and to determine the effect of the added nitrogen and oxygen on the structure of the base pure sulfide glass Na4P2S7, x = 0.0. The nitrogen content increased linearly with the addition of NaPON, but was found, through quantitative 31P MAS NMR analysis, to be approximately half that expected at each value of x. Despite the small amount of nitrogen retained in these glasses, profound increases in the glass transition (Tg) and crystallization temperatures (Tc) were found with increasing x. For the intermediate values of x, 0.2 and 0.3, no crystallization of the supercooled melt was observed even 250 °C above the Tg. It was found that the addition of NaPON to the series caused a disproportionation reaction, where the oxide and oxy-nitride SRO species preferentially formed covalent, networking phosphate chains, forcing the sodium modifier to ionic sulfide units with large fractions of nonbridging sulfurs (NBSs). This disproportionation reaction was also observed in the NaPO3 doped series of glasses, but to a smaller extent. Oxygen was found in both bridging oxygen (BO) and nonbridging oxygen (NBOs) structures while the sulfur was predominantly found in nonbridging sulfur (NBS) structures. N 1s XPS and 31P NMR studies provided insight into the nitrogen bearing phosphorus units and the wt % of nitrogen that was retained in the quenched glasses. It was found that trigonally coordinated nitrogen (Nt) was preferentially retained in the melt, whereas it is proposed that the linearly coordinated (doubly bonded) nitrogen (Nd) accounts for the lost nitrogen in the glasses.