Mixed Network Former Effects in Oxide Glasses: Spectroscopic Studies in the System (M₂O)_1/3[(Ge₂O₄)_x(P₂O₅)_1–x]_2/3

The structure of mixed-network former glasses in the system (M 2 O) 0.33 [(Ge 2 O 4 ) x (P 2 O 5 ) 1– x ] 0.67 .(M = Na, K) has been studied by 31 P and 23 Na high-resolution and dipolar solid state nuclear magnetic resonance (NMR) techniques, O-1s X-ray photoelectron spectroscopy, and Raman spectroscopy. Using an iterative fitting procedure, a quantitative structural model has been developed that is consistent with all of the experimental data and which provides a detailed description of network connectivities, network modification processes, and spatial cation distributions. Formation of heteroatomic P–O–Ge linkages is generally preferred over homoatomic P–O–P and Ge–O–Ge linkages, as shown by a detailed comparison with a random linkage model. An exception occurs in glasses with low germanium contents ( x = 0.2) where a pronounced nonlinear dependence of the glass transition temperature on x can be related to a cross-linking of the sodium ultraphosphate network by fully polymerized germanium species, possibly including also 5- and 6-fold coordination states. At higher x values, the Ge component is modified as well, however, the fraction of anionic nonbridging oxygen atoms bound to germanium is always lower than expected for proportional modifier sharing between both network formers. Rather, the phosphate component is preferentially modified by the cations, leading to the formation of P (1) units at high x values. Consequently, the local coordination of the cations is dominated by phosphorus, as is clearly evident from the 23 Na{ 31 P} rotational echo double resonance (REDOR) results. This preferred association, combined with the formation of P (1) units, results in partially clustered cation distributions, which can be detected by 23 Na spin echo decay spectroscopy. Finally, the joint interpretation of all of the data from NMR, Raman, XPS, and thermal analysis measurements offers indirect evidence for the formation of higher germanium coordination states in this glass system.