The 11B and 207Pb NMR spectra have been used to study the structure of glasses in the system PbO–B2O3–SiO2. The results indicate that the glasses do not contain an appreciable number of BO3 units, and the network‐forming lead atoms play an important role in the compositional behavior of N4 (the fraction of boron atoms in BO4 units). The measured values of N4 are analyzed according to a simplified theoretical equation. It is concluded from the N4 analysis that the Pb+2 ions are shared almost evenly between the boron–oxygen and silicon–oxygen networks.

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