Neutron diffraction has been performed on two samples from the PbO-Ga2
O3 glass-forming system with 67 mol% PbO and 80 mol% PbO. The results
show that the structure involves a network based on GaO4 tetrahedra, T
he PbO has an essential oxygen-providing role in the formation of the
network. The high lead limit of the glass-forming range, similar to 83
mol% PbO, is shown to correspond to the connectivity of the Ga-O netw
ork going to zero, The abrupt change in some physical properties at si
milar to 75 mol% PbO is shown to correspond to the initial formation o
f GaO4 tetrahedra with a connectivity of zero, The low lead limit of t
he glass-forming range is higher than the theoretical equimolar limit
due to the constraining effect of the Pb-O coordination shell on the b
ond and torsion angles of the Ga-O network.