The nature of phase separation in binary oxide melts and glasses. III. Borate and germanate systems

A review of immiscibility data in binary borate and germanate systems was performed in order to compare miscibility gap consolute temperatures with ionic potentials and radii of their associated cations. The trends obtained demonstrate that a selective solution mechanism similar to the one identified for the binary silicate systems is present in the borate and germanate binaries. More importantly, the borate and germanate immiscibility data permitted the identification of a new group of cations depicting an immiscibility behaviour different from the ones identified in binary silicate systems. The new group involves highly polarizable cations possessing a lone pair of electrons. This lone pair of electrons together with oxygen bonded by strong covalent bonds to modifier cations provides efficient shielding to the cations' nuclei which considerably reduces the coulombic repulsions and produces miscibility gaps with very low consolute temperatures. A new group of cations having an homogenizing effect on melts (i.e. a capacity to make immiscible melts single phase) is thus reported. Experimental and spectroscopic data suggest that miscibility gaps associated with cations having a lone pair of electrons exist in binary silicate systems such as TlO_1/2-SiO₂, PbO-SiO₂, SnO-SiO₂ and Bi₂O₃-SiO₂. The consolute temperature of their miscibility gaps is expected to be relatively low and metastable.