The nature of phase separation in binary oxide melts and glasses. II. Selective solution mechanism

A comprehensive review of structural data in binary silicate systems indicates that the tetrahedral critical radius (87.2 pm) of binary silicate melts (or glasses) is associated with the silicon tetrahedral network that defines the structure of the melt. In a binary system, most of the cages present in the melt are made of six and five-membered rings of silicon tetrahedra. Cages bounded by six or more-membered rings can host cations of all sizes. However, cations that enter in cages made of five-membered rings are discriminated by their ionic radius. Cations with ionic radii larger than about 87.2 pm (network modifiers) cannot enter in pentagonal apertures; cations with radii smaller than 87.2 pm (amphoteric cations) can. Cages bounded by pentagonal rings play a key role in phase separation by selecting which cations can fit in them, adopt a four-fold coordination, and reduce the size of miscibility gaps, i.e. the cages permit explaining why some cations are amphoteric. This result is important because it shows that a structural control is exerted by the solvent (here SiO₂) upon immiscibility which creates a selective solution mechanism that affects small (<87.2 pm) cations in binary silica-rich melts.