This work contributes to better understand iron redox reactions and mechanisms in silicate melts. It was conducted on compositions in both Na2O-B2O3-SiO2-FeO et Na2OAl2O3- SiO2-FeO systems. The influence of boron-sodium and aluminum-sodium substitutions and iron content on properties and structure of glasses and on the iron redox kinetics has been studied by Raman, Mössbauer and XANES spectroscopies at the B and Fe K-edges. In borosilicate glasses, an increase in iron content or in the Fe3+/ΣFe redox state implies a structural rearrangement of the BO4 species in the glass network whereas the BO3 and BO4 relative proportions remain nearly constant. In all studied glasses and melts, Fe3+ is a network former in tetrahedral coordination, unless for aluminosilicates of ratio Al/Na>1 where Fe3+ is a network modifier in five-fold coordination. Near Tg, diffusion of network modifying cations controls the iron redox kinetics along with a flux of electron holes. At liquidus temperatures, oxygen diffusion is considered to be the mechanism that governs redox reactions. This study shows the role played by the silicate network polymerization on the redox kinetics. In borosilicate melts, iron redox kinetics depends on the boron speciation between BO3 and BO4 that depends itself on the sodium content. Furthermore, an increase in the network-former/network-modifier ratio implies a decrease in oxygen diffusion that results in a slowing down of the redox kinetics. The obtained results allow a description of the iron redox kinetics for more complex compositions as natural lavas or nuclear waste model glasses.
