Structure–property relations of binary ferrite melts

Molten ferrite systems are used in the smelting and refining processes in steelmaking, to reduce the loss of metals in slags and to accelerate reaction rates. Here, high-energy x-ray diffraction experiments have been performed on aerodynamically levitated molten spheres of 43BaO–57FeOₓ and 43SrO–57FeOₓ at 1873 K using laser beam heating. The composition was varied within the range of x = 1–1.5 by changing the oxygen partial pressure of the levitation gas. The corresponding x-ray pair distribution functions have been interpreted using empirical potential structure refinement (EPSR) modeling. In oxygen-rich melts (x = 1.5), our EPSR models indicate very similar structures for the different alkaline-earth liquids, with both the Ba–O and Sr–O coordination numbers to be ∼8.4 and the total Fe–O coordination numbers ∼5.7. However, our models show that in reducing environments, the Fe³⁺ and Fe²⁺ ions exhibit very different behaviors in the Ba- and Sr-ferrite liquids. In the Ba-ferrite melt, the Fe³⁺–O coordination number decreases from 5.7 (at x = 1.5) to 5.2 (at x = 1.07), whereas Fe²⁺–O remains constant at ∼5.0 across the same compositional range. In the Sr melts, both the Fe²⁺–O and Fe³⁺–O coordination numbers rise from ∼5.7 (at x = 1.5) to 6.3 (at x = 1.07). All models show the structures to be heterogeneous with intertwined nanometer sized clusters or channels of Ba/Sr–O and Fe–O polyhedra that grow as oxygen content is reduced. Changes in the viscosity and electrical properties are interpreted in terms of the number of bridging and non-bridging oxygens associated with FeO₄ tetrahedra and concentration of charge carriers, respectively.

Mots clés

• high-energy X rays
• flux melting
• binary liquid
• chemical bonding
• microheterogeneity
• Monte Carlo methods