Formation of a Network Structure in the Gaseous Reduction of Magnetite Doped with Alumina

Reduction of un-doped magnetite is developed topochemically with the formation of a dense iron shell. However, the reduction of alumina-doped magnetite to wüstite proceeds with the formation of a network-like structure which consists of criss-crossed horizontal and vertical plates of wüstite. Reduction of magnetite includes the conversion of Fe³⁺ to Fe²⁺ and the movement of iron cations from the tetrahedral sites on the {400} and {220} planes of magnetite to the octahedral sites on the {200} planes of wüstite. Alumina has a negligibly small solubility in wüstite. In the reduction of magnetite doped with Al₂O₃, rejected Al³⁺ cations from wüstite diffuse to the magnetite–hercynite solid solution. Enrichment of the Fe₃O₄–FeAl₂O₄ solution with alumina in the vicinity of the reduction interface restricts the growth of {220} planes of wüstite and nucleation of {220} planes adjusted to the existing planes, preventing the merging of wüstite plates during the reduction process. Reduction of magnetite from the magnetite–hercynite solid solution practically stops when the Al³⁺ content at the interface approaches the solubility limit. Wüstite in the separated plates is reduced further to iron.