Sustainable hydrogen-based direct reduction (HyDR) of iron oxide is an effective approach to reduce carbon emissions in steel production. As the reduction behaviour is closely related to the microstructure evolution, it is important to understand the microscopic reduction mechanisms. Industrial hematite pellets are microstructurally intricate systems with inherent porosity, defects, and impurities. Therefore, in the present study we investigated the HyDR of single crystal hematite (at 700 °C) to elucidate the reduction behaviour and microstructure evolution in a model system. The reduction kinetics of the single crystal (SC) were compared to those of industrial polycrystalline porous pellets using thermogravimetric analysis. Additional SC samples were prepared such that their faces are parallel to the (0001), (101¯0) and (12¯10) crystallographic planes of hematite, and then partially reduced to 16 and 80 % reduction degree. Their microstructure was thoroughly examined by scanning electron microscopy and electron backscatter diffraction (EBSD). Reaction fronts were thus shown to advance into the hematite by a shrinking core model while creating a percolating pore network in the magnetite layer; this was closely followed by wüstite and iron formation, as well as pore coarsening, with the retained oxides proceeding to reduce homogenously throughout the sample abiding by the pore/grain models. Notably, a “cell-like” morphology develops in the magnetite near the hematite/magnetite interface, with finely porous “cell interiors” surrounded by coarsely porous “cell walls”. Furthermore, the hierarchal pore formation, phase transformations, texture, and orientation relationships are considered.

The co-reduction of metal oxide mixtures using hydrogen as a reductant in conjunction with compaction and sintering of the evolving metallic blends offers a promising alternative toward sustainable alloy production through a single, integrated, and synergistic process. Herein, we provide fundamental insights into hydrogen-based direct reduction (HyDR) of distinct oxide precursors that differ by phase composition and morphology. Specifically, we investigate the co-reduction of multicomponent metal oxides targeting a 25Co-25Fe-25Mn-25Ni (at.%) alloy, by using either a compacted powder (mechanically mixed oxides) comprising Co3O4-Fe2O3-Mn2O3-NiO or a pre-sintered compound (chemically mixed oxides) comprising Co,Ni-rich halite and Fe,Mn-rich spinel phases. Thermogravimetric analysis (TGA) at a heating rate of 10 °C/min reveals that the reduction onset temperature for the compacted powder was ∼175 °C, whereas it was significantly delayed to ∼525 °C for the pre-sintered sample. Nevertheless, both sample types attained a similar reduction degree (∼80 %) after isothermal holding for 1 h at 700 °C. Phase analysis and microstructural characterization of reduced samples confirmed the presence of metallic Co, Fe, and Ni alongside MnO. A minor fraction of Fe remains unreduced, stabilized in the (Fe,Mn)O halite phase, in accordance with thermodynamic calculations. Furthermore, ∼1 wt.% of BCC phase was found only in the reduced pre-sintered sample, owing to the different reduction pathways. The kinetics and thermodynamics effects were decoupled by performing HyDR experiments on pulverized pre-sintered samples. These findings demonstrate that initial precursor states influence both the reduction behavior and the microstructural evolution, providing critical insights for the sustainable production of multicomponent alloys.