Complexions at the Iron-Magnetite Interface (2408.09213v2)

Abstract: Synthesizing distinct phases and controlling the crystalline defects in them are key concepts in materials and process design. These approaches are usually described by decoupled theories, with the former resting on equilibrium thermodynamics and the latter on nonequilibrium kinetics. By combining them into a holistic form of defect phase diagrams, we can apply phase equilibrium models to the thermodynamic evaluation of defects such as vacancies, dislocations, surfaces, grain boundaries, and phase boundaries, placing the understanding of material imperfections and their role on properties on solid thermodynamic and theoretical grounds. In this study, we characterize an interface-stabilized phase between Fe and Fe3O4 (magnetite) with differential phase contrast (DPC) imaging in scanning transmission electron microscopy (STEM). This method uniquely enables the simultaneous imaging of both heavy Fe atoms and light O atoms, providing precise mapping of the atomic structure and chemical composition at this heterogeneous metal-oxide interface. We identify a well-ordered two-layer interface-stabilized phase state (referred to as complexion) at the Fe[001]/Fe3O4[001] interface. Using density-functional theory (DFT), we not only explain the observed complexion but also map out various interface-stabilized phases as a function of the O chemical potential. We show that the formation of complexions influences the properties of the interface, increasing its adhesion by 20 % and changing the charge transfer between adjacent materials, also leveraging impact on the transport properties across such interfaces. Our findings highlight the potential of tunable phase states at defects as a new asset in advanced materials design, paving the way for knowledge-based and optimized corrosion protection, catalysis, magnetism, and redox-driven phase transitions.