Hydrostatic pressure-induced reversible phase transformation in iron oxide nanoparticles†

We report hydrostatic pressure-induced reversible phase transformation in maghemite γ-Fe₂O₃ nanoparticles (cubic → tetragonal → cubic) using an in situ diamond anvil cell (DAC) technique. Thermal arc plasma-synthesized nanoparticles, particularly in a He gas medium, exhibit the reversible phase transformation under pressure ranging from 0 to 2.58 GPa. Rietveld refinement reflects that cubic to tetragonal maghemite phase transformation coexists with a cubic metallic Fe phase at 0.55 GPa pressure. The generation of two new superlattice reflections at 6.93° and 8.11°, respectively, reflects the phase transformation. The presence of a core–shell-type nanostructure observed from transmission electron microscopy micrographs is found to exhibit a spin glass shell-type behavior. This triggers pressure-induced fluctuating magnetization and interparticle interaction-induced surface anisotropy and spin disorder with broken bonds, translational symmetry, and incomplete coordination. This leads to overcoming the nucleation barrier at the surface, subsequently denser nucleation sites and increased nucleation probability. This further leads to an atomic rearrangement and tetragonality in the maghemite phase. Furthermore, with increasing pressure, the reversible structural change, i.e. from the tetragonal to cubic maghemite phase, has been explained in the light of the “internal stress model”. The grains are again forced back to the cubic phase via generation of uniform compression along the c-axis and tension along the a and b axes. The spin glass behavior of the core–shell nanostructure along with the “internal stress model” explain the whole reversible phase transformation phenomenon in the γ-Fe₂O₃ phase.