The Verwey transition in nanostructured magnetite produced by a combination of chimie douce and spark plasma sintering

Magnetite nanoparticles about 10 nm sized were synthesized by the polyol method. Zero-field-cooled (ZFC)-FC measurements showed a blocking temperature ∼170 K and the absence of the Verwey transition. They were subsequently consolidated by spark plasma sintering at 750 °C for 15 min, leading to a high density (92% of the theoretical density), solid body, with grains in the 150 nm range. X-ray diffraction patterns exhibited a spinel single phase with cell parameters corresponding to the magnetite structure. Magnetic measurements showed a decrease of coercivity from 685 Oe (54.5 kA/m) at 118 K to 90 Oe (7.2 kA/m) at 139 K. ZFC measurements at 25 Oe presented a three-fold magnetization increase as temperature increased; a small transition between 116 and 117.5 K, followed by a larger one from 117.6 to 124 K. The first transition can be associated with a complex crystallographic transition and delocalization of Fe²⁺-Fe³⁺, while the second one can be attributed to spin reorientation due to the magnetocrystalline anisotropy constant (K₁) change of sign as previously observed only in magnetite single crystals.