Size-induced structural phase transitions and hyperfine properties of microcrystalline Fe₂O₃

Microcrystalline particles of Fe 2 O 3 having different sizes (varying between 70 and 5 nm) have been synthesised using a novel three-component micro-emulsion technique. A succession of crystal-size-induced structural transitions was observed. While alpha -Fe 2 O 3 was found to nucleate for a particle size above 30 nm, gamma -Fe 2 O 3 was preferentially formed for a size below 30 nm, whereas amorphous Fe 2 O 3 was formed at a particle size of 5 nm. These structural transformations have been related to the increase in the unit-cell volume that occurs as the particle size is decreased. The size dependence of the lattice parameter is shown to arise from a coupling of the surface energy to the dilatational lattice mode. A model Hamiltonian which incorporates this interaction and displays size-induced phase transitions is defined. The Mossbauer hyperfine field in the microcrystalline samples at 4.2 K was found to be substantially smaller than in the 'bulk'. The hyperfine parameters of the amorphous sample were found to be similar to those pertaining to samples prepared by conventional techniques such as melt quenching. A large anisotropy in the ionic vibrational amplitudes was detected in samples with particles smaller than about 10 nm.