Morin transition in hematite: Size dependence and thermal hysteresis

Hematite is a frequently used mineral in paleomagnetic and environmental magnetic studies. Just below room temperature, it undergoes a magnetic phase transition, the Morin transition, whose nature is an important part of our basic understanding of hematite's magnetism and magnetic memory. We have determined the temperature T-M of the Morin transition from saturation remanence warming curves to be 250-261 K for 0.5-6 mm hematite natural single crystals, 257-260 K for 45-600 mu m sieved crystal fractions, and 241-256 K for submicron synthetic hematites with grain sizes between 120 and 520 nm. The variation must be due to differences in crystal morphology, lattice strain, and crystal defects common in both synthetic and natural crystals. Our results are compatible with published data for 100 nm to 10 mm hematites and show that TM is nearly size independent, decreasing very gradually as particle size decreases over this broad range, which includes both multidomain (MD) and single-domain (SD) structures. However, TM decreases sharply between 90 and 30 nm. Below 20 nm, the transition disappears entirely as near-surface spins deviate strongly from the antiferromagnetic easy axis. Our SD and MD hematites exhibit a thermal hysteresis in the Morin transition: the values of TM in cooling and in heating are different. For the same cooling/warming rate, Delta T-M is much greater for submicron hematites than for larger crystals. We attribute the lag in the transition in both cooling and heating to crystal imperfections and resulting internal stresses, and speculate that defects may serve to pin and stabilize surface spins. Preventing spin rotation in a region large enough to trigger the phase transition would inhibit destabilization of the weakly ferromagnetic phase in cooling and the antiferromagnetic phase in heating. The wide distribution of particle sizes in our submicron samples may also play a role.