Changes in the structural and magnetic properties of Ni?substituted hematite prepared from metal oxinates

Samples prepared by the novel method based on the thermal decomposition at 700 °C in air of mixed Fe and Ni oxinates were characterized by thermogravimetric analysis, X-ray diffraction, magnetization measurements, and variable-temperature Mossbauer spectroscopy. It is found that the combustion treatment produces Ni-hematite and trevorite, the fraction of the latter increasing with the increment of Ni in the metal oxinates. Results indicate that the substitution of Ni2+ for Fe3+ in the hematite structure, which was found to be less than 5.3 mol%, is accompanied by the presence of oxygen and structural vacancy sites. Both the metal replacement and the presence of defects cause the a and c cell hematite parameters to decrease. The Neel temperature and the difference between the saturation fields for the antiferromagnetic AF and the weakly ferromagnetic WF phases are also found to decrease with nickel content. These effects are due to the fact that the magnetic behavior of hematite depends on the presence of Ni, vacancy sites, and lattice distortion. The large decrease in the Neel temperature with Ni doping suggests that structural vacancies are also present On the contrary, Ni incorporation does not appreciably affect the Morin temperature and the temperature range in which both AF and WF phases coexist. It is suggested that these effects are probably due to the differing effects that Ni and defects can produce on the magnetic dipolar and the single ion anisotropies.