Cation distributions and magnetism of Al-substituted CoFe2O4 - NiFe2O4 solid solutions synthesized by sol-gel auto-combustion method

Aluminium substituted cobalt-nickel ferrite nanoparticles were synthesized by citrate gel auto-combustion method followed by annealing at 1000 degrees C for 1 h in air. Scanning electron micrographs of all the samples show crystalline particles of irregular morphology with a small variation in particle sizes (similar to 110-160 nm). From the analysis of the X-ray diffraction results we observed that the unit cell parameter decreases linearly with increase in aluminium concentration due to the smaller ionic radius of the Al3+ ions substituting the other cations such as Co2+, Ni2+ and Fe3+ ions in the compounds. The room temperature Mossbauer spectra of the samples show Zeeman split sextet patterns corresponding to the tetrahedral (Th) and octahedral (Oh) interstitial iron (Fe3+) cations. The observed magnetic hyperfine field (B-hf) decreases with increase in Al-concentration due to the distribution of diamagnetic Al3+ in the environment of Fe-57 probe atoms. The saturation magnetization measured by Vibrating Sample Magnetometer (VSM) shows a similar trend like that of Bhf. The distributions of the cations obtained from the Rietveld refinement and Mossbauer spectroscopy results indicate an increase in Fe3+(Th)/Fe3+ (Oh) occupancy-ratio on increasing Al3+ concentration, and Ni-2 cations prefer the octahedral site, whereas Co-2 and Al3+ ions redistribute themselves in tetrahedral and octahedral sites, in the ratio 2:3.