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Abstract:
Based on the crystal structure of spinel, we applied the thermodynamic ternary sublattices model to investigate the site occupancy ordering behaviors of Zn 2+ , Ni 2+ , Mn 2+ and Fe 3+ on the 8a and 16d sublattices in the Zn x Mn 1-x Fe 2 O 4 and NixMn 1-x Fe 2 O 4 by combining thermodynamic calculations with first-principles calculations. Our results suggest that in the manganese ferrites, Mn 2+ occupies the 8a sublattice completely, and Fe 3+ occupies the 16d sublattice at room temperature, which belongs to a normal spinel. The site configuration is (Fe 3+ 1.91 Mn 2+ 0.09 ) [Fe 3+ 1.91 Mn 2+ 0.09 ]O 4 , when the ferrite is subjected to the heat treatment of 1 273 K. When the temperature increases to 1 473 K, the site configuration is (Fe 3+ 0, 11 Mn 2+ 0.89 [Fe 3+ 1.89 Mn 2+ 0.11 ]O 4 , which agrees well with the available reliable experimental results. In the zinc ferrites, Zn 2+ occupies the 8a sublattice completely, and Fe 3+ completely occupies the 16d sublattice at room temperature. It also belongs to normal spinel, and the cations trend to exchange the site occupancy each other at higher temperature. In the Ni ferrites, all Ni 2+ occupies the 16d sublattice, and the Fe 3+ cations occupy both the 8a and the 16d sublattices, which agrees with the experimental results. It belongs to an inverse spinel. Then, the relationship between the occupancy behaviors and the composition, as well as the heat treatment temperature in the Zn x Mn 1-x Fe 2 O 4 and Ni X Mn 1-x XFe 2 O 4 were established based on theoretically predictions. © 2017, Chinese Chemical Society. All rights reserved.
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Chinese Journal of Inorganic Chemistry
ISSN: 1001-4861
Year: 2017
Issue: 3
Volume: 32
Page: 377-385
0 . 6 5 4
JCR@2017
0 . 8 0 0
JCR@2023
ESI HC Threshold:226
JCR Journal Grade:4
CAS Journal Grade:4
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ESI Highly Cited Papers on the List: 0 Unfold All
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30 Days PV: 7
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