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Structural and Mössbauer studies of nanocrystalline Mn2+-doped Fe3O4 particles


Nanocrystalline Mn2+-doped magnetite (Fe 3O4) particles of the composition Mn x Fe 3−y O4 \(\left (x = 0.0, 0.1, 0.2, 0.3, 0.4 \text { and } 0.5; y = \frac {2x}{3}\right )\), prepared using chemical precipitation under reflux with the Mn2+ ions substituting for Fe3+ ions rather than Fe2+ ones, are characterized mainly with XRD and 57Fe Mössbauer spectroscopy. All samples were found to have spinel-related structures with average lattice parameters that increase linearly with the Mn2+ concentration, x. The particle size for the samples varied from ∼8 nm to 23 nm. The oxidation of Fe2+ to Fe3+ at surface layers of the Fe 3O4 nanoparticles leading to the formation of maghemite (γ-Fe 2O3) was found to considerably weaken with increasing Mn2+ concentration. The percentage of the nanoparticles that exhibit short range magnetic ordering due to cationic clustering and/or superparamagnetism increases from 17% to 32% with increasing x. The dependence of isomer shifts of the 57Fe nuclei at the tetrahedral and octahedral sites on dopant Mn2+ concentration is emphasized. The electric quadrupole shifts indicate that the Mn x Fe 3−y O4 particles undergo Verwey transition. The effective hyperfine magnetic fields at both crystallographic sites decrease with increasing Mn2+ concentration reflecting a size effect as well as a weakening in the magnetic super-exchange interaction. The Mössbauer data indicate that for x ≤ 0.2, the dopant Mn2+ ions substitute solely for octahedral Fe3+ ions whereas for x > 0.2 they substitute for Fe3+ at both tetrahedral and octahedral sites.

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This research is supported by Sultan Qaboos University (Research Grant: SQU/Sci/Phys/04/16). KSA acknowledges the support of Sultan Qaboos University in the form of a PhD scholarship.

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Correspondence to H. M. Widatallah.

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This article is part of the Topical Collection on Proceedings of the International Conference on the Applications of the Mössbauer Effect (ICAME 2017), Saint-Petersburg, Russia, 3–8 September 2017.

Edited by Valentin Semenov

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Al-Rashdi, K.S., Widatallah, H.M., Al Ma’Mari, F. et al. Structural and Mössbauer studies of nanocrystalline Mn2+-doped Fe3O4 particles. Hyperfine Interact 239, 3 (2018).

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  • Magnetite
  • Maghemite
  • Doping
  • Defects
  • Nanocrystalline particles
  • Mössbauer spectroscopy
  • XRD