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Phase transitions, dielectric properties and valence of magnetic ions in PbFe0.5−x Cr x Nb0.5O3 multiferroic ceramics

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Abstract

Ceramic PbFe0.5−x Cr x Nb0.5O3 (x = 0.025, 0.05, 0.10, 0.15) perovskite solid solutions are synthesized using a solid-state reaction method. The samples of solid solutions are studied using the methods of X-ray diffraction, dielectric, Mössbauer and X-ray photoelectron spectroscopy, electron microscopy, and X-ray microanalysis. XRD studies have shown that the content of the parasitic pyrochlore phase increases dramatically with x, approaching 50% for x = 0.15. The averaged lattice parameter and the temperature of ferroelectric phase transition decrease monotonically with x. Concentration dependence of the magnetic phase transition temperature for PbFe0.5−x Cr x Nb0.5O3 is very similar to that in the Pb(Fe0.5Nb0.5)1−x M x O3 (M = Ti, Zr, Sn) solid solutions implying the lack of magnetic exchange between Fe3+ and Cr3+ ions. Bulk and surface elemental compositions are found to differ from each other and from nominal composition. XPS studies revealed that the PbFe0.5−x Cr x Nb0.5O3 (x = 0.05, 0.10) samples contain Cr3+, Cr4+, Cr5+, and Cr6+ ions. It is assumed that the presence of Cr5 + and Cr6+ ions is due to the formation of a small amount of non-perovskite phases, e.g., Pb 2+ n Cr6+O3+n and Fe3+Cr5+O4. This assumption is supported by the presence of weak reflections of the Pb2 2+Cr6+O5 phase in the XRD pattern of the composition with x = 0.15.

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Acknowledgements

This work was supported by the Ministry of Education and Science of the Russian Federation (Projects 3.6105.2017/8.9 and 3.5346.2017/8.9), and the Russian Foundation for Basic Research (Grant 16-52-00072 Bel_a).

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Authors and Affiliations

  1. Research Institute of Physics, Southern Federal University, 194 Stachki, Rostov-on-Don, Russia, 344090

    A. T. Kozakov, A. V. Nikolskii, I. P. Raevski, S. P. Kubrin, V. V. Titov, M. A. Malitskaya, I. N. Zakharchenko & S. I. Shevtsova

  2. Rostov State Transport University, 2 Narodnogo Opolcheniya, Rostov-on-Don, Russia, 344038

    A. G. Kochur

  3. Faculty of Physics, Southern Federal University, 5 Zorge, Rostov-on-Don, Russia, 344090

    I. P. Raevski & S. I. Raevskaya

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  1. A. T. Kozakov
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Kozakov, A.T., Kochur, A.G., Nikolskii, A.V. et al. Phase transitions, dielectric properties and valence of magnetic ions in PbFe0.5−x Cr x Nb0.5O3 multiferroic ceramics. J Mater Sci 52, 10140–10155 (2017). https://doi.org/10.1007/s10853-017-1234-z

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