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Effect of Transition Metal Ion Doping on the Microstructure, Defect Evolution, and Magnetic and Magnetocaloric Properties of CuFeO2 Ceramics

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Abstract

The polycrystalline CuFeO2 (CFO) and CuFe1-xMxO2 (M = Ti, Hf, Zr, M-CFO) samples are synthesized by solid-state reaction method. The doping effect of tetravalent nonmagnetic transition metal M4+ ions on the microstructure, defect evolution, and magnetic and magnetocaloric properties of the CFO system are comparatively investigated. The substitution of M4+ for Fe3+ increases lattice parameters, changes the bond length of Fe/Cu-O and bond angle of Fe-O-Fe, and improves the microstructure to some extent. Positron annihilation spectroscopy results indicate that M4+ doping induces the agglomeration of small-sized vacancy defects manifested as the increase in vacancy-type defect size and the suppression of inherent defect concentration. Magnetic measurements show that the antiferromagnetic stability of CFO system is clearly affected by M4+ doping, and Ti4+ doping has a more noticeable impact than Hf4+ and Zr4+ doping. Meanwhile, the coexistence of weak ferromagnetism and antiferromagnetism is detected in all doped samples, while Ti-doped system exhibits extraordinary magnetic properties. Especially for Ti-CFO2 (x = 0.03) sample, the maximum magnetization reaches as high as 11.81 emu/g at 0.5 T, which enhanced one order of magnitude than that of undoped CFO. Isothermal M-H data at different temperatures show that entropy change (ΔSM) and refrigerant capacity (RC) for CFO and M-CFO2 samples are significantly weakening with M4+ substitution in bulk CFO. The maximum ΔSM = 4.79 J·kg−1 K−1 and RC = 12.79 J·kg−1 for undoped CFO are obtained near the transition temperature TN2 = 12 K, with the applied fields up to 6 T. The possible reasons for the above observations are discussed in detail.

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Funding

This work is supported by the National Natural Science Foundation of China (Project Nos. 11675149, 11775192).

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Authors and Affiliations

  1. School of Physics and Electronic Engineering, Zhengzhou University of Light Industry, Zhengzhou, 450002, China

    Mingsheng Xu, Haiyang Dai, Tao Li, Ke Peng, Jing Chen, Zhenping Chen & Yuncai Xue

  2. Multi-discipline Research Center, Institute of High Energy Physics (CAS), Beijing, 100049, China

    Xingzhong Cao & Baoyi Wang

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  1. Mingsheng Xu
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  2. Haiyang Dai
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Correspondence to Zhenping Chen.

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Xu, M., Dai, H., Li, T. et al. Effect of Transition Metal Ion Doping on the Microstructure, Defect Evolution, and Magnetic and Magnetocaloric Properties of CuFeO2 Ceramics. J Supercond Nov Magn 33, 2881–2890 (2020). https://doi.org/10.1007/s10948-020-05550-x

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