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Enhanced electrical properties and large electrocaloric effect in lead-free Ba0.8Ca0.2ZrxTi1−xO3 (x = 0 and 0.02) ceramics

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Abstract

The effects of 2% Zr introduction in Ba0.8Ca0.2TiO3 (BCT) system on its electrical and electrocaloric properties was investigated. BCT and Ba0.8Ca0.2Zr0.02Ti0.98O3 (BCZT) ceramics synthesized by solid-state processing were crystallized in a pure perovskite phase with a group space P4mm. After Zr insertion, the enhanced dielectric constant was obtained around the Curie temperature (Tc) in BCZT ceramic (εr = 6330 at Tc = 388 K) compared to BCT ceramic (εr = 5080 at Tc = 388.6 K). Moreover, the large-signal piezoelectric coefficient \((d_{33}^{*} )\) was improved from 270 to 310 pm/V in BCT and BCZT ceramics, respectively, under a moderate electric field of 25 kV/cm. The electrocaloric effect was determined via indirect and direct methods. In the indirect approach, the electrocaloric temperature change (ΔT) was calculated via Maxwell relation, and the measured ferroelectric polarization P (E, T) extracted from the P–E curves recorded at 24 kV/cm. The maximum values of ΔT = 0.68 K and the electrocaloric responsivity ζ = 0.283 K mm/kV obtained at 385 K in BCZT ceramic were found to be higher than those observed in BCT ceramic (ΔT = 0.37 K and ζ = 0.154 K mm/kV at 387 K). In the direct approach, ΔT was measured utilizing a modified high-resolution calorimeter at 14 kV/cm. As the direct method is more sensitive to the latent heat, it provided larger values for smaller applied field, i.e., ΔT = 0.474 and 0.668 K for BCT and BCZT ceramics, respectively. A significant ζ of 0.477 K mm/kV was obtained in BCZT at 385 K and 14 kV/cm that matches the values found in lead-based materials. These results suggest that BCZT lead-free ceramics could have an excellent potential to be used in solid-state refrigeration applications.

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Acknowledgements

The authors gratefully acknowledge the generous financial support of CNRST Priority Program PPR 15/2015, the Slovenian research agency grants P1-0125, J1-9147, and the European Union’s Horizon 2020 Research and Innovation Program under the Marie Skłodowska-Curie Grant Agreement No. 778072.

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Authors and Affiliations

  1. IMED-Lab, Cadi Ayyad University, 40000, Marrakesh, Morocco

    Soukaina Merselmiz, Zouhair Hanani, Said Ben Moumen, Daoud Mezzane, Zahra Abkhar, Lahoucine Hajji & M’barek Amjoud

  2. ICMCB, University of Bordeaux, 33600, Pessac, France

    Zouhair Hanani

  3. Jozef Stefan Institute, 1000, Ljubljana, Slovenia

    Aleksander Matavž, Nikola Novak, Dejvid Črešnar, Zdravko Kutnjak & Brigita Rožič

  4. LPMC, University of Picardy Jules Verne, 80039, Amiens, France

    Yaovi Gagou

  5. IM2NP, Aix-Marseille University, UMR 7334, 13397, Marseille, France

    Khalid Hoummada

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  1. Soukaina Merselmiz
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Merselmiz, S., Hanani, Z., Ben Moumen, S. et al. Enhanced electrical properties and large electrocaloric effect in lead-free Ba0.8Ca0.2ZrxTi1−xO3 (x = 0 and 0.02) ceramics. J Mater Sci: Mater Electron 31, 17018–17028 (2020). https://doi.org/10.1007/s10854-020-04259-w

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