Single-phase formation mechanism and dielectric properties of sol-gel-derived Ba(Ti0.2Zr0.2Sn0.2Hf0.2Ce0.2)O3 high-entropy ceramics

doi:10.1016/j.jmst.2022.05.012

Abstract

Abstract:

Single-phase Ba(Ti_0.2Zr_0.2Sn_0.2Hf_0.2Ce_0.2)O₃ (BTZSHC) high-entropy ceramics (HECs) with the perovskite structure were successfully prepared via the sol-gel method. The results reveal that the as-prepared ceramics exhibit a single cubic phase belonging to the Pm$\bar{3}$m space group. The high entropy is the driving force of the formation of single-phase ceramics. A larger entropy (ΔS_mix) and a negative enthalpy (ΔH_mix) are conducive to the formation of single-phase compounds. Herein, ΔS_mix = 0.323R mole^–1 and ΔH_mix = −43.88 kJ/mol. The sluggish-diffusion effect ensures the thermal stability of high-entropy systems. Dielectric measurements reveal that the as-prepared BTZSHC high-entropy ceramics are relaxor ferroelectrics, and the degree of relaxor (γ) is 1.9. The relaxor behavior of the as-prepared ceramics can be ascribed to the relaxation and thermal evolution of their polar units (PUs). The findings of this work provide a theoretical basis and technical support for the preparation of single-phase high-entropy ceramics.

Key words: High-entropy ceramics, Single-phase formation mechanism, Perovskite structure, Sol-gel method, Dielectric properties

Jia Liu, Cuiying Ma, Lianli Wang, Ke Ren, Hongpei Ran, Danni Feng, Huiling Du, Yiguang Wang. Single-phase formation mechanism and dielectric properties of sol-gel-derived Ba(Ti_0.2Zr_0.2Sn_0.2Hf_0.2Ce_0.2)O₃ high-entropy ceramics[J]. J. Mater. Sci. Technol., 2022, 130: 103-111.

Figures/Tables 8

Fig. 1. FTIR absorption spectrum and TG-DSC curve of the BTZSHC xerogel: (a) FTIR absorption spectrum and (b) TG-DSC curve.

Fig. 2. Phase evolution of the BTZSHC high-entropy ceramics: (a) XRD patterns of the BTZSHC high-entropy ceramics after calcination at 600, 800, 900, 1000, 1100, and 1200 °C for 2 h; (b) magnified patterns in the range from 25° to 35°.

Fig. 3. Phase structure of the BTZSHC ceramic powders after calcination at 1200 °C for 2 h: (a) XRD pattern; (b) magnified pattern in the range from 40° to 46°; (c) refined XRD data.

Table 1. The ionic radii of Ba2+, Ti4+, Zr4+, Sn4+, Hf4+, Ce4+, and O2-.

Ion	Ba²⁺	Ti⁴⁺	Zr⁴⁺	Sn⁴⁺	Hf⁴⁺	Ce⁴⁺	O^2-
Ionoic radius (Å)	1.61	0.605	0.72	0.69	0.71	0.87	1.4

Fig. 4. Microstructure and elemental distribution of the BTZSHC ceramic powders after calcination at 1200 °C for 2 h: (a) HRTEM image, (b) SAED pattern, and (c) EDS elemental maps.

Fig. 5. Phase stability of the BTZSHC high-entropy ceramics: (a) XRD patterns of the BTZSHC ceramic powders after annealing at 800, 900, 1000, 1100, and 1200 °C for 4 h and quenching in the air; (b) magnified patterns in the range from 40° to 48°.

Fig. 6. Morphology and elemental distribution of the dense BTZSHC high-entropy ceramics: (a) surface morphology, (b) high-magnification morphology of the area surrounded by the rectangle in (a), and (c) EDS elemental maps.

Fig. 7. Dielectric properties of the BTZSHC high-entropy ceramics: (a) dielectric constant of the as-sintered BTZSHC ceramics as a function of temperature in the frequency range from 1 kHz to 1 MHz; (b) fitted ln(1/εr ? 1/εm) vs ln(T ? Tm) curve.

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Single-phase formation mechanism and dielectric properties of sol-gel-derived Ba(Ti_0.2Zr_0.2Sn_0.2Hf_0.2Ce_0.2)O₃ high-entropy ceramics

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