Microstructure and Properties of PIN-PZN-PZ-PT Piezoelectric Ceramics Designed by MPB Linear Rules

doi:10.15541/jim20250098

Abstract

Abstract: High-performance piezoelectric ceramics are indispensable in modern electromechanical systems, and multi-component materials like quaternary Pb(In₁_/₂Nb₁_/₂)O₃-Pb(Zn₁_/₃Nb₂_/₃)O₃-PbZrO₃-PbTiO₃ (PIN-PZN-PZ-PT) have attracted significant attention due to their unique properties at the morphotropic phase boundary (MPB). The aim of this study was to design and optimize the MPB compositions by precisely adjusting the PbTiO₃ (PT) content in order to achieve enhanced piezoelectric and thermal performance. To accomplish this, the ceramics were synthesized using a conventional solid-state reaction method, and the MPB compositions were initially predicted by employing a linear combination rule that accounts for the contributions of each component; the predicted phases were then confirmed by X-ray diffraction (XRD) analysis, followed by comprehensive electrical tests to measure the piezoelectric constant (d₃₃) and Curie temperature (T_C). Experimental results reveal that the MPB position is strongly influenced by the PT content: as the PT fraction increases, the rhombohedral phase gradually decreases while the tetragonal phase becomes predominant, thus shifting the phase equilibrium. Specifically, the optimal composition ranges were determined to be x = 0.245~0.265 for (1-x)(0.3PIN-0.6PZN-0.1PZ)-xPT, x = 0.290~0.330 for (1-x)(0.3PIN-0.5PZN-0.2PZ)-xPT, and x = 0.305~0.345 for (1-x)(0.3PIN-0.4PZN-0.3PZ)-xPT. Notably, the 0.735(0.3PIN-0.6PZN-0.1PZ)-0.265PT sample exhibited superior performance with a d₃₃ of 425 pC/N and a T_c of 253 ℃. These findings demonstrate that precise modulation of the PT content is crucial for controlling the phase balance at the MPB and thereby optimizing the piezoelectric properties. In conclusion, this study successfully identifies the optimal MPB compositions for PIN-PZN-PZ-PT ceramics, highlighting their promising potential for advanced piezoelectric applications and laying a solid foundation for future process improvements and long-term stability research.

Key words: morphotropic phase boundary, piezoelectric constant, Curie temperature, phase structure, perovskite

CLC Number:

TM282

XU Xiaoyu, ZHOU Liyang, FENG Xiaoying, WANG Hui, YAN Bin, XU Jie, GAO Feng. Microstructure and Properties of PIN-PZN-PZ-PT Piezoelectric Ceramics Designed by MPB Linear Rules[J]. Journal of Inorganic Materials, DOI: 10.15541/jim20250098.

References

[1] EITEL R E, RANDALL C A, SHROUT T R,et al. New high temperature morphotropic phase boundary piezoelectrics based on Bi(Me)O₃-PbTiO₃ ceramics. Journal of Applied Physics, 2001, 40(10): 5999.
[2] ZHANG S J, LEE S M, KIM D H,et al. Electromechanical properties of PMN-PZT piezoelectric single crystals near morphotropic phase boundary compositions. Journal of the American Ceramic Society, 2007, 90(12): 3859.
[3] LI F, ZHANG S J, YANG T N.The origin of ultrahigh piezoelectricity in relaxor-ferroelectric solid solution crystals.Nature Communications, 2016, 7: 13807.
[4] YAMAMOTO N, YAMASHITA Y, HOSONO Y,et al. Electrical and physical properties of repoled PMN-PT single crystal sliver transducer. Sens. Actuators A-Phys., 2013, 200(1): 16.
[5] WANG D, CAO M, ZHANG S J,et al. Phase diagram and properties of Pb(In_1/2Nb_1/2)O₃-Pb(Mg_1/3Nb_2/3)O₃-PbTiO₃ polycrystalline ceramics. Journal of the European Ceramic Society, 2012, 32(2): 433.
[6] WU J, CHANG Y F, YANG B,et al. Densification behavior and electrical properties of CuO-doped Pb(In_1/2Nb_1/2)O₃-Pb(Mg_1/3Nb_2/3)O₃-PbTiO₃ ternary ceramics. Ceramics International, 2016, 42(6): 7223.
[7] RAMESH G, RAMACHANDRA M S, SIVASUBRAMANIAN V, ,et al. Electrocaloric effect in. Electrocaloric effect in (1-x)PIN-xPT relaxor ferroelectrics. Journal of Alloys Compounds, 2016, 663: 444.
[8] RAMESSH G, RAMACHANDRA M S, SIVASUBRAMANIAN V,et al. Electrocaloric effect in (1-x)PIN-xPT relaxor ferroelectrics. Journal of Alloys Compounds, 2016, 663: 444.
[9] QI X D, SUN E W, WANG J J,et al. Electromechanical properties of Mn-doped Pb(In_1/2Nb_1/2)O₃-Pb(Mg_1/3Nb_2/3)O₃-PbTiO₃ piezoelectric ceramics. Ceramics International, 2016, 42(14): 15332.
[10] LUO N, ZHANG S J, QIANG L,et al. New Pb(Mg_1/3Nb_2/3)O₃-Pb(In_1/2Nb_1/2)O₃-PbZrO₃-PbTiO₃ quaternary ceramics: morphotropic phase boundary design and electrical properties. ACS Applied Materials & Interfaces, 2016, 8(24): 15506.
[11] LI C C, XU B, LIN D B.Atomic-scale origin of ultrahigh piezoelectricity in samarium-doped PMN-PT ceramics.Physical Review B, 2020, 101(14): 140102.
[12] FENG X Y, LIU J T, GAO F,et al. Effect of sintering atmosphere on the microstructure and electrical properties of Pb(Zr_1/2Ti_1/2)O₃-Pb(Zn_1/3Nb_2/3)O₃-Pb(Ni_1/3Nb_2/3)O₃ ceramics. Journal of Materials Science: Materials in Electronics, 2022, 33: 11613.
[13] FENG X Y, LI L L, XU X Y,et al. Microstructure evolution and properties of textured, Pb(Zr_1/2Ti_1/2)O₃-Pb(Zn_1/3Nb_2/3)O₃-Pb(Ni_1/3Nb_2/3)O₃ ceramics with plate-like BaZr_0.1Ti_0.9O₃ template. Journal of Alloys and Compounds, 2024, 1002: 175439.
[14] LI F, ZHANG S J, XU Z.Piezoelectricity-an important property for ferroelectrics during last 100 years.Acta Physica Sinica, 2020, 69(21): 217703.
[15] XU X Y, FENG X Y, GAO F,et al. Phase structure and electrical properties of 0.28PIN-0.32PZN-(0.4-x)PT-xPZ piezoelectric ceramics. Crystals, 2023, 13(9): 1362.
[16] LIM J B, ZHANG S J, SHROUT T R. Modified Pb(Yb,Nb)O₃-PbZrO₃-PbTiO₃ ternary system for high temperature applications.Ceramics International, 2012, 38(1): 277.
[17] YOO J Y, LEE S H, LEE K S.Piezoelectric and dielectric properties of low temperature sintering Pb(Zn_1/2W_1/2)O₃-Pb(Mn_1/3Nb_2/3)O₃-Pb(Zr,Ti)O₃ ceramics.Transactions on Electrical and Electronic Materials, 2008, 9(3): 91.
[18] GUO Q H, LI F, XIA F Q,et al. Piezoelectric ceramics with high piezoelectricity and broad temperature usage range. Journal of Materiomics, 2021, 7: 683.
[19] WANG P B, GUO Q H, LI F,et al. Pb(In_1/2Nb_1/2)O₃-PbZrO₃-PbTiO₃ ternary ceramics with temperature-insensitive and superior piezoelectric property. Journal of European Ceramic Society, 2022, 42: 3848.
[20] WEI D D, HUANG H.Low-temperature sintering and enhanced piezoelectric properties of random and textured PIN-PMN-PT ceramics with Li₂CO₃.Journal of the American Ceramic Society, 2017, 100(3): 1073.
[21] LIN D, ZHANG S J, GORZKOWSKI E,et al. Investigation of morphotropic phase boundaries in PIN-PSN-PT relaxor ferroelectric ternary systems with high Tr-t and Tc phase transition temperatures. Journal of the European Ceramic Society, 2017, 37(8): 2813.