Phase diagram and properties of Pb(In1/2Nb1/2)O3–Pb(Mg1/3Nb2/3)O3–PbTiO3 polycrystalline ceramics

doi:10.1016/j.jeurceramsoc.2011.08.025

Journal of the European Ceramic Society

Volume 32, Issue 2, February 2012, Pages 433-439

https://doi.org/10.1016/j.jeurceramsoc.2011.08.025 Get rights and content

Abstract

yPb(In_1/2Nb_1/2)O₃–(1 − x − y)Pb(Mg_1/3Nb_2/3)O₃–xPbTiO₃ (yPIN–(1 − x − y)PMN–xPT) polycrystalline ceramics with morphotropic phase boundary (MPB) compositions were synthesized using columbite precursor method. X-ray diffraction results indicated that the MPB of PIN–PMN–PT was located around PT = 0.33–0.36, confirmed by their respective dielectric, piezoelectric and electromechanical properties. The optimum properties were found for the MPB composition 0.36PIN–0.30PMN–0.34PT, with dielectric permittivity ɛ_r of 2970, piezoelectric coefficient d₃₃ of 450 pC/N, planar electromechanical coupling k_p of 49%, remanent polarization P_r of 31.6 μC/cm² and T_C of 245 °C. According to the results of dielectric and pyroelectric measurements, the Curie temperature T_C and rhombohedral to tetragonal phase transition temperature T_R–T were obtained, and the “flat” MPB for PIN–PMN–PT was achieved, indicating that the strongly curved MPB in PMN–PT system was improved by adding PIN component, offering the possibility to grow single crystals with high electromechanical properties and expanded temperature usage range (limited by T_R–T).

Introduction

Relaxor-PbTiO₃ (PT) based single crystals, such as Pb(Mg_1/3Nb_2/3)O₃–PbTiO₃ (PMN–PT) and Pb(Zn_1/3Nb_2/3)O₃–PbTiO₃ (PZN–PT), were found to possess extra high electromechanical coupling factor (k₃₃ > 0.9) and piezoelectric coefficient (d₃₃ > 1500 pC/N) that far out perform polycrystalline PZT-based ceramics (k₃₃ ∼0.7 and d₃₃ ∼400–600 pC/N), making them promising candidates for medical ultrasonic imaging, sonar transducers, and solid-state actuators.1, 2, 3 Although relaxor-PT based single crystals have excellent piezoelectric and electromechanical properties, their relatively low Curie temperature (T_C ∼130–170 °C) becomes a critical limitation for applications, where the thermal stability is required, in terms of dielectric and piezoelectric property variations and depolarization as a result of post-fabrication process in transducers.³ Their usage temperature ranges are further restricted by ferroelectric rhombohedral to ferroelectric tetragonal phase transition (T_R–T ∼60–95 °C), occurring at significantly lower temperatures due to the strongly curved morphotropic phase boundary (MPB).3, 4, 5

A broader temperature operating range would allow for greater device design flexibility and therefore a wider range of potential applications. Thus, new piezoelectric single crystal compositions, which will be able to operate at higher temperature than current state-of-the-art PMN–PT/PZN–PT single crystals, are desirable.⁶ In order to find the possibility of single crystals for the next generation of transduction devices, numerous studies are focused on exploring new high performance ferroelectric systems with higher T_C/T_R–T over the past few years.7, 8, 9, 10

Perovskite Pb(In_1/2Nb_1/2)O₃ (PIN) is a typical relaxor ferroelectric material with a T_C of about 90 °C. The solid solution of the PIN–PT binary system exhibits a MPB near 37 mol% PT, where high piezoelectric and dielectric properties can be obtained. The Curie temperature of PIN–PT with MPB composition is about 320 °C, much higher than that of PMN–PT.¹¹ Consequently, it is promising to improve the T_C/T_R–T of PMN–PT system by adding PIN component. Recently, the new relaxor-PT based ternary single crystal system Pb(In_1/2Nb_1/2)O₃–Pb(Mg_1/3Nb_2/3)O₃–PbTiO₃ (PIN–PMN–PT) was reported to possess higher T_C > 170 °C and T_R–T > 120 °C, and comparable piezoelectric properties to the binary crystal systems PMN–PT, indicating that PIN–PMN–PT crystals are promising candidates for electromechanical devices where high temperature usage and thermal stability are required.12, 13, 14 However, studies of PIN–PMN–PT system have been focused on the PIN in the range of 0.23–0.35, with T_R–T less than 135 °C, T_C/T_R–T of PIN–PMN–PT are needed to be further improved to satisfy practical applications for higher temperature range. Thus, it is necessary to investigate the PIN–PMN–PT ternary system with higher PIN content level.

In this work, in order to obtain higher T_C/T_R–T in PIN–PMN–PT ternary system, PIN–PMN–PT ceramics with high PIN content were synthesized using columbite precursor method. Dielectric- and pyroelectric-temperature measurements were used to determine the T_C/T_R–T. Phase structure, dielectric, piezoelectric and ferroelectric properties of PIN–PMN–PT ceramics were studied in detail.

Section snippets

Experimental

The PIN–PMN–PT ternary ceramics with compositions of yPb(In_1/2Nb_1/2)O₃–(1 − x − y)Pb(Mg_1/3Nb_2/3)O₃–xPbTiO₃ (yPIN–(1 − x − y)PMN–xPT, x = 0.28–0.37 and y = 0.36, 0.46) were prepared using two-step columbite precursor method.11, 15, 16, 17 The studied compositions are shown in Fig. 1. Raw materials of MgCO₃ (99.9%, Alfa Aesar, Ward Hill, MA), Nb₂O₅ (99.9%, Alfa Aesar) and In₂O₃ (99.9%, Alfa Aesar) were used to synthesize columbite precursors of MgNb₂O₆ and InNbO₄ at 1000 °C and 1100 °C, respectively. Pb₃O₄

Results and discussion

XRD patterns of the studied compositions for yPIN–(1 − x − y)PMN–xPT are shown in Fig. 2. All the samples were found to be pure perovskite except the compositions with 0.36PIN, where small peaks of pyrochlore phase were indicated in Fig. 2(a). The typical tetragonal phase symmetry for perovskite at room temperature is characterized by (2 0 0) peak splitting around 2θ = 45°, which was used to determine the MPB compositions, separating rhombohedral and tetragonal phases.21, 22 It was found that with

Conclusions

In conclusion, PIN–PMN–PT ternary ceramics with MPB compositions were prepared using two-step columbite precursor method. Phase structure, dielectric, piezoelectric and ferroelectric properties were investigated. The optimum properties were found for the MPB composition 0.36PIN–0.30PMN–0.34PT, with d₃₃ of 450 pC/N, k_p of 49%, Q_m of 130, ɛ_r of 2970, tanδ of 1.1%, P_r of 31.6 μC/cm², E_C of 9.8 kV/cm and T_C of 245 °C. According to the dielectric- and pyroelectric-temperature measurements, the T_C/T_R–T

Acknowledgements

The authors thank Prof. Thomas R. Shrout for the helpful discussion. Authors from Beijing Institute of Technology acknowledge the National Natural Science Foundation of China under Grant Nos. 50742007, 50872159 and 50972014, and the National High Technology Research and Development Program of China under Grant No. 2007AA03Z103. The author (D.W. Wang) wishes to acknowledge the support from the China Scholarship Council. The work was supported by ONR.

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Phase diagram and properties of Pb(In1/2Nb1/2)O3–Pb(Mg1/3Nb2/3)O3–PbTiO3 polycrystalline ceramics

Abstract

Introduction

Section snippets

Experimental

Results and discussion

Conclusions

Acknowledgements

Solid State Commun

J Cryst Growth

J Alloys Compd

Ultrasonics

Mater Res Bull

J Alloys Compd

J Alloys Compd

Characteristics of relaxor-based piezoelectric single crystals for ultrasonic transducers

IEEE Trans Ultrasonics Ferroelectr Frequency Control

Ultrahigh strain and piezoelectric behavior in relaxor based ferroelectric single crystals

J Appl Phys

Relaxor-PT single crystals: observations and developments

IEEE Trans Ultrasonics Ferroelectr Frequency Control

Electric-field, temperature, and stress-induced phase transitions in relaxor ferroelectric single crystals

Phys Rev B

Characterization of Pb(In1/2Nb1/2)O3–Pb(Mg1/3Nb2/3)O3–PbTiO3 ferroelectric crystal with enhanced phase transition temperatures

J Appl Phys

Characterization of perovskite piezoelectric single crystals of 0.43BiScO3–0.57PbTiO3 with high Curie temperature

J Appl Phys

Phase diagram and properties of Pb(In_1/2Nb_1/2)O₃–Pb(Mg_1/3Nb_2/3)O₃–PbTiO₃ polycrystalline ceramics

Characterization of Pb(In_1/2Nb_1/2)O₃–Pb(Mg_1/3Nb_2/3)O₃–PbTiO₃ ferroelectric crystal with enhanced phase transition temperatures

Characterization of perovskite piezoelectric single crystals of 0.43BiScO₃–0.57PbTiO₃ with high Curie temperature