Preparation and characterization of Pb(Lu1/2Nb1/2)O3–Pb(In1/2Nb1/2)O3–PbTiO3 ternary ferroelectric ceramics with high phase transition temperatures

To explore new relaxor‐PbTiO₃ systems for high‐power and high‐temperature electromechanical applications, a ternary ferroelectric ceramic system of Pb(Lu_1/2Nb_1/2)O₃–Pb(In_1/2Nb_1/2)O₃–PbTiO₃ (PLN–PIN–PT) have been investigated. The phase structure, dielectric, piezoelectric, and ferroelectric properties of the as‐prepared PLN–PIN–PT ceramics near the morphotropic phase boundary (MPB) were characterized. A high rhombohedral‐tetragonal phase transition temperature T_R‐T of 165°C and a high Curie temperature T_C of 345°C, together with a good piezoelectric coefficient d₃₃ of 420 pC/N, were obtained in 0.38PLN–0.20PIN–0.42PT ceramics. Furthermore, for (0.8?x)PLN–0.2PIN–xPT ceramics, the temperature‐dependent piezoelectric coefficients, coercive fields and electric‐field‐induced strains were further studied. At 175°C, their coercive fields were found to be above 9.5 kV/cm, which is higher than that of PMN–PT and soft P5H ceramics at room temperature, indicating PLN–PIN–PT ceramics to be one of the promising candidates in piezoelectric applications under high‐driven fields. The results presented here could benefit the development of relaxor‐PbTiO₃ with enhanced phase transition temperatures and coercive fields.     

High‐Performance Ferroelectric Solid Solution Crystals: Pb(In1/2Nb1/2)O3–Pb(Zn1/3Nb2/3)O3–PbTiO3

A series of regular shaped Pb(Zn_1/3Nb_2/3)O₃‐based ternary ferroelectric single crystals (1 ? x)Pb(In_1/2Nb_1/2)O₃–0.33Pb(Zn_1/3Nb_2/3)O₃–xPbTiO₃ (PIN–PZN–PT) have been grown by means of the top‐seeded solution growth method that prevented pyrochlore phase and promoted [001] or [111] growth. The nucleation and crystallization behavior of the Pb(Zn_1/3Nb_2/3)O₃‐based ferroelectric single crystals differed from other relaxor‐based ferroelectric single crystals was discovered. Di‐/piezo‐/ferro‐/pyroelectric properties were characterized systematically. The PIN–PZN–PT single crystals showed large coercive fields E_c, high Curie temperature T_C and high pyroelectric coefficient P, presenting similar performance but better thermal stability compared with the PZN–PT single crystals, and making it a promising material for transducers and IR detectors in a wider temperature range.     

The Charge Release and Its Mechanism for Pb(In1/2Nb1/2)–Pb(Mg1/3Nb2/3)–PbTiO3 Ferroelectric Crystals Under One‐Dimensional Shock Wave Compression

The charge release and related mechanisms for Pb(In_1/2Nb_1/2)–Pb(Mg_1/3Nb_2/3)–PbTiO₃ (PIN–PMN–PT) ferroelectric crystals under one‐dimensional shock wave compression were investigated using discharge current profile measurement, by which the piezoelectric stress coefficient e₃₁ and the phase transition (from tetragonal to orthorhombic phase) pressure were obtained, being ?2.9 C/m² and 2.3 GPa, respectively. Based on experiment results and thermodynamics analysis, it was found that the one‐dimensional shock compression favored ferroelectric phase, being different from the effect of hydrostatic pressure, which favored paraelectric phase. This phenomenon can be attributed to the crystal anisotropy and electromechanical coupling effects as one‐dimensional shock compression is applied to PIN–PMN–PT ferroelectric crystals.     

Phase Diagram and Properties of High TC/TR−T Pb(In1/2Nb1/2) O3–Pb(Zn1/3Nb2/3)O3–PbTiO3 Ferroelectric Ceramics

A ternary ferroelectric ceramic system, (1?x?y)Pb(In_1/2Nb_1/2)O₃–xPb(Zn_1/3Nb_2/3)O₃–yPbTiO₃ (PIN–PZN–PT, x = 0.21, 0.27, 0.36, 0.42), was prepared using a two‐step precursor method. The phase structure, dielectric, piezoelectric, and ferroelectric properties of the ternary ceramics were systematically investigated. A morphotropic phase boundary (MPB) was identified by X‐ray diffraction. The optimum piezoelectric and electromechanical properties were achieved for a composition close to MPB (0.5PIN–0.21PZN–0.29PT), where the piezoelectric coefficient d₃₃, planar electromechanical coupling factor k_p, and remnant polarization P_r are 660 pC/N,72%, and 45 μC/cm², respectively. The Curie temperature T_C and rhombohedral to tetragonal phase transition temperature T_R?T were also derived by temperature dependence of dielectric measurements. The strongly “bended” MPB in the PIN–PT system was found to be “flattened” after addition of PZN in the PIN–PT–PZN system. The results demonstrate a possibility of growing ferroelectric single crystals with high electromechanical properties and expanded range of application temperature.     

Structural Evolution and Properties of 0.3Pb(In1/2Nb1/2)O3–0.38Pb(Mg1/3Nb2/3)O3–0.32PbTiO3 Ferroelectric Ceramics with Different Sintering Times

The structural evolution and properties of 0.3Pb(In_1/2Nb_1/2)O₃–0.38Pb(Mg_1/3Nb_2/3)O₃–0.32PbTiO₃ (0.3PIN‐0.38PMN‐0.32PT) ferroelectric ceramics with different sintering times have been investigated. The content of the tetragonal phase is increased in samples sintered for more than 6 h, despite that the composition falls in the rhombohedral region of the previously established phase diagram. The results show that the metastable tetragonal phase at room temperature is induced and stabilized by the tensile residual stresses. Excessively long sintering time generally leads to grain coarsening, loss of lead, and deterioration of properties, while the increasing amount of the tetragonal phase, and the large residual tensile stress appear to improve the dielectric and electromechanical properties. This study offers new insights into the sintering of Pb‐based ferroelectric ceramics with complex compositions.     

ZnO-activated formation of phase pure perovskite Pb(In1/2Nb1/2)O3-Pb(Zn1/3Nb2/3)O3-PbTiO3 powder

This paper reports on the phase formation of perovskite Pb(In_1/2Nb_1/2)O₃-Pb(Zn_1/3Nb_2/3)O₃-PbTiO₃ (PIN-PZN-PT) powder when doped with 0.04 to 0.83 mol% ZnO. Air calcination of undoped powder mixtures for 4 hours at 800°C resulted in a mixture of Pb₂Zn_0.29Nb_1.71O_6.565 pyrochlore, PIN-PZN-PT perovskite, and In₂O₃. ZnO dopant concentrations as low as 0.04 mol% increased the rate of perovskite formation and resulted in near phase pure perovskite powder of 0.5 μm particle size when heated at 800°C in air. In all cases PbTiO₃ and Pb(In_1/2Nb_1/2)O₃ formed prior to PIN-PZN-PT formation. ZnO doping promotes perovskite phase formation by increasing the reactivity of the intermediate pyrochlore phase by substituting Zn²⁺ on Nb⁵⁺ sites and forming oxygen vacancies when heated in air. Heating in high resulted in an incomplete reaction and a mixture of perovskite and pyrochlore whereas low resulted in phase separation into a mixture of rhombohedral perovskite, tetragonal perovskite, and pyrochlore. The sensitivity clearly shows that oxygen vacancies due to ZnO-doping are critical for synthesis of phase pure PIN-PZN-PT powder.     

High‐Temperature Dielectric Relaxation in Pb(Mg1/3Nb2/3)O3–PbTiO3 Single Crystals

We reported the dielectric properties of Pb(Mg_1/3Nb_2/3)O₃–PbTiO₃ single crystal in the temperature range of 300–1073 K and the frequency range of 100 Hz–10 MHz. Our results showed the coexistence of both true‐ and pseudo‐relaxor behaviors in the crystal. The true relaxor behavior related to the paraelectric‐ferroelectric phase transition occurs at~423 K. The pseudo‐relaxor behavior appearing at~773 K was found to be related to oxygen vacancies. Further investigation reveals that the pseudo‐relaxor behavior has fine structure: it contains two oxygen‐vacancy‐related relaxation processes. The low‐temperature relaxation process is a dipolar relaxation created by the hopping motions of the oxygen vacancies, and the high‐temperature relaxation process is a Maxwell‐Wagner relaxation caused by the sample/electrode contacts.     

Anisotropic domain structures of Pb(Mg1/3Nb2/3)O3–PbZrO3–PbTiO3 single crystals with high ferroelectric phase transition temperature

The anisotropic domain structures and local piezoresponse of rhombohedral Pb(Mg_1/3Nb_2/3)O₃–PbZrO₃–PbTiO₃ single crystals with high ferroelectric phase transition temperature (T_FE‐FE≥120°C) were systematically investigated by vector piezoresponse force microscopy. The typical size of labyrinthine domain pattern for [001]_C sample was in the range of 100‐200 nm, revealing its relaxor feature. While the [011]_C sample exhibited ordered ribbon‐shaped domain pattern with preferential alignment along <011> direction since the modulation effect of polar nanoregions. For [111]_C sample, it had messy and featureless domain patterns. For as‐grown crystal, the incorporation of Zr⁴⁺ cation in Pb(Mg_1/3Nb_2/3)O₃–PbTiO₃ system resulted in that the long‐range coulomb interactions of the charged ions in the short range order regions were weakened, leading to an increased relaxor feature. Concurrently, the incorporation of Zr⁴⁺ cation enhanced the Pb‐B repulsion intensity, resulting in an improved T_FE‐FE. Temperature‐dependent properties of as‐grown crystal exhibited good temperature stability from 30 to 120°C, indicating it is a promising material for actuator and ultrasonic transducer applications.     

Fabrication of Transparent Pb(Mg1/3Nb2/3)O3–PbTiO3 Based Ceramics by Conventional Sintering

Transparent 0.9Pb(Mg_1/3Nb_2/3)O₃–0.1PbTiO₃ (PMN‐PT) based ceramics were prepared by a conventional solid‐state synthesis without using a hot‐press method. The ceramics became transparent when they were sintered in an O₂ atmosphere. The optical transmission increased with decreasing diameter of the calcined powder, which was controlled by the size of zirconia ball‐milling media. Substitution of 3 mol% La for Pb in PMN‐PT further increased the optical transmission to 68% at the wavelength of 2000 nm, which was comparable to that of hot‐pressed Pb(Mg_1/3Nb_2/3)O₃‐PbTiO₃ based transparent ceramics.     

Optimisation of matrix composition for texturing of morphotropic phase boundary Pb(Mg1/3Nb2/3)O3–PbZrO3–PbTiO3 piezoelectric ceramics using BaTiO3 template

Texturing is an innovative method for fabricating high-performance piezoelectric ceramics. However, the optimal conditions for successful texturing must be evaluated to obtain high performance. Herein, the texturing behaviour of Pb(Mg_1/3Nb_2/3)O₃–PbZrO₃–PbTiO₃ (PMN–PZ–PT) piezoelectric ceramics using plate-like BaTiO₃ crystals as a template was found to be strongly dependent on the chemical composition of the matrix. Given that the solubility of BaTiO₃ in the matrix increased with the PZ content, an excessive amount (>20 mol%) of the BaTiO₃ template was necessary for texturing a 0.2PMN–0.38PZ–0.42PT, while 3 mol% of the BaTiO₃ template could texture a 0.4PMN–0.22PZ–0.38PT. Owing to well-aligned textured grains and the complete consumption of randomly oriented matrix particles, a textured 0.4PMN–0.22PZ–0.38PT sample prepared by tape-casting under optimised conditions yielded a Lotgering factor of 97 % and an induced strain of 0.2 % with an electric field of 2 kV/mm.     

High radiation tolerance of electrocaloric (1-x)Pb(Mg1/3Nb2/3)O3–xPbTiO3

High radiation tolerance of functional materials in harsh environments is the key requirement for the operation of particle accelerators, medical devices, nuclear power plants, satellites, and spacecraft. Neutron and gamma (γ) radiation can seriously affect the functional properties of the irradiated materials and thus the performance of the entire device. In this work, the feasibility of using (1-x)Pb(Mg_1/3Nb_2/3)O₃–xPbTiO₃ (PMN–100xPT) electrocaloric materials in applications where the material is exposed to high neutron and γ-radiation is investigated. For this purpose, three different compositions of PMN–100xPT ceramics (x = 0, 0.1, and 0.35) were prepared and their dielectric, ferroelectric and electrocaloric properties were investigated before and after neutron and γ-irradiation. The samples were irradiated with a neutron fluence of 10¹⁵ to 10¹⁷ neutrons cm^?2 with an energy of 1 MeV, which exceeds the largest expected neutron irradiation in the European Council for nuclear Research (CERN) and simultaneously exposed to γ-irradiation. The neutron and γ-radiation partially affect the functional properties of the PMN–35PT, the ceramic with distinct ferroelectric and weakened relaxor features, with some differences observed in the domain switching behavior, measured by conventional polarization versus electric field (P–E) hysteresis, at the highest radiation dose of 10¹⁷ neutrons cm^?2. In contrast, the functional properties of the irradiated PMN and PMN–10PT samples with relaxor behavior are quite similar to those of the pristine samples, therefore, we conclude that these materials can be used as working materials in EC coolers exposed to such harsh environments.     

Effects of InNbO4 Fabrication on Perovskite PIN‐PMN‐PT

Effects of InNbO₄ (IN) fabrication on phase purity of the perovskite 23Pb(In_1/2Nb_1/2)O₃‐45Pb(Mg_1/3Nb_2/3)O₃‐32PbTiO₃ (PIN‐PMN‐PT) were studied. Excess In₂O₃ and annealing process on the phase of the synthesized IN were investigated. In addition, the precalcined IN and mixed IN powders on the phases of PIN‐PMN‐PT were discussed. The experimental results indicated that excess In₂O₃ have has minimal influence on the phase of IN due to the higher chemical activity of In₂O₃, IN powder with 3% In₂O₃ excess was in gray color because of the reaction, In₂O₃→In₂O, which can be changed to white color by annealing at 850°C in air. It was apparent that the mixed IN would benefit the pyrochlore‐free PIN‐PMN‐PT rather than precalcined IN powders. An optimized way for preparing PIN‐PMN‐PT materials was also proposed in this article.     

High permittivity (1−x)Bi1/2Na1/2TiO3‐xPbMg1/3Nb2/3O3 ceramics for high‐temperature‐stable capacitors

(1?x)Bi_1/2Na_1/2TiO₃‐xPbMg_1/3Nb_2/3O₃[(1?x)BNT‐xPMN] ceramics have been fabricated via a conventional solid‐state method for compositions x ≤ 0.3. The microstructure, phase structure, ferroelectric, and dielectric properties of ceramics were systematically studied as high‐temperature capacitor materials. XRD pattern certified perovskite phase with no secondary phase in all compositions. As PMN concentration increased, the phase of (1?x)BNT‐xPMN ceramics transformed from ferroelectric to relaxor gradually at room temperature, with prominent enhancement of dielectric temperature stability. For the composition x = 0.2, the temperature coefficient of capacitance (TCC) was <15% in a wide temperature range from 56 to 350°C with high relative permittivity (>3300) and low dielectric loss (<0.02) at 150°C, which indicated promising future for (1?x)BNT‐xPMN system as high‐temperature stable capacitor materials.     

High electric field-induced strain properties in La-doped Pb(In1/2Nb1/2)O3–PbZrO3–PbTiO3 relaxor ferroelectric ceramics

Piezoelectric ceramics with high strain response and low hysteresis are highly in demand for high-performance actuator applications. Unfortunately, the trade-off relationship between large field-induced strain and low hysteresis in piezoelectric ceramics is a key challenge for designing high-performance piezoelectric actuators. Herein, ymol%La-doped 0.10 Pb(In_1/2Nb_1/2)O₃-xPbZrO₃-(0.90–x)PbTiO₃ [0.10PIN-xPZ-(0.90-x)PT: ymol%La] ternary relaxor ferroelectric ceramics were prepared by conventional solid-state reaction technique. Pb(In_1/2Nb_1/2)O₃ (PIN) as a relaxor end member was introduced into (Pb,La) (Zr,Ti)O₃ (PLZT) system to improve relaxor characteristics and strain properties. A giant strain of 0.23% was obtained in 0.10PIN-0.59PZ-0.31 PT: 8mol%La ceramic at the electric field of 20 kV/cm, with a high piezoelectric d₃₃* of 1150 pm/V and low hysteresis H_y of 6.4%, exhibiting a potential application in high-performance piezoelectric actuators. Furthermore, the effects of La ion doping and components on the ferroelectric, dielectric and electric field-induced strain properties were investigated, and provides a new way for improve the strain properties of piezoelectric materials.     

Anisotropic domain switching in Pb(Mg1/3Nb2/3)O3‐0.30PbTiO3 single crystals with rhombohedral structure

Anisotropic domain switching paths in [001]‐, [011]‐, and [111]‐poled Pb(Mg_1/3Nb_2/3)O₃‐0.30PbTiO₃ single crystals were studied by in situ polarized light microscopic driven by an antiparallel electric field. Orientation‐dependent electric field induced polarization and strain behaviors were investigated systematically. For [001]‐oriented crystals, only one‐step 71° switching occurred during the domain switching process, resulting in the appearance of stripe domain walls whose traces on (001) plane were along 45° or 135° with respect to [100] direction. But for [011]‐oriented samples, a two‐step 71° switching was observed during 109° switching and the projections of formed twin domain walls on the (011) plane are along 35.3° or 144.7° with respect to [01] direction. Moreover, a three‐step 71° switching was found during 180° switching in [111]‐oriented samples. It was demonstrated by the produced domain walls whose projections on the (10) plane are along 35.3°, 90° or 160.6° with respect to [11] direction. The energetically motivated mechanism based on multistep polarization switching process was also proposed to explain the anisotropic domain switching paths. Our results provided a visualized observation on the ferroelectric domain switching process and also laid the solid foundations for controlling polarization order parameter in ferroelectric single crystals.     

Tunability properties in the paraelectric state of the Pb(Mg1/3Nb2/3)O3 ceramics

Pb(Mg_1/3Nb_2/3)O₃ ceramics prepared via columbite method exhibit high crystallinity and high density after sintering at 1200 °C. Typical relaxor behavior are demonstrated by the dielectric data. Although showing a diffuse phase transition, at room temperature the system is in its paraelectric state, i.e. the PMN structure is fully cubic. The dc-tunability was investigated above the room temperature, when other field-induced contributions than ferroelectric polarization might cause non-linearity. A random non-interacting dipolar unit in a double well potential was employed to describe the ?(E) non-linearity. The temperature-dependence of the average polarization corresponding to the polar nanoregions in the paraelectric state of the PMN relaxor was calculated from the ?(E) data at various temperatures above T_m. A similar trend of decreasing as increasing temperature shows the spin-glass local order parameter determined from the dielectric constant data in the paraelectric state. The local order parameter in the paraelectric state is determined by the nanopolar domains size and correlations.     

Growth and electrical properties of high-Curie point rhombohedral Mn-Pb(In1/2Nb1/2)O3-Pb(Mg1/3Nb2/3)O3-PbTiO3 thin films

High-quality ternary relaxor ferroelectric (100)-oriented Mn-doped 0.36Pb(In_1/2Nb_1/2)O₃-0.36Pb(Mg_1/3Nb_2/3)O₃-0.28PbTiO₃ (Mn-PIMNT) thin films were grown on SrRuO₃-buffered SrTiO₃ single-crystal substrate in a wide deposition temperature range of 550-620°C using the pulsed laser deposition method. The phase structure, ferroelectric, dielectric, piezoelectric properties, and nanoscale domain evolution were studied. Under the deposition temperature of 620°C, the ferroelectric hysteresis loops and current-voltage curves showed that the film owned significantly enhanced remnant ferroelectric polarization of 34.5 μC/cm² and low leakage current density of 2.7 × 10⁻¹⁰ A/cm². Moreover fingerprint-type nanosized domain patterns with polydomain structures and well-defined macroscopic piezoelectric properties with a high normalized strain constant of 40 pm/V was obtained. Under in situ DC electric field, the domain evolution was investigated and 180° domain reversal was observed through piezoelectric force microscope. These global electrical properties make the current Mn-PIMNT thin films very promising in piezoelectric MEMS applications.     

Normal‐Relaxor‐Diffuse Ferroelectric Phase Transition and Electrical Properties of Bi(Mg1/2Ti1/2)3–PbZrO3–PbTiO3 Solid Solution Ceramics Near the Morphotropic Phase Boundary

Perovskite‐type xBi(Mg_1/2Ti_1/2)O₃–(0.56 ? x)PbZrO₃–0.44PbTiO₃ (xBMT–PZ–PT) ternary solid solution ceramics were synthesized via a conventional solid‐state reaction method. The phase transition behaviors, dielectric, ferroelectric, and piezoelectric properties were investigated as a function of the BMT content. The X‐ray diffraction analysis showed that the tetragonality of xBMT–PZ–PT was enhanced with increasing the BMT content, and a morphotropic phase boundary (MPB) between rhombohedral and tetragonal phases was identified approximately in the composition of x = 0.08. In addition, the dielectric diffuseness and frequency dispersion behavior were induced with the addition of BMT and a normal‐relaxor‐diffuse ferroelectric transformation was observed from the PZ‐rich side to the BMT‐rich side. The electrical properties of xBMT–PZ–PT ceramics exhibit obviously compositional dependence. The x = 0.08 composition not only possessed the optimum properties with ε^T₃₃/ε₀ = 1450, Q_m = 69, d₃₃ = 390 pC/N, k_p = 0.46, P_r = 30 μC/cm², E_c = 1.4 kV/mm, T_c = 325°C, and a strain of 0.174% (d₃₃^* = 436 pm/V) under an electric field of 4 kV/mm as a result of the coexistence of two ferroelectric phases near the MPB, but also owned a good thermal‐depolarization behavior with a d₃₃ value of >315 pC/N up to 290°C and a frequency‐insensitive strain behavior.     

Ferroelectric to Relaxor Transition in BaTiO3–Bi(Zn2/3Nb1/3)O3 Ceramics

The (1?x)BaTiO₃–xBi(Zn_2/3Nb_1/3)O₃ (x = 0.01–0.30) ceramics were synthesized by solid‐state reactions. The solubility limit was determined to be x = 0.20. A systematic structural transition from a tetragonal phase (x ≤ 0.034), to a mixture of tetragonal and rhombohedral phases (0.038 ≤ x ≤ 0.20), and finally to a pseudocubic phase (x ≥ 0.22) at room temperature was identified. Dielectric measurement revealed a ferroelectric (x ≤ 0.04) to relaxor (x ≥ 0.06) transition with permittivity peak broadening and flattening, which was further verified by Raman spectroscopy and differential scanning calorimetry (DSC). Activation energies obtained from the Vogel–Fulcher model displayed an increasing trend from ~0.03 eV for x ~ 0.05, to unusually high values (>0.20 eV) for the compositions with x ≥ 0.15. With the increase in Bi(Zn_2/3Nb_1/3)O₃ content, the polarization hysteresis demonstrated a tendency from high nonlinearity to sublinearity coupled with the reduction in remnant polarization and coervice field. The deconvolution of the irreversible/reversible polarization contribution was enabled by first‐order reversal curve distributions, which indicates that the decreasing polarization nonlinearity with the increase in Bi(Zn_2/3Nb_1/3)O₃ concentration could be related with the change from the ferroelectric domain and domain wall contributions to the weakly coupled relaxor behaviors.     

Metastable Ferroelectric Phase Induced by Electric Field in xPb(Zn1/3Nb2/3)O3–(1–x)Pb(Zr0.95Ti0.05)O3 Ceramics

A xPb(Zn_1/3Nb_2/3)O₃–(1–x)Pb(Zr_0.95Ti_0.05)O₃ (xPZN–(1–x) PZT) system close to antiferroelectric–ferroelectric (AFE–FE) morphotropic phase boundary has been prepared and investigated. The XRD results reveal PZN addition induces a phase transition from the orthorhombic (AFE) to rhombohedral (FE) phase through a phase coexistence region (AFE+FE). The polarization–electric field (P–E) measurements indicate that the AFE phase can be induced into a metastable FE (FE_m) phase. And the FE_m can recover to AFE around a critical temperature indicated by temperature‐dependent P–E loops. A composition‐temperature phase diagram was generalized within a certain range of PZN content in which an AFE–FE phase boundary connecting orthorhombic antiferroelectric to rhombohedral ferroelectric phase zones is formed near room temperature.