Large strains accompanying field-induced ergodic phase-polar ordered phase transformations in Bi(Mg0.5Ti0.5)O3–PbTiO3–(Bi0.5Na0.5)TiO3 ternary system

A composition-induced pseudocubic–tetragonal structural transition was found to be accompanied by a relaxor phase transformation in xBi(Mg_0.5Ti_0.5)O₃–(0.75 − x)PbTiO₃–0.25(Bi_0.5Na_0.5)TiO₃ ternary solid solutions. Dielectric and ferroelectric measurements suggest the coexistence of ergodic and nonergodic relaxor phases within a single pseudocubic phase zone for samples with 0.50 < x < 0.51 where large electromechanical strains of up to 0.43% (S_max/E_max = 621 pm/V) can be generated. The mechanism was mainly ascribed to the accumulated effects of field-modulated continuous and reversible transformations from a pseudocubic ergodic phase to a rhombohedral short-range ordered phase (but not nonergodic polar phase), and finally to a long-range ordered ferroelectric tetragonal phase. These procedures were found to be strongly dependent on the applied field magnitudes. These findings were reasonably approved by a couple of measurements such as dielectric–temperature–frequency spectrum, ferroelectric polarization/strain hysteresis loops, polarization current density curves and particularly ex situ Raman spectrum and in situ high-resolution synchrotron X-ray diffraction.     

Giant strain response and structure evolution in (Bi0.5Na0.5)0.945−x(Bi0.2Sr0.7□0.1)xBa0.055TiO3 ceramics

The microstructure, electric-field-induced strain, polarization, and dielectric permittivity in (Bi_0.5Na_0.5)_0.945−x(Bi_0.2Sr_0.7□_0.1)_xBa_0.055TiO₃ (BNBT–xBST) (0 ≤ x ≤ 0.08) electroceramics are investigated. An irreversible transition from rhombohedral and monoclinic coexistence phase to single rhombohedral phase is indicated with the remnant strain S_r = 0.330% at x = 0. As the BST content increases, the ferroelectric order is disrupted resulting in a degradation of the remnant polarization, coercive field, and the ferroelectric-to-relaxor transition temperature (T_F–R). The coexistence of ferroelectric relaxor and ferroelectric phase is observed for the optimum composition x = 0.02 at ambient temperature with a large strain of 0.428% at 60 kV/cm (normalized strain S_max/E_max = 713 pm/V). The large strain is contributed by both ferroelectric domain reorientation behavior and the reversible relaxor to ferroelectric phase transition.     

Composition‐ and Temperature‐Dependent Large Strain in (1−x)(0.8Bi0.5Na0.5TiO3–0.2Bi0.5K0.5TiO3)– xNaNbO3 Ceramics

Ternary solid solutions of (1 ? x)(0.8Bi_0.5Na_0.5TiO₃–0.2Bi_0.5K_0.5TiO₃)– xNaNbO₃ (BNKT–xNN) lead‐free piezoceramics were fabricated using a conventional solid‐state reaction method. Pure BNKT composition exhibited an electric‐field‐induced irreversible structural transition from pseudocubic to ferroelectric rhombohedral phase at room temperature. Accompanied with the ferroelectric‐to‐relaxor temperature T_F‐R shifted down below room temperature as the substitution of NN, a compositionally induced nonergodic‐to‐ergodic relaxor transition was presented, which featured the pinched‐shape polarization and sprout‐shape strain hysteresis loops. A strain value of ~0.445% (under a driving field of 55 kV/cm) with large normalized strain of ~810 pm/V was obtained for the composition of BNKT–0.04NN, and the large strain was attributed to the reversible electric‐field‐induced transition between ergodic relaxor and ferroelectric phase.     

Phase structure,piezoelectric, ferroelectric,and electric-field-induced strain properties of Nb-modified 0.8Bi0.5Na0.5TiO3−0.2Sr0.85Bi0.1TiO3 ceramics

0.8Bi_0.5Na_0.5Ti_(1-x)Nb_xO₃−0.2Sr_0.85Bi_0.1TiO₃ (BNT-SBT-xNb, x = 0.00, 0.01, 0.02, and 0.03) piezoelectric ceramics were prepared by traditional solid state reaction and the influence of Nb substitution on the phase structure, ferroelectric, piezoelectric, and electric-field-induced strain properties in BNT-SBT ceramics were studied. XRD results exhibited that Nb⁵⁺ ions could fully diffuse into BNT-SBT structure to form a solid solution when x = 0.01. P-E loops and S-E curves suggested that the ferroelectric phase transformed to ergodic relaxor state (FE-to-ER) with the increasing the amount of Nb additive, indicating the ferroelectric long-ranged order was disturbed by the excess of Nb. With increasing Nb doping, phase transition temperature from normal ferroelectric to ergodic relaxor (short for T_F-R) could be reduced from 120 °C to 40 °C. Furthermore, for sample with x = 0.01, the normalized strain d₃₃^* got a maximum value ~571 pm/V due to the phase transition from ergodic relaxor to ferroelectric (ER-to-FE) under electric field.     

Dielectric,ferroelectric and field-induced strain response of lead-free (Fe,Sb)-modified (Bi0.5Na0.5)0.935Ba0.065TiO3 ceramics

Lead-free piezoelectric ceramics (Bi_0.5Na_0.5)_0.935Ba_0.065Ti_1−x(Fe_0.5Sb_0.5)_xO₃ (BNBT6.5–xFS, x=0.005, 0.010, 0.015, 0.020) were prepared by a conventional solid sintering technique. The effects of B-site doping of (Fe, Sb) on the phase structure, microstructure, dielectric, ferroelectric, and piezoelectric properties of BNBT6.5 ceramics were systematically investigated. Results showed that (Fe, Sb) can completely diffuse in the BNBT6.5 lattice in the all studied components. The addition of (Fe, Sb) destroyed the ferroelectric long-range order, and thus promoted the electric field induced strain response. The maximum electric field-induced strain (S_max=0.37%) with normalized strain (d₃₃*=S_max/E_max=454 pm/V) at an applied electric field of 80 kV/cm was obtained at x=0.015. Temperature dependent measurements of both polarization and strain from room temperature to 120 °C suggested that the origin of the large strain is due to a reversible field-induced ergodic relaxor to ferroelectric phase transformation.     

Phase structure,ferroelectric properties,and electric field-induced large strain in lead-free 0.99[(1−x)(Bi0.5Na0.5)TiO3-x(Bi0.5K0.5)TiO3]–0.01Ta piezoelectric ceramics

Lead-free 0.99[(1−x)(Bi_0.5Na_0.5)TiO₃-x(Bi_0.5K_0.5)TiO₃]–0.01Ta piezoelectric ceramics were prepared by a conventional solid-state reaction process. The ferroelectric properties, and strain behaviors were characterized. Increase of the (Bi_0.5K_0.5)TiO₃ content induces a phase transition from coexistence of ferroelectric tetragonal and rhombohedral to a relaxor pseudocubic phase. Accordingly, the ferroelectric order is disrupted significantly with the increase of (Bi_0.5K_0.5)TiO₃ content and the destabilization of the ferroelectric order is accompanied by an enhancement of the unipolar strain, which peaks at a value of 0.35% (corresponding to a large signal d₃₃ of 438 pm/V) in samples with 20 mol% (Bi_0.5K_0.5)TiO₃ content. Temperature dependent measurements of both polarization and strain from room temperature to 120 °C suggested that the origin of the large strain is due to a reversible field-induced nonpolar pseudocubic-to-polar ferroelectric phase transformation.     

The electrical properties of (1−x)(Bi0.5Na0.5TiO3–Bi0.5K0.5TiO3–BaTiO3)–xCaZrO3 lead-free piezoelectric ceramics

Lead-free (1−x)(0.0852Bi_0.5Na_0.5TiO₃–0.12Bi_0.5K_0.5TiO₃–0.028BaTiO₃)–xCaZrO₃ piezoelectric ceramics (BNT−BKT−BT−xCZ, x=0, 0.01, 0.02, 0.03, 0.04 and 0.05) were prepared by using a conventional solid-state reaction method. The effects of CZ-doping on the structural, dielectric, ferroelectric and piezoelectric properties of the BNT−BKT−BT−xCZ system were systematically investigated. The polarization and strain behaviors indicated that the long-range ferroelectric order in the unmodified BNT−BKT−BT ceramics was disrupted by the increase of CZ-doping content, and correspondingly the depolarization temperature (T_d) shifted down from 109 °C to below room temperature. When x>0.03, accompanied with the drastic decrease in the remnant polarization (P_r) and piezoelectric coefficient (d₃₃), the electric-field-induced strain was enhanced significantly. A large unipolar strain of 0.35% under an applied electric field of 70 kV/cm (S_max/E_max=500 pm/V) was obtained in the BNT−BKT−BT−0.04CZ ceramics at room temperature, which was attributed to the reversible electric-field-induced phase transition between the relaxor and ferroelectric phases.     

Lead-free Bi1/2(Na0.82K0.18)1/2TiO3 relaxor ferroelectrics with temperature insensitive electrostrictive coefficient

The electric field-induced strain of Bi_1/2(Na_0.82K_0.18)_1/2TiO₃ (BNKT) ceramics modified with BaZrO₃ (BZ) was investigated as a function of composition and temperature. Unmodified BNKT ceramics revealed a typical ferroelectric butterfly-shaped bipolar S–E loop at room temperature, whose normalized strain (S_max/E_max) showed a significant temperature coefficient of 0.38 pm/V/K. As the BZ content increased in the solid solution up to 5 mol%, the ferroelectric BNKT gradually transformed to a relaxor. Finally, 5 mol% BZ-modified BNKT ceramics showed a typical electrostrictive behavior with a thermally stable electrostrictive coefficient (Q₃₃) of 0.025 m⁴/C², which is comparable to that of Pb(Mg_1/3Nb_2/3)O₃ (PMN) ceramics that have been primarily used as Pb-based electrostrictive materials.     

Large strain response in (Mn,Sb)–modified (Bi0.5Na0.5)0.935Ba0.065TiO3 lead–free piezoelectric ceramics

Lead–free piezoelectric ceramics (Bi_0.5Na_0.5)_0.935Ba_0.065Ti_1–x(Mn_0.5Sb_0.5)_xO₃ (BNBT6.5–xMS, x=0.005, 0.010, 0.015, 0.020) were prepared by conventional solid state reaction sintering technique. All ceramics present a pure perovskite phase structure, indicating that (Mn, Sb) has completely diffused into the BNBT6.5 lattice in the studied components. The addition of (Mn, Sb) disrupted the ferroelectric long–range order and promoted the electric field induced strain response. At x=0.015, a large electric field–induced unipolar strain of 0.48% (at an applied electric field of 80 kV/cm) with normalized strain d₃₃^*(S_max/E_max) of 602 pm/V are achieved. Temperature dependent measurements of both polarization and strain from room temperature to 120 °C were also studied, and the results suggest that the origin of the large strain is due to a reversible field–induced non–polar relaxor phase to polar ferroelectric phase transformation.     

Giant electromechanical strain response in lead‐free SrTiO3‐doped (Bi0.5Na0.5TiO3–BaTiO3)–LiNbO3 piezoelectric ceramics

Lead‐free 0.985[(0.94?x)Bi_0.5Na_0.5TiO₃–0.06BaTiO₃–xSrTiO₃]–0.015LiNbO₃ [(BNT–BT–xST)–LN, x=0‐0.05] piezoelectric ceramics were prepared using a conventional solid‐state reaction method. It was found that the long‐range ferroelectric order in the unmodified (BNT–BT)–LN ceramic was disrupted and transformed into the ergodic relaxor phase with the ST substitution, which was well demonstrated by the dramatic decrease in remnant polarization (P_r), coercive field (E_c), negative strain (S_neg) and piezoelectric coefficient (d₃₃). However, the degradation of the ferroelectric and piezoelectric properties was accompanied by a significant increase in the usable strain response. The critical composition (BNT–BT–0.03ST)–LN exhibited a maximum unipolar strain of ~0.44% and corresponding normalized strain, S_max/E_max of ~880 pm/V under a moderate field of 50 kV/cm at room temperature. This giant strain was associated with the coexistence of the ferroelectric and ergodic relaxor phases, which should be mainly attributed to the reversible electric‐field‐induced transition between the ergodic relaxor and ferroelectric phases. Furthermore, the large field‐induced strain showed relatively good temperature stability; the S_max/E_max was as high as ~490 pm/V even at 120°C. These findings indicated that the (BNT–BT–xST)–LN system would be a suitable environmental‐friendly candidate for actuator applications.     

Tuning the ferroelectric-relaxor transition temperature in NBT-based lead-free ceramics by Bi nonstoichiometry

In this study, the Bi-nonstoichiometric 0.99Bi_x(Na_0.8K_0.2)_0.5TiO₃-0.01SrTiO₃ (BNKST) ceramics with x = 0.5–0.535 mol (Bi50-Bi53.5) were prepared by a conventional solid-state reaction method. The effects of Bi excess on structural transition and ferroelectric stability of BNKST ceramics were systematically investigated by the Raman spectra, dielectric analyses and electromechanical measurements. The introduction of excess Bi³⁺ could significantly break the long-range ferroelectric order and favor the presence of relaxor phase, then the ferroelectric-relaxor transition temperature (T_FR) can be effectively tuned to around room temperature by Bi nonstoichiometry, giving rise to an enhanced room-temperature strain property. The positive strain S_pos and dynamic piezoelectric constant d₃₃^* of Bi52.5 critical composition reach 0.33% and 440 pm/V, respectively at 6 kV/mm. The high recoverable strain of Bi52.5 sample can be attributed to the electric-field-induced reversible relaxor-ferroelectric phase transition. The present work may be helpful for further understanding and designing high-performance NBT-based lead-free ceramics for piezoelectric actuator applications.     

Dielectric,ferroelectric and field-induced strain behavior of K0.5Na0.5NbO3-modified Bi0.5(Na0.78K0.22)0.5TiO3 lead-free ceramics

Lead-free piezoelectric (1 ? x)Bi_0.5(Na_0.78K_0.22)_0.5TiO₃–xK_0.5Na_0.5NbO₃ (BNKT–xKNN, x = 0–0.10) ceramics were synthesized using a conventional, solid-state reaction method. The effect of KNN addition on BNKT ceramics was investigated through X-ray diffraction (XRD), dielectric, ferroelectric and electric field-induced strain characterizations. XRD revealed a pure perovskite phase with tetragonal symmetry in the studied composition range. As the KNN content increased, the depolarization temperature (T_d) as well as maximum dielectric constant (?_m) decreased. The addition of KNN destabilized the ferroelectric order of BNKT ceramics exhibiting a pinched-type hysteresis loop with low remnant polarization (11 μC/cm²) and small piezoelectric constant (27 pC/N) at 3 mol% KNN. As a result, at x = 0.03 a significant enhancement of 0.22% was observed in the electric field-induced strain, which corresponds to a normalized strain (S_max/E_max) of ～434 pm/V. This enhancement is attributed to the coexistence of ferroelectric and non-polar phases at room temperature.     

Large electric field-induced strain in AgNbO3-modified 0.76Bi0.5Na0.5TiO3-0.24SrTiO3 lead-free piezoceramics

Bi_0.5Na_0.5TiO₃-based lead-free piezoceramics with large strain output are of great importance in the application of piezoelectric actuators. AgNbO₃-modified 0.76Bi_0.5Na_0.5TiO₃-0.24SrTiO₃ (BNT-24ST) lead-free piezoceramics were synthesized by conventional solid-state reaction method. The effects of AgNbO₃ on the structures, dielectric, ferroelectric and piezoelectric properties were carefully investigated. A large electrostrain and normalized strain (d₃₃* = S_max/E_max) of 0.27% and 700?pm/V, were obtained respectively at low electric field (40?kV/cm) for 1?mol.% AgNbO₃-doped BNT-24ST. AgNbO₃ doping modified the phase composition which contained moderate amounts of tetragonal and rhombohedral phase by shifting its T_F-R to below room temperature. Moreover, the reversible field-induced phase transition between relaxor and ferroelectric made contributions to its large strain related properties. This work has confirmed that the actuating performance of BNT-ST-based piezoceramics can be further improved by an easy and cost-effective composition engineering method and showed it a promising candidate for lead-free actuator material.     

Temperature dependent,large electromechanical strain in Nd-doped BiFeO3-BaTiO3 lead-free ceramics

Lead-free piezoceramics with the composition 0.7(Bi_1-xNd_x)FeO₃-0.3BaTiO₃+0.1 wt% MnO₂ (BNxF-BT) were prepared using a conventional solid state route. X-ray diffraction and temperature dependent permittivity measurements indicated a transition from a composition lying at a morphotropic phase boundary (MPB) to a pseudocubic phase as a function of Nd concentration. The highest maximum strain (S_max ∼ 0.2% at 60 kV/cm) and effective piezoelectric coefficient (d₃₃* = 333 pm/V) were obtained at room temperature for the composition BN0.02F-BT. The decrease in remanent polarization (P_r) and Berlincourt d₃₃ with increase in Nd concentration can be attributed to the coexistence of ferroelectric and relaxor phases. In-situ polarisation and strain measurements revealed an increase in P_r and d₃₃* with temperature and a reduction in the coercive field E_C. Presumably this behavior is due to a combination of thermally activated domain wall motion and lowering of the activation energy for a field induced relaxor-ferroelectric transition, as the Curie maximum is approached.     

The effect of high-energy ball milling on the electromechanical strain properties of Bi-based lead-free relaxor matrix ferroelectric composite ceramics

The crystal structure, ferroelectric, and electric-field-induced strain (EFIS) properties of Bi-based lead-free ferroelectric/relaxor composite materials are investigated. Bi_1/2(Na_0.82K_0.18)_1/2TiO₃ as a ferroelectric material and 0.98Bi_1/2(Na_0.78K_0.22)_1/2TiO₃‒0.02LaFeO₃ as a relaxor were synthesized via conventional ceramic processing routes while the relaxor (matrix phase) was prepared via high-energy ball milling (HEBM) after calcination. The average particle size was decreased via HEBM treatment. As a result, a high d₃₃^* value of over 600 pm/V was obtained at 4 kV/mm for 30-min HEBM-treated composites. This demonstrates that HEBM treatment is effective in enhancing the strain properties of lead‒free piezoelectric composite materials.     

Low temperature sintering of lead-free Bi0.5(Na0.82K0.18)0.5TiO3 piezoelectric ceramics by co-doping with CuO and Nb2O5

Effect of excess CuO additive on the sintering behavior and piezoelectric properties of Bi_0.5(Na₈₂K_0.18)_0.5TiO₃ ceramics was investigated. The addition of small amount of excess CuO as low as 1 mol% was quite effective to lower the sintering temperature (T_s) of BNKT ceramics down to 975 °C while their piezoelectric properties were degraded by Cu doping. However, the electric field-induced strain was markedly enhanced by further addition of Nb₂O₅ with CuO without elevating T_s. The normalized strain S_max/E_max of 427 pm/V was obtained with a specimen sintered with 0.02 mol CuO and 0.03 mol Nb₂O₅ in excess.     

Phase–composition and temperature dependence of electrocaloric effect in lead–free Bi0.5Na0.5TiO3–BaTiO3–(Sr0.7Bi0.2□0.1)TiO3 ceramics

The (0.94–x)Bi_0.5Na_0.5TiO₃–0.06BaTiO₃–x(Sr_0.7Bi_0.2□_0.1)TiO₃ (BNT–BT–xSBT, 0 ≤ x ≤ 0.24) solid solution ceramics were synthesized via a conventional solid–state reaction method and the correlation of phase structure, piezoelectric, ferroelectric properties and electrocaloric effect (ECE) was investigated in detail. The ECE in lead–free BNT–BT–xSBT ceramics was measured directly using a home–made adiabatic calorimeter with maximum adiabatic temperature change ΔT = 0.4 K with x = 0.08 under the electric field E = 6 kV/mm at room temperature. The position of maximum ECE was found in the vicinity of nonergodic and ergodic phase boundary, where the maximum change in entropy occurs as a result of the field–induced phase transformation between the ergodic and long–range ferroelectric phase. Besides, the mechanism for the shift of ECE peak is discussed in detail. Finally, the temperature dependence of ECE for BNT–BT–xSBT (x = 0, 0.04 and 0.08) was also investigated. This work may present a guideline for designing BNT–based ferroelectric relaxor ceramics for EC cooling technologies.     

Large strain and relaxation behavior in CeO2 doped Bi0.487Na0.427K0.06Ba0.026TiO3 piezoceramics

xCeO₂-doped Bi_0.487Na_0.427K_0.06Ba_0.026TiO₃ lead-free piezoelectric ceramics (BNTC1000x, x=0, 0.3, 0.6, 0.8, 1.0, 1.2, 1.4 wt%), were synthesized by the solid-state reaction method. XRD patterns showed that all BNTC1000x ceramics exhibit pure single perovskite phase. At the critical composition BNTC12, a large electric-field-induced strain of 0.39% with normalized strain (S_max/E_max) of 561 pm/V was obtained under an electric field of 65 kV/cm. The ferroelectric phase was fully poled with electric field, and depoled once the applied electric field was removed. During that cycle, the non-180°-domains repeated switching and back-switching and the large strain was induced. The relaxation behavior was involved in BNTC1000x ceramics and induced by oxygen vacancy migration. Besides, this behavior was more predominant in BNTC12 than in BNTC0.     

Polarization and strain behaviors of 0.74BiNaTiO3–0.26SrTiO3/Bi0.5(Na0.8K0.2)0.5TiO3 ceramic composite

We investigated the temperature- and frequency-dependent polarization and strain of two bismuth-based perovskite materials, a matrix material and a seed material, with which we formed a composite whose properties we likewise investigated. The chosen matrix material is 0.74Bi_0.5Na_0.5TiO₃–0.26SrTiO₃ (BNT-ST) which has a transition point of ~65 °C, from the relaxor to the ferroelectric phase (T_R-F). The seed material was Bi_0.5(Na_0.8K_0.2)_0.5TiO₃ (BNKT), which possesses a T_R-F of 120 °C. Different polarization and strain behaviors were observed in the BNT-ST/BNKT composite at different test temperatures. At T=25 °C (<T_R-F of the relaxor BNT-ST), the composite exhibited a hysteretic polarization loop and parabolic strain curves which involve an ergodic relaxor-to-normal ferroelectric phase transition with application of an external electric field and the reverse ferroelectric-to relaxor phase transition with removal of the field. When T=80 and 100 °C (>T_R-F °f the relaxor BNT-ST and <T_R-F of the ferroelectric BNKT), the BNT-ST/BNKT has a slim polarization loop and strain magnitudes that are slightly increased from those of pure BNT-ST. When T=120 °C (~T_R-F of the ferroelectric BNKT), the composite has a very slim polarization loop and strain behavior with values that are almost same as those of pure BNT-ST. In addition, the P-S relation for the BNT-ST/BNKT is identical to that of BNT-ST as the operating frequency increases up to 100 Hz. This may be because the polarization of BNT-ST is lower than that of BNKT. The electric field-induced polarization and strain of the BNT-ST/BNKT composite with respect to the temperature and frequency are related to the thermal stability of the ferroelectric seed and the degree of the phase transition in the relaxor matrix.     

Low-temperature sintered Bi0.5Na0.5TiO3-SrTiO3 incipient piezoceramics and the co-fired multilayer piezoactuator thereof

Lead-free Bi_0.5Na_0.5TiO₃-SrTiO₃ incipient piezoceramics with Li₂CO₃ and MnO₂ additives were successfully fabricated at low firing temperature for applications in co-fired multilayer piezoactuators. The addition of Li₂CO₃ effectively shifted the sintering temperature from 1230 °C down to 1075 °C, where the ceramics were co-fired with a Ag/Pd (75/25) inner electrode. The prototype actuators were prepared by tape-casting method using ceramics with the composition of 0.74Bi_0.5Na_0.5TiO₃-0.26 SrTiO₃ + 0.15 wt%MnO₂ + 0.45 wt%Li₂CO₃. The total number of active layers was 13, and each ceramic layer had a thickness of 60 μm. The actuator output a large strain up to ∼0.20% at a driving field of 4 kV/mm, due to the field-induced phase transition between the ergodic relaxor and ferroelectric phases. The excellent voltage-displacement performance of the prototype actuator demonstrates the potential for industrial applications.