In Situ Domain Structure Observation and Giant Magnetoelectric Coupling for PMN‐PT/Terfenol‐D Multiferroic Composites

In situ observations of ferroelectric domain structure evolution, and magnetoelectric (ME) coupling are investigated for PMN‐28PT/Terfenol‐D (abbreviation of Pb(Mg_1/3Nb_2/3)O₃‐28PbTiO₃/Tb_0.3Dy_0.7Fe₂) and PMN‐33PT/Terfenol‐D composites under the magnetic loadings. The composite of PMN‐33PT/Terfenol‐D shows stronger ME coupling than that in PMN‐28PT/Terfenol‐D. At a thickness of 0.10–0.12 mm for the single crystal plate, a giant magnetoelectric coefficient (α_ME) up to 2 V/cm·Oe is obtained for PMN‐33PT/Terfenol‐D at a static magnetic field of 200 Oe and 1 kHz of the alternating magnetic field. In situ domain structure observations reveal the domain morphology change during the applied magnetic loadings. In PMN‐28PT, the domains are of predominantly rhombohedral (R) phase and they change into monoclinic M_A phase upon the magnetic loading via the strain transferred between Terfenol‐D plate and PMN‐PT single crystal. In PMN‐33PT, domains of orthorhombic (O), R, and monoclinic M_C coexist and phase transitions from O to M_C and further to R phase occur upon the magnetic loading. The undulation and diversity of the domain structure makes the domains more susceptible to the magnetic loading via strain transferred between Terfenol‐D plate and PMN‐PT single crystal, and consequently, a strong ME coupling in the composites.     

Domain structure and evolution in ZnO-modified Pb(Mg1/3Nb2/3)O3–0.32PbTiO3 ceramics

The doping of ZnO is efficient to improve the piezoelectric property and thermal stability of Pb(Mg_1/3Nb_2/3)O₃–PbTiO₃ (PMN–PT) based ceramics. However, the underlying physics, especially the local domain structures of the ZnO modified PMN–PT ceramics, which is strongly associated with the electric properties, is not clear yet. In this paper, we investigated the local domain structures and their evolution as a function of x in PMN–0.32PT:xZnO ceramics. It was found that, the domain evolution is mainly caused by the growth of grain size induced by the sintering aiding effect of ZnO at x < 0.04, and the domain evolution can be attributed to the phase transition induced by the partial replacement of Mg²⁺ by Zn²⁺ in the B-site of PMN–PT lattice at x > 0.06. Furthermore, we also investigated the domain structure evolution as functions of temperature and local external electric field in PMN–0.32PT:0.06ZnO ceramics, which exhibited superior piezoelectric property relative to other compositions. We found that the irregular nanodomains are more stable at high-temperature range, and the regular non-180° domains exhibited more complex rotation behavior under local electric field, which probably leads to the thermal stability and piezoelectric property enhancement in the ZnO-modified PMN–0.32PT ceramics.     

Domain Structure Evolutions During the Poling Process for [011]‐Oriented PMN–xPT Crystals Across the MPB Region

The poling effect on the [011]‐oriented (1?x)Pb(Mg_1/3Nb_2/3)O₃‐xPbTiO₃ (PMN–xPT) single crystals across the morphotropic phase boundary (MPB) was studied. The dielectric and piezoelectric properties were investigated as a function of the poling field. Domain structure evolutions during the poling process were recorded. In the unpoled PMN–xPT phase diagram, an apparent rhombohedral (R)‐tetragonal (T) phase boundary exists. With room‐temperature poling, the structure transformation sequence strongly depends on the composition. The crystal experiences a direct transition to the 2R/2T domain state in the rhombohedral or tetragonal phase field beyond the MPB region, whereas within the MPB zone it is hard to achieve the 2R/2T engineered configuration although the initial state is either rhombohedral or tetragonal as well. The piezoelectric responses of the MPB·PMN–xPTs are extraordinary weak (d₃₃ ~ 250 pC/N), in contrast to the [011]‐oriented multidomain PMN–xPTs with ultrahigh‐piezoelectric coefficient (d₃₃ > 1000 pC/N). We demonstrate that a slight composition variation near the MPB will significantly influence the domain evolution route and piezoelectricity for the [011]‐oriented PMN–xPT crystals. We also confirm the feasibility to realize the 2R/2T engineered domain configuration for the [011]‐oriented MPB crystals, which will extend the desired portion of the Bridgeman‐grown boules with optimal piezoelectric properties.     

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.     

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.     

Dielectric Relaxor Evolution and Frequency‐Insensitive Giant Strains in (Bi0.5Na0.5)TiO3‐Modified Bi(Mg0.5Ti0.5)O3–PbTiO3 Ferroelectric Ceramics

The 0.45Bi(Mg_0.5Ti_0.5)O₃–(0.55 ? x)PbTiO₃–x(Bi_0.5Na_0.5)TiO₃ (BMT–PT–xBNT) ternary solid solution ceramics were prepared via a conventional solid‐state reaction method; the evolution of dielectric relaxor behavior and the electrostrain features were investigated. The XRD and dielectric measurements showed that all studied compositions own a single pseudocubic perovskite structure and undergo a diffuse‐to‐relaxor phase transition owing to the evolution of the domain from a frozen state to a dynamic state. The formation of the above dielectric relaxor behavior was further confirmed by a couple of measurements such as polarization loops, polarization current density curves, as well as bipolar strain loops. A large strain value of ~0.41% at a driving field of 7 kV/mm (normalized strain d₃₃* of ~590 pm/V) was obtained at room temperature for the composition with x = 0.32, which is located near the boundary between ergodic and nonergodic relaxor. Moreover, this electric field‐induced large strain was found to own a frequency‐insensitive characteristic.     

High temperature‐insensitive ferro‐/piezoelectric properties and nanodomain structures of Pb(In1/2Nb1/2)O3–PbZrO3–Pb(Mg1/3Nb2/3)O3–PbTiO3 relaxor single crystals

For rhombohedral (R) Pb(In_1/2Nb_1/2)O₃–PbZrO₃–Pb(Mg_1/3Nb_2/3)O₃–PbTiO₃ (PIN–PZ–PMN–PT) relaxor single crystal, high temperature‐insensitive behaviors under different external stimuli were observed (remnant polarization P_r from 30°C to 180°C and piezoelectric strain d₃₃* from 30°C to 116°C). When electric field E ≥ 50 kV/cm in the case of an activation field E_a = 40‐50 kV/cm was applied, it was found that the domain switching was accompanied by a phase transition. The high relaxor nature of the R phase PIN–PZ–PMN–PT was speculated to account for the large E_a and high piezoelectric response. The short‐range correlation lengths extracted from the out‐of‐plane (OP) and in‐plane (IP) nanodomain images, were 64 nm and 89 nm, respectively, which proved the high relaxor nature due to In³⁺ and Zr⁴⁺ ions entering the B‐site in the ABO₃‐lattice and enhancing the disorder of B‐site cations in the R phase PIN–PZ–PMN–PT. The switching process of R nanodomain variants under the step‐increased tip DC voltage was visually revealed. Moreover, the time‐dependent domain evolution confirmed the high relaxor nature of the R phase PIN–PZ–PMN–PT single crystal.     

Large Piezoelectric Response and Polarization in Relaxor Ferroelectric PbTiO3–Bi(Ni1/2Zr1/2)O3

New binary system (1?x) PbTiO₃?xBi(Ni_1/2Zr_1/2)O₃ (PT–100x BNZ) with x ≤ 0.45 were synthesized via solid‐state reaction route. A morphotropic phase boundary (MPB) was identified around x = 0.40 by X‐ray diffraction (XRD) method. The ceramics with MPB composition exhibit enhanced ferroelectric properties. A large piezoelectric coefficient (d₃₃) up to 400 pC/N was obtained for the PT–40BNZ, which is comparable with the PbTiO₃–BiScO₃ (PT–BS, 450 pC/N).The frequency dependence of dielectric permittivity of PT–40BNZ shows characteristic of a strong relaxor feature and a transition temperature around 290°C (1 MHz). Temperature effect on the unipolar strain was also investigated. The present system with high d₃₃ is a competitive piezoelectric material, as no expensive oxide is used here compared with the PT–BS.     

Synthesis,structural evolution,and dielectric properties of a new perovskite solid solution (Pb0.5Sr0.5)(Zr0.5Ti0.5)O3–PbTiO3

To explore lead-reduced dielectric materials in the SrTiO₃–PbTiO₃–PbZrO₃ ternary system, a novel solid solution between relaxor ferroelectric (Pb_0.5Sr_0.5)(Zr_0.5Ti_0.5)O₃ and ferroelectric PbTiO₃, namely (1 − x)(Pb_0.5Sr_0.5) (Zr_0.5Ti_0.5)O₃–xPbTiO₃ (lead–strontium–zirconate–titanate [PSZT]–PT), has been synthesized in the perovskite structure by high-temperature solid-state reaction method in the form of ceramics. The crystal structure and phase symmetry of the materials synthesized were analyzed and resolved based on X-ray powder diffraction (XRD) data through both the Pawley and Rietveld refinements. The results of the structural refinements indicate that at low PT-concentration end of the solid solution system, for example, x = 0.05, the PSZT–PT solid solution exhibits a cubic structural symmetry (with the space group Pm-3m). As the PT concentration (x) increases, the structure of (1 − x)PSZT–xPT gradually transforms from the cubic to a tetragonal (P4mm) phase. In the composition range of x = 0.10–0.25, a mixture of the cubic and tetragonal phases was identified. As the concentration of PT increases, the proportion of the tetragonal phase increases at the expense of the cubic phase. For a composition of x > 0.25, a pure tetragonal phase is observed. The dielectric properties of the materials were studied by measuring the permittivity as a function of temperature at various frequencies. For the composition of x = 0.05, the temperature dependence of dielectric constant shows typical relaxor behavior. For x = 0.35, the dielectric peaks indicate a normal ferroelectric phase transition. Overall, a structural transformation from a central-symmetric, nonpolar cubic phase to a non-centrosymmetric, polar tetragonal phase is induced by the substitution of PT for PSZT in the pseudo-binary solid solution of (1 − x)PSZT–xPT, which also reveals an interesting relaxor to ferroelectric crossover phenomenon.     

Systematic study of structure and piezoelectric properties of Pb(Ni1/3Nb2/3)O3-PbTiO3 by in situ synchrotron diffraction

Lead-based ferroelectric materials are extensively employed in industrial applications and everyday life due to their excellent ferroelectric and piezoelectric performance. Pb(Ni_1/3Nb_2/3)O₃-PbTiO₃ (PNN-PT) is a typical binary relaxor ferroelectric system, whose refined structure and piezoelectric properties have not been systematically investigated. In this study, evolution of electric field-based crystal structure and variation of ferroelectric, piezoelectric, as well as dielectric properties with composition and temperature of (1 − x)PNN-xPT (0.32 ≤ x ≤ 0.36) ceramics were studied in full detail. The optimal performance is obtained at 0.66PNN-0.34PT with maximum piezoelectric coefficient d₃₃ of 560 pC/N and large dielectric constant of 28 684. In situ high-energy synchrotron diffraction was employed to determine structural origins of enhanced properties of 0.66PNN-0.34PT. Interestingly, crystal structure of poled 0.66PNN-0.34PT ceramic is determined to be single monoclinic phase. Furthermore, both its lattice parameters and volume variation present butterfly shape under electric field. It is demonstrated that macroscopic strain of 0.66PNN-0.34PT stems mainly from intrinsic structure. The present study provides evidence for the relationship between microstructure and macroscopic properties, which is beneficial to the design of new materials with piezoelectric properties.     

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.     

Effect of CuO Addition on the Microstructure and Electric Properties of Low‐Temperature Sintered 0.25PMN–0.40PT–0.35PZ Ceramics

Low‐temperature sintering of 0.25PMN–0.40PT–0.35PZ ceramics was investigated using CuO as a sintering aid. Effect of CuO on the sinterability, microstructure, and electric properties of 0.25PMN–0.40PT–0.35PZ system was systematically studied. The CuO addition significantly reduced the sintering temperature of 0.25PMN–0.40PT–0.35PZ from 1260°C to 950°C. SEM results indicated that a dense microstructure without any second phase was obtained when the amount of CuO was 0.25 wt%, which gave rise to high values of d₃₃ = 532 pC/N and k_p = 58.4%. A large field‐induced longitudinal strain ~2.28% (at 30 kV/cm) can also be obtained for 0.25 wt% CuO‐added specimens, which shows a great promise for multilayer actuator applications.     

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.     

Investigations on electric properties and domain structures of Nd-doped 0.70Pb(Mg1/3Nb2/3)O3–0.30PbTiO3 relaxor ferroelectric ceramics with high piezoelectric properties

Although rare earth neodymium (Nd) doping is common in Pb(Mg1/3Nb2/3)O₃–PbTiO₃ (PMN–PT) single crystals, it is rarely reported in PMN–PT ceramics. To explore the effect of Nd doping on PMN–PT ceramics, PMN–30PT:xNd³⁺ (x = 0%, 1%, 2%, and 3%) relaxor ferroelectric ceramics were fabricated using a solid-state method via two-step sintering. An enhanced piezoelectric charge coefficient (d₃₃) of ∼870 pC/N and a high piezoelectric strain coefficient (d₃₃*) of ∼1025 pm/V were achieved for x = 2%. Through Rayleigh analysis of polarization–electric field (P–E) hysteresis loops under small electric fields, it was found that the dielectric property was mainly influenced by the intrinsic contribution (local lattice distortion). Furthermore, by investigating domain configurations, high piezoelectric properties were found to be associated with the domain size reduction and local structural heterogeneity. The results indicate that the PMN–30PT:xNd³⁺ ceramics is a promising material for electronic devices, and that rare earth Nd doping is an efficient strategy for improving the electronic performance of Pb-based relaxor ferroelectrics.     

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.     

Characterization of the High‐Temperature Ferroelectric (100−x−y)BiScO3–(x)Bi(Zr0.5Zn0.5)O3–(y)PbTiO3 Perovskite Ternary Solid Solution

Ternary compositions based on Bi(B′B″)O₃–PbTiO₃‐type compounds have been investigated for high‐temperature piezoelectric applications. Compositions in the ternary were chosen to be near the binary morphotropic phase boundary (MPB) composition of BiScO₃–PbTiO₃ (BS–PT). Ternary compositions in (100?x?y)BiScO₃–(x)Bi(Zr_0.5Zn_0.5)O₃–(y)PbTiO₃ [(100?x?y)BS–xBZZ–yPT] have been investigated with x ≤ 7.5. For compositions with x > 10, the Curie temperature (T_C) decreased below 400°C. Dielectric, piezoelectric, and electromechanical properties were characterized as a function of temperature, frequency, and electric field. Small additions of BZZ were shown to increase the electromechanical properties with only a small loss in T_C. The electromechanical properties were temperature stable up to the depoling temperature. The most promising composition exhibited a T_C of 430°C, piezoelectric coefficient (d₃₃) of 520 pC/N, and a planar coupling factor (k_p) of 0.45 that remained unchanged up to depoling temperature at 385°C.     

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.     

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.     

Domain Structure Evolution and Polarization Degradation of [101]‐Oriented 0.74Pb(Mg1/3Nb2/3)O3‐0.26PbTiO3 Single Crystal underCyclic Electric Loadings

The polarization degradation of ferroelectrics, reflected in the hysteresis loop as a decrease of remnant polarization, is a serious concern in applications. In situ observation of the polarization and domain structure evolution are carried out for [101]‐Oriented 0.74Pb(Mg_1/3Nb_2/3)O₃‐0.26PbTiO₃ (PMN‐26PT) single crystal under cyclic electric field. Measurements of the polarization hysteresis loops are conducted under a polarized light microscope (PLM), which is effective in detecting the domain structure of the single crystal. Prior to the polarization measurements, the crystal was poled. Upon cyclic electric field, reversal of monoclinic (M_B) takes place, and the phase transition from M_B to orthorhombic (O) phase occurs under positive field, but not under negative field of an electric cycle at a field magnitude up to 840 V/mm. The polarization loop is asymmetrical with the positive coercive field (+E_c) much less than the negative one (?E_c). As the field cycles, micro‐cracking occurs preferably in [101] direction, and a sudden drop appears in the curves of polarization versus number of cycles. Upon electric cycling at a field magnitude of 840 V/mm, the negative polarization increases slightly with the cycle number, indicating the rotation of a M_B phase toward the applied field direction.     

Pyroelectric energy harvesting using low–TC (1–x)(Ba0.7Ca0.3)TiO3–xBa(Zr0.2Ti0.8)O3 bulk ceramics

Lead‐free ferroelectric ceramics (1–x)(Ba_0.7Ca_0.3)TiO₃–xBa(Zr_0.2Ti_0.8)O₃ (BCTZ100x) with x = 0.20, 0.30, 0.40, 0.50, 0.60, 0.70, and 0.80 were evaluated for their pyroelectric energy harvesting performance, using the Olsen cycle. As the composition ratio x increased, the crystal phase changed to tetragonal, orthorhombic, rhombohedral, and cubic; the phase boundaries crossed each other in the vicinity of BCTZ70. The crossover phase transition behavior between first‐order and diffuse phase transition changed to only the diffusion phase transition with increasing x. A pinching effect occurred because an increase in dielectric constant was also observed. Energy densities N_D of 229 mJ/cm³ and 256 mJ/cm³ for BCTZ50 and BCTZ80 were obtained, respectively, in temperature of 30°C‐100°C and an electric field of 0‐30 kV/cm. These N_D values are over two times higher than that of soft–Pb(Ti,Zr)O₃ (PZT), which exhibits piezoelectric performance equivalent to BCTZ50 at room temperature. Compared with soft–PZT, BCTZ50 and BCTZ80 exhibited larger N_D values owing to their lower Curie temperatures (T_C ~ 50°C‐110°C). We conclude that low–T_C ferroelectrics are useful for pyroelectric energy conversion based on the Olsen cycle even if they are unsuitable for piezoelectric applications at high temperatures.