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.     

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.     

Enhanced energy storage properties of BiAlO3 modified Bi0.5Na0.5TiO3–Bi0.5K0.5TiO3 lead-free antiferroelectric ceramics

Lead-free (1−x)(0.75Bi_0.5Na_0.5TiO₃–0.25Bi_0.5K_0.5TiO₃)–xBiAlO₃ (BNT–BKT–100xBA, x=0–0.10) ceramics were prepared by two-step sintering method and their phase structure, micro morphology and electrical properties were systematically investigated. X-ray diffraction analysis indicates a pure perovskite phase for x≤0.06 as well as a structural evolution from a tetragonal toward a pseudocubic phase. Transmission electron microscopy study of the x=0.04 composition reveals the existence of antiferroelectric phase with a⁰a⁰c⁺ oxygen octahedron tilting which is in the form of nano-domains. Polarization-electric field and current-electric field hysteresis loops demonstrate that the increase of BA concentration destroys the ferroelectric order and strengthens antiferroelectric order. A much enhanced energy storage density of 1.15 J/cm³ and efficiency of 73.2% is achieved under 105 kV/cm at x=0.06. In addition, its energy storage property is found to depend weakly on temperature within the measurement range of 25–150 °C.     

Morphotropic phase boundary and electrical properties of 1−x[Bi0.5Na0.5]TiO3 –xBa[Zr0.25Ti0.75]O3 lead-free piezoelectric ceramics

Lead-free solid solutions (1?x)Bi_0.5Na_0.5TiO₃ (BNT)–xBaZr_0.25Ti_0.75O₃ (BZT) (x=0, 0.01, 0.03, 0.05, and 0.07) were prepared by the solid state reaction method. X-ray diffraction (XRD) and Rietveld refinement analyses of 1?x(BNT)–x(BZT) solid solution ceramic were employed to study the structure of these systems. A morphotropic phase boundary (MPB) between rhombohedral and cubic structures occured at the composition x=0.05. Raman spectroscopy exhibited a splitting of the (TO₃) mode at x=0.05 and confirmed the presence of MPB region. Scanning electron microcopy (SEM) images showed a change in the grain shape with the increase of BZT into the BNT matrix lattice. The temperature dependent dielectric study showed a gradual increase in dielectric constant up to x=0.05 and then decrease with further increase in BZT content. Maximum coercive field, remanent polarization and high piezoelectric constant were observed at x=0.05. Both the structural and electrical properties show that the solid solution has an MPB around x=0.05.     

Morphotropic phase boundary and electrical properties of lead-free (K0.5Bi0.5)TiO3–Bi(Ni0.5Ti0.5)O3 relaxor ferroelectric ceramics

Lead-free relaxor ferroelectric ceramics (1?x)(K_0.5Bi_0.5)TiO₃–xBi(Ni_0.5Ti_0.5)O₃ were prepared by a conventional solid-state route, the phase transition behavior and corresponding electrical properties were investigated. A typical morphotropic phase boundary (MPB) between rhombohedral and tetragonal ferroelectric phases was identified to be in the range of 0.05<x<0.07 where the optimum piezoelectric and electromechanical properties of d₃₃=126 pC/N and k_P=18% were achieved. Most importantly, a high Curie temperature ~320 °C, around which the material shows a typical relaxor ferroelectric behavior characterized by the presence of diffuse phase transition and frequency dispersion, was obtained in MPB compositions, significantly higher than those of some existing MPB lead-free titanate systems. These results demonstrate a tremendous potential of the studied system for device applications.     

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.     

Enhanced piezoelectric properties of Sr(1.7)(Na0.5Bi0.5)0.3Bi4Ti5O18 ceramics in the system Sr(2−x)(Na0.5Bi0.5)xBi4Ti5O18 (where 0 ≤ x ≤ 0.5)

Fine powders synthesized via sol-gel route were employed to fabricate Sr_(2−x)(Na_0.5Bi_0.5)_xBi₄Ti₅O₁₈ (SNBT, where x = 0, 0.1, 0.25, 0.3, 0.4, and 0.5) ceramics. The composition (x)-dependent structural changes associated with SNBT ceramics were analyzed using X-ray powder diffraction, transmission electron microscopy, and Raman spectroscopic techniques. Average grain size analyses carried out on the SNBT ceramics by scanning electron microscopy revealed an important role played by the dopants in inhibiting the grain growth. Dielectric constants and the Curie temperature of the ceramics were found to decrease and increase, respectively, with increase in x. The increase in Curie temperature with increase in x was attributed to the decrease in the tolerance factor. The specific composition (x = 0.3) of the SNBT ceramics exhibited improved piezo- and ferroelectric properties associated with a higher Curie temperature (569 K). The piezoelectric coefficient (d₃₃) and the planar electromechanical coupling coefficient (k_p) of SNBT(x = 0.3) were enhanced by 25% and 42%, respectively, as compared to the undoped ceramics.     

Enhanced dielectric energy storage performance of A-site Ca2+-doped Na0.5Bi0.5TiO3–BaTiO3–BiFeO3 Pb-free ceramics

(1-x) (0.98Na_0.5Bi_0.5TiO₃–0.01BaTiO₃–0.01BiFeO₃)–xCaTiO₃ (NBB-xCT) ceramics were produced using traditional solid-state synthesis methods. The surface morphology, domain structure, and electrical properties of the ceramic samples were systematically studied. In addition, the temperature and frequency stabilities of the NBB-15CT sample at 200 kV/cm were tested. Generally, NBB-xCT ceramics exhibit a typical single perovskite phase structure. The results indicate that the NBB-15CT ceramics showed a high energy density of 3.14 J/cm³ at 250 kV/cm. The piezoresponse force microscopy (PFM) results showed that the addition of CT broke the macrodomains of the 0.98Na_0.5Bi_0.5TiO₃-0.01BaTiO₃-0.01BiFeO₃ ceramic and helped to form nanodomains, leading to an improved energy storage performance. The above performance indicates that the specimens possess very good temperature-and frequency-dependent energy storage performances at 30–150 °C and 1–100 Hz. Moreover, the electric energy storage and release in the NBB-15CT ceramic indicated that the power density could reach 55.30 MV/cm³ at 180 kV/cm. Therefore, the NBB-15CT ceramic is a promising material for electrical capacitors.     

Electrocaloric effect and pyroelectric energy harvesting of (0.94 − x)Na0.5Bi0.5TiO3-0.06BaTiO3-xSrTiO3 ceramics

Ceramics with the composition (0.94 − x)Na_0.5Bi_0.5TiO₃–0.06BaTiO₃–xSrTiO₃ (NBBSTx) where x = 0.10, 0.15, 0.20, and 0.25 were synthesized by a conventional solid-state reaction method to investigate their electrocaloric effect (ECE) and pyroelectric energy harvesting (PEH) properties. The ferroelectric, dielectric, and pyroelectric properties of the prepared ceramics were measured and discussed. It is found that the strontium titanate (ST) content and bias field greatly affect the ferroelectric–relaxor transition. Increasing ST content lowers the depolarization temperature of the ceramics, and both the ECE and PEH behavior of the ceramics strongly depend on their ST content because of the composition-induced decrease of the ferroelectric–relaxor transition temperature. The present investigation demonstrates that the ECE and PEH properties of NBBSTx ceramics can be tuned by introducing ST. Furthermore, a high PEH density of 425 kJ/m³ is obtained for NBBST0.20, which is much higher than those of conventional Pb-based ferroelectrics.     

Analysis of the rhombohedral–tetragonal symmetries coexistence in lead-free 0.94(Bi0.5Na0.5)TiO3–0.06BaTiO3 ceramics from nanopowders

Ceramics with perovskite-type structure and 0.94(Bi_0.5Na_0.5)TiO₃–0.06BaTiO₃ (BNBT) composition have been studied by conventional powder X-ray diffraction in Bragg–Brentano geometry. Ceramics were obtained from sol–gel autocombustion nanopowders and processed either by hot pressing and subsequent recrystallisation or pressureless sintering in two steps. These methods provided single-phase, sub-micron grain size (<700?nm), dense ceramics with good piezoelectric performance (96–94% of theoretical density and d₃₃?=?143–124?pC?N^–1, respectively). For the considered ceramics, the splitting of the peaks of the cubic perovskite-type structure with 111 and 200 Miller indices has been repeatedly used as a symmetry identification criterion. In this work a simple, yet powerful, procedure to validate the consistency of the mentioned splitting interpretation is presented. Based on peaks fitting and well-known crystallographic expressions, the rhombohedral and tetragonal symmetries' coexistence is verified. The suggested procedure can be applied to the study of peak splitting in ceramics at Morphotropic Phase Boundaries in a general way. In a given series of BNBT ceramics, inconsistencies for interplanar distances, intensities' ratios and the evolution of these from not-poled to poled samples have been found. In poled ceramics, special care has been taken when carrying out this analysis, due to the anisotropic strains arising from ferroelectric (FE) domain orientation. Poling gives rise to a displacement of the peaks angular positions and modification of the intensity ratios. However, the interplanar distance changes associated with the angular deviations here observed are one order of magnitude higher than those expected from anisotropic strains. These results set up a doubt on the sufficiency of the [rhombohedral?+?tetragonal] model to characterise the considered ceramics. A model of a mesoscopic FE phase with rhombohedral symmetry, a mesoscopic and globally weakly polar phase, with cubic symmetry, and a nanosised phase, also cubic, is presented as a plausible alternative.     

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.     

Structural,dielectric and piezoelectric properties of (Bi0.5Na0.5)TiO3–(Bi0.5K0.5)TiO3–Bi(Zn0.5Ti0.5)O3 thin films prepared by sol–gel method

Lead free (1−x)(0.8Bi_0.5Na_0.5Ti_0.5O₃–0.2Bi_0.5K_0.5TiO₃)–xBiZn_0.5Ti_0.5O₃ (x=0–0.06) (BNT–BKT–BZT) thin films were deposited on Pt(111)/Ti/SiO₂/Si(100) substrates by a sol–gel processing technique. The effects of BZT content on the structural, dielectric, ferroelectric and piezoelectric properties of the BNT–BKT–BZT thin films were investigated systematically. The BNT–BKT–BZT thin films undergo a transition from ferroelectric to relaxor phase with increasing temperature. The phase transition temperature decreases with the increase of BZT content. The BNT–BKT–BZT thin film with x=0.04 exhibits the best ferroelectric properties (P_max=40 µC/cm² and P_r=10 µC/cm²), largest dielectric constant (ε=560) and piezoelectric constant (d₃₃=40 pm/V). This finding demonstrates that the BNT–BKT–BZT thin film has an excellent potential for demanding high piezoelectric properties in lead free films.     

Structure,relaxation behaviors and nonlinear dielectric properties of BaTiO3–Bi(Ti0.5Mg0.5)O3 ceramics

(1−x)BaTiO₃–xBi(Mg_1/2Ti_1/2)O₃ (BT–BMT, x=0–0.2, abbreviated as BT–BMT100x) ceramics were prepared by using a solid state reaction process. Their crystal structure, microstructure, conduction behavior, dielectric and tunability properties were investigated. It is found that the tetragonal phase and a pseudocubic phase coexist for x≤0.15 and transform to a pseudocubic phase at x=0.20. With the incorporation of BMT, BT–BMT becomes more insulating. The activation energies of the conduction are respectively 1.15(1) and 1.54(1) eV for grain and grain boundary of BT–BMT20. Furthermore, an abnormal nonlinear dielectric tunable behavior is observed. The dielectric permittivity first slightly increases until reaching the threshold electric field, and then suddenly decreases. This abnormal nonlinear dielectric behavior is attributed to the synergetic effects of the clamped oxygen vacancies and excessive aggregation of Bi at the grain boundaries.     

CeO2、Sb2O3掺杂(Na0.88K0.12)0.5Bi0.5TiO3无铅陶瓷的压电性能研究

采用传统陶瓷的制备方法制备了CeO2(0～1.0wt%)和Sb2O3(0～0.6wt%)掺杂的(Na0.88K0.12)0.5Bi0.5TiO3无铅压电陶瓷。运用XRD技术研究了样品的晶体结构,测试并分析了样品的介电、压电性能以及谐振频率温度系数。结果表明:所有组成均呈三方结构的钙钛矿型固溶体特征。在适当掺杂剂用量范围内,压电陶瓷的压电常数、介电常数和介电损耗升高,而平面机电耦合系数降低。CeO2和Sb2O3掺杂均改善了(Na0.88K0.12)0.5Bi0.5TiO3压电陶瓷频率温度稳定性。     

Na0.5Bi0.5TiO3–K0.5Bi0.5TiO3–BaTiO3–SrTiO3陶瓷的准同型相界与电性能

采用固相法制备了 Na0.5Bi0.5TiO3–K0.5Bi0.5TiO3–BaTiO3–SrTiO3（NBT–KBT–BT–ST）陶瓷,该体系是按（1–2x）（0.8NBT–0.2KBT）–x（0.94NBT–0.06BT）–x（0.74NBT–0.26ST） （x = 0.10、0.20、0.25、0.30、0.35、0.40、0.45）组合而成的,研究了该系陶瓷的结构与电性能。结果表明：所有样品都处于三方–四方准同型相界区域。该系陶瓷在准同型相界附近表现出了优异的压电性能,压电常数 d33、机电耦合系数 kp和剩余极化强度 Pr随 x 的增加先升高后降低,其中 x=0.35 陶瓷的电性能最佳：d33= 210 pC/N,kp= 0.319,Pr= 39.3 μC/cm2,Ec= 20.2 kV/cm,是一种良好的无铅压电陶瓷候选材料。依据准同型相界组成的线性组合规律来寻找具有优异压电性能的 NBT–KBT–BT–ST 陶瓷准同型相界组成是可行的。     

Destabilization of the ferroelectric order in Na0.5Bi0.5TiO3–6 wt% BaTiO3 ceramics through doping

One of the most promising candidates to replace lead-based compounds in actuator applications are Na_0.5Bi_0.5TiO₃ (NBT)-based materials. K_0.5Na_0.5NbO₃ (KNN)-modified NBT-BaTiO₃ (NBT-BT) solid solutions exhibit giant large-signal strain–electric-field coefficients (S_max/E_max) exceeding 500 pm V^?1. However, despite the promising properties of the ceramics reported in the literature, the synthesis of these materials remains challenging, leaving gaps in the understanding of the synthesis-property relationship. In this contribution, we investigate the microstructure and the electrical properties while changing the composition to destabilize the ferroelectric order in the material, which is the key to achieve large strain response. Measurements of dielectric and ferroelectric properties reveal that Na- or Ti-deficiency or excess of Bi decrease the ferroelectric-to-relaxor transition temperature and remnant polarization, indicating a destabilization of the ferroelectric order. Additionally, the use of KNO₃ instead of K₂CO₃ as the potassium source in KNN results in an additional destabilizing effect on the ferroelectric order, which can be attributed to better incorporation of K⁺ into the perovskite structure. The results identify the key aspects of the synthesis of NBT-BT-KNN ceramics to obtain high S_max/E_max values.     

Thermal and dynamic mechanical analyses on Bi0.5Na0.5TiO3–BaTiO3 ceramics synthesized with citrate method

Bi_0.5Na_0.5TiO₃–xBaTiO₃ (BNT–xBT) nano-powders are successfully synthesized by a modified citrate method. The as-prepared BNT-BT powders and the sintered ceramics are homogeneous with a pure perovskite crystal structure. The effects of Ba²⁺ substitutions for (Bi_0.5Na_0.5)²⁺ in the A-sites of Bi_0.5Na_0.5TiO₃ on its phase transformations are explored. The transformations among ferroelectric (FE), anti-ferroelectric (AFE) and paraelectric (PE) states in these ceramics are characterized using ferroelectric hysteresis tests, modulated differential scanning calorimetry and dynamic mechanical analysis. The FE-AFE transition in BNT–xBT with 0≤x≤0.15 is found to relate with a structural transformation which is a first-order phase transition. The mechanical and thermal analyses provide evidence that AFE state (0≤x≤0.15) could be associated with the incommensurate modulation of rhombohedral structures while the mechanisms of forming AFE state in BNT–xBT (x>0.15) could be different.     

Quantification of relaxor behavior in (1 − x)Na0.5Bi0.5TiO3 – xCaTiO3 lead-free ceramics system

This work examines the relaxor behavior of lead-free ceramic (1 − x)Na_0.5Bi_0.5TiO₃–xCaTiO₃ systems. A stable rhombohedral (R3c) phase is detected at room temperature for all compositions by XRD and Raman spectroscopy. Relaxor behavior was observed in the temperature range 300 K - 400 K for all materials. Ceramics exhibit normal ferroelectric properties at room temperature, and then they develop relaxor characteristics with increasing temperature showing the same dispersive properties. This work quantifies the relaxor phenomenon at low temperature. For instance, the maximum temperature of relaxor and the order of dispersion were determined at the strongest dispersion. Finally, the substitution by low CT concentration unaltered the relaxor behavior at low temperature.