Effect of WO3 doping on dielectric and ferroelectric properties of 0.94(Bi0.5Na0.5)TiO3–0.06BaTiO3 ceramics

WO₃(0–6 mol%)-doped 0.94Bi_0.5Na_0.5TiO₃–0.06BaTiO₃ lead-free ceramics were synthesized by conventional solid-state reaction. The effect of WO₃ addition on the structure and electrical properties were investigated. The result revealed that a small amount of WO₃ (≤1 mol%) can diffuse into the lattice and does not significantly affect the phase structure, however, more addition will result in distortion and enlargement of the unit cells. The maximum permittivity temperature (T_m) is suppressed dramatically as the dopant increasing, while the depolarization temperature (T_d) fall to the minimum with 1 mol% WO₃ additive. The remanent polarization (P_r) was enhanced and coercive field (E_c) was reduced by doping with WO₃. The strain shows the largest value for 1 mol% doped sample, which is due to a field-induced antiferroelectric–ferroelectric phase transition.     

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 transition behavior and electrical properties of lead-free (Bi0.5K0.5)TiO3–LiNbO3 relaxor ferroelectric ceramics

(1?x)(Bi_0.5K_0.5)TiO₃–xLiNbO₃ ((1?x)BKT–xLN) lead-free relaxor ferroelectric ceramics were prepared by a conventional solid-state route and their phase transition behavior and the corresponding electrical properties were investigated. A morphotropic phase boundary separating rhombohedral and tetragonal phases was identified in the composition range of 0.015<x<0.03, where the improved electrical properties of piezoelectric constant d₃₃=75 pC/N and electromechanical coupling factor k_p=0.18 were obtained. Moreover, all samples show typical relaxor behavior characterized by the presence of diffuse phase transition and frequency dispersion. It was found that the dielectric relaxation behavior of BKT ceramics can be obviously enhanced with the addition of LN. In addition, the effect of the LN addition on the ferroelectric properties was also investigated by measuring polarization versus electric field hysteresis loops.     

Enhancing the dielectric and energy storage properties of lead-free Na0.5Bi0.5TiO3–BaTiO3 ceramics by adding K0.5Na0.5NbO3 ferroelectric

A novel strategy of enhancing the dielectric and energy storage properties of Na_0.5Bi_0.5TiO₃–BaTiO₃ (NBT–BT) ceramics by introducing a K_0.5Na_0.5NbO₃ (KNN) ferroelectric phase is proposed herein, and its underlying mechanism is elucidated. The lead-free KNN ceramic decreases the residual polarisation and increases the electric breakdown strength of the NBT–BT matrix through the simultaneous modification of its A-sites and B-sites. The obtained NBT?BT?x?KNN ceramics have a perovskite structure with unifying grains. A bulk 0.9NBT–BT–0.1KNN ceramic sample with a thickness of 0.2 mm possesses a high energy storage density of 2.81 J/cm³ at an applied electric field of 180 kV/cm. Moreover, it exhibits good insulation properties and undergoes rapid charge and discharge processes. Therefore, the obtained 0.9NBT–BT–0.1KNN ceramic can be potentially used in high-power applications because of its high energy density, good insulation properties, and large discharge rate.     

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.     

Structure,dielectric and ferroelectric properties of 0.92Na0.5Bi0.5TiO3–0.06BaTiO3–0.02K0.5Na0.5NbO3 lead-free ceramics: Effect of Co2O3 additive

0.92Na_0.5Bi_0.5TiO₃–0.06BaTiO₃–0.02K_0.5Na_0.5NbO₃+x wt% Co₂O₃ (NBKT–xCo, x=0, 0.2, 0.4, 0.6, 0.8) lead-free ferroelectric ceramics were prepared via a conventional solid state reaction method. Effects of Co₂O₃ additive on crystallite structure, microstructure, dielectric and ferroelectric properties of the NBKT–xCo ceramics were studied. X-ray diffraction results showed that the rhombohedral–tetragonal morphotropic phase boundary existed in all the ceramics, with relative amount of tetragonal phase varying with the content of Co₂O₃. Average grain size, maximum value of dielectric constant, Curie temperature and ferroelectric properties of the ceramics were close related to the content of Co₂O₃. The dielectric anomaly caused by the phase transition between the ferroelectric phase and the so-called “intermediate phase” was observed in the ceramics with x≤0.2, while it disappeared with further increasing x. All the ceramics showed a diffuse phase transition between the “intermediate phase” and the paraelectric phase. The change in the ferroelectric properties with changing the content of Co₂O₃ was discussed by considering the competitive effects among grain size, relative amount of the tetragonal phase and oxygen vacancies.     

High permittivity and excellent high-temperature energy storage properties of X9R BaTiO3–(Bi0.5Na0.5)TiO3 ceramics

We fabricated x(Bi_0.5Na_0.5)TiO₃–(1−x)[BaTiO₃–(Bi_0.5Na_0.5)TiO₃–Nb] (BNT-doped BTBNT-Nb) dielectric materials with high permittivity and excellent high-temperature energy storage properties. The initial powder of Nb-modified BTBNT was first calcined and then modified with different stoichiometric ratios of (Bi_0.5Na_0.5)TiO₃ (BNT). Variable-temperature X-ray diffraction (XRD) results showed that the ceramics with a small amount of BNT doping consisted of coexisting tetragonal and pseudocubic phases, which transformed into the pseudocubic phase as the test temperature increased. The results of transmission electron microscopy (TEM) showed that the ceramic grain was the core-shell structure. The permittivity of the 5 mol% BNT-doped BTBNT-Nb ceramic reached up to 2343, meeting the X9R specification. The discharge energy densities of all samples were 1.70-1.91 J/cm³ at room temperature. The discharge energy densities of all samples fluctuated by only ±5% over the wide temperature range from 25°C to 175°C and ±8% from 25°C to 200°C. The discharge energy density of the 50 mol% BNT-doped BTBNT-Nb ceramic was 2.01 J/cm³ at 210 kV/cm and 175°C. The maximum energy efficiencies of all ceramics were up to ~91% at high temperatures and were much better than those at room temperature. The stable dielectric properties within a wide temperature window and excellent high-temperature energy storage properties of this BNT-doped BTBNT-Nb system make it promising to provide candidate materials for multilayer ceramic capacitor applications.     

Dielectric,ferroelectric, and depolarization properties of B-site manganese-doped 0.925(Bi0.5Na0.5)TiO3–0.075BaTiO3 solid solutions

(Bi_0.5Na_0.5)_0.925Ba_0.075(Ti_1−xMn_x)O₃ (x=0, 0.2, 1.0, and 2.0 mol%) ceramics were prepared by solid-state-reaction method to study dielectric, ferroelectric, and depolarization properties. The manganese (Mn) doping can suppress dielectric permittivity and increase relaxor behavior. Coercive field (E_c) increases, while remanent polarization (P_r) decreases as the Mn content increases. P_r exhibits discontinuous anomalies as a function of temperature in all compositions, implying a polarization reorganization of local domains. The depolarization temperature (T_d) reaches the highest value (~152 °C) in 0.2%Mn, and decreases as MnO₂ content increases. The increased T_d in 0.2%Mn is due to two-phase coexistence and structural thermal stability induced by Mn ions. This work suggests that the moderate Mn doping can enhance T_d in lead-free piezoceramics for applications at elevated temperatures.     

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.     

Ferroelectric properties and large electric field-induced strain of Eu3+-doped Na0.5Bi0.5TiO3–BaTiO3 lead-free ceramics

Eu³⁺-doped lead-free piezoelectric ceramics, 0.937Na_0.5Bi_0.5?xEu_xTiO₃-0.063BaTiO₃ (abbreviated as NBE_xT-BT, where x = 0, 0.003, 0.005, 0.01, 0.013, 0.015, 0.017, and 0.02), were synthesized using a conventional solid-state synthesis method. All the component samples were crystallized in a pure perovskite structure without a secondary phase. The introduction of Eu³⁺ caused the evident variation of the dielectric, ferroelectric and luminescence properties. The remanent polarization and coercive field of the pure NBT-BT are P_r ～29.24 μC/cm², E_c～39.33 kV/cm, respectively. The maximum of the remanent polarization P_r of ～38.02 μC/cm² at room temperature and the highest dielectric constant of 6899 with a frequency of 1 kHz were obtained for NBE_0.003T-BT. The maximum bipolar strain S_max of ～0.91% and the minimum of coercive field E_c ～18.45 kV/cm were achieved by the NBE_0.015T-BT, resulting from the formation of a double hysteresis loop. For all the components, Eu³⁺ doping stabilized the antiferroelectric phenomenon at high temperature. Furthermore, the polarized NBE_0.015T-BT had the strongest fluorescence luminescence intensity as well as a fluorescence lifetime reaching 785.98 μs.     

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.     

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.     

Microstructure,ferroelectric and piezoelectric properties of Bi0.5K0.5TiO3-modified BiFeO3–BaTiO3 lead-free ceramics with high Curie temperature

The effects of composition, sintering temperature and dwell time on the microstructure and electrical properties of (0.75 ? x)BiFeO₃–0.25BaTiO₃–xBi_0.5K_0.5TiO₃ + 1 mol% MnO₂ ceramics were studied. The ceramics sintered at 1000 °C for 2 h possess a pure perovskite structure and a morphotropic phase boundary of rhombohedral and pseudocubic phases is formed at x = 0.025. The addition of Bi_0.5K_0.5TiO₃ retards the grain growth and induces two dielectric anomalies at high temperatures (T₁ ～ 450–550 °C and T₂ ～ 700 °C, respectively). After the addition of 2.5 mol% Bi_0.5K_0.5TiO₃, the ferroelectric and piezoelectric properties of the ceramics are improved and very high Curie temperature of 708 °C is obtained. Sintering temperature has an important influence on the microstructure and electrical properties of the ceramics. Critical sintering temperature is 970 °C. For the ceramic with x = 0.025 sintered at/above 970 °C, large grains, good densification, high resistivity and enhanced electrical properties are obtained. The weak dependences of microstructure and electrical properties on dwell time are observed for the ceramic with x = 0.025.     

Growth and electrical properties of Na0.5Bi0.5TiO3–K0.5Bi0.5TiO3 lead-free single crystals by the TSSG method

A series of NBT-KBT lead-free crystals with dimensions of Φ 35×10 mm were successfully grown by the TSSG method. The as-grown crystals possess rhombohedral perovskite structure at room temperature. The curves ε(T) for all crystals show two abnormal dielectric peaks. The depolarization temperatures T_d derived from the first peak of curves tan δ(T) vary with the KBT content, which are 130, 150, 140, and 115 °C respectively, for (100−x)NBT−xKBT (x=5, 8, 12, 15) crystals, being well consistent with the T_d obtained from the temperature dependence of k_t. A notable thermal hysteresis, ΔT≈35 °C, for ferroelectric-antiferroelectric phase transition was also disclosed for 92NBT-8KBT crystal. The investigation of orientation dependence for electrical properties disclosed the dielectric parameters show weak anisotropy. The piezoelectric constants (d₃₃) are 147, 175, 205, 238 pC/N and the values of k_t are 38%, 52%, 52%, 54%, respectively for (100−x)NBT−xKBT (x=5, 8, 12, 15) crystals.     

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。     

High- and low-field dielectric responses and ferroelectric properties of (Bi0.5Na0.5)Zr1−xTixO3 ceramics

Bismuth sodium zirconate titanate (Bi_0.5Na_0.5)Zr_1?xTi_xO₃ with (x=0, 0.1, 0.2, 0.3, 0.4, 0.5 and 0.6) ceramics was fabricated by a conventional sintering technique at 850–1000 °C for 2 h. From X-ray diffraction study, three regions of different phases were observed in the ceramic system; i.e., orthorhombic phase region (0≤x≤0.2), mixed-phase region (0.3≤x≤0.4), and rhombohedral phase region (0.5≤x≤0.6). It was observed that the phase evolution from orthorhombic to rhombohedral symmetry resulted in a noticeable increase of the dielectric properties. The results from the high- and low-field dielectric responses indicated that the dielectric properties of both BNZ and BNZT ceramics were dominantly attributed to the reversible contribution. It was also noticed that grain size showed only partial influence on the increase of low-field dielectric constant in Ti-rich BNZT ceramic.     

Structural,dielectric and ferroelectric properties of Ba1−x(Bi0.5Na0.5)xTiO3 ceramics

Lead free Ba_1?x(Bi_0.5Na_0.5)_xTiO₃ (x=0, 0.02, 0.04, 0.06, 0.08, 0.1) ferroelectric ceramics were synthesized by conventional solid state reaction technique. Sintering was done at 1200 °C for 2 h in air atmosphere. The final products have tetragonal symmetry with decreasing c/a ratio confirmed by X-ray diffraction analysis. The grain size varies between 300 nm to 1000 nm for x=0 to 0.1. With increase in Bi_0.5Na_0.5TiO₃ [BNT] content, the room temperature permittivity decreases whereas the Curie temperature (T_c) increases and its highest value was found to be 155 °C for 10 mol% of BNT addition. The ceramics show stable and low dielectric loss characteristics. The remnant polarization (P_r) and the coercive field (E_c) increases monotonously with increase in BNT content. The highest value of 2P_r (=17 μC/cm²) and 2E_c (=22 Kv/cm) was obtained for x=10 mol% BNT addition.     

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.