(Bi0.5Na0.5)TiO3 ferroelectric ceramics: Achieving high depolarization temperature and improved piezoelectric properties

(Bi_1/2Na_1/2)TiO₃-based materials have received much attention due to large electro-strain and high piezoelectric constant (d₃₃), but the tough issue is that the existence of inherent depolarization temperature (T_d) limits the temperature stability and application temperature range. Previously, reports about the formation of BNT/oxide (i.e., ZnO, Al₂O₃) composites thought that T_d can be deferred to a higher temperature and then thermal depolarization improves. However, the deferred T_d of BNT/oxide composites is limited, accompanied by a low d₃₃. Here, we design the {[Bi_0.5(Na_0.8K_0.2)_0.5]_1-xPb_x}TiO₃ ceramics, leading to a big shift of T_d from 77 ℃ to 390 ℃. Large d₃₃ (140 pC/N) and high T_d (∼263 ℃) can be simultaneously achieved for the sample with Pb=0.05, and T_d could be further deferred higher (390 ℃) for Pb=0.20. The off-centre displacement of Pb induced by Pb-O hybridization in the PbO₁₂ polyhedron and ferroelectric order stabilized by the addition of Pb can provide the driving force to strengthen the ferroelectric order, and then promote the thermal stability.     

Mechanism of Bi0.5Na0.5TiO3 and Bi4.5Na0.5Ti4O15 template synthesis during topochemical microcrystal conversion and texturing of Bi0.5(Na0.8K0.2)0.5TiO3 piezoelectric ceramics

The mechanism by which Bi_0.5Na_0.5TiO₃ and Bi_4.5Na_0.5Ti₄O₁₅ templates are synthesized via a topochemical microcrystal conversion method using Bi₄Ti₃O₁₂ precursor and TiO₂ particles was investigated based on their crystal structures. The Bi_0.5Na_0.5TiO₃ template consisted of a mixture of plate-like and equiaxed particles, whereas the Bi_4.5Na_0.5Ti₄O₁₅ template consisted only of plate-like particles. The size of the plate-like and equiaxed particles was dependent on the size of the Bi₄Ti₃O₁₂ precursor and TiO₂ particles, respectively. The Lotgering factor and piezoelectric constant of textured Bi_0.5(Na_0.8K_0.2)_0.5TiO₃ ceramics prepared using the Bi_0.5Na_0.5TiO₃ template were lower than those of the textured Bi_0.5(Na_0.8K_0.2)_0.5TiO₃ ceramics prepared from the Bi_4.5Na_0.5Ti₄O₁₅ template. This can be attributed to the small amount of plate-like particles in the Bi_0.5Na_0.5TiO₃ template caused by the inevitable co-existence of equiaxed particles.     

Influence of secondary phases on ferroelectric properties of Bi0.5Na0.5TiO3 ceramics

The effects of secondary phases on ferroelectric properties of Bi_0.5Na_0.5TiO₃ (BNT) have been studied. Ceramic powders were prepared by solid state reaction employing different sintering temperatures and characterized by X-ray diffraction (XRD), Scanning Electron Microscopy and impedance spectroscopy. The perovskite structure was detected by XRD; together with small peaks corresponding to a secondary phase assigned to the Na₂Ti₆O₁₃-based phase in calcined powders. In addition, morphology and the content of the secondary phase were modified by the sintering temperatures, affecting the ferroelectric properties, and ac and dc conductivities. We believe that our results can benefit not only the understanding of BNT ceramics, but also expand the range of applications.     

Synthesis of Na0.5Bi0.5TiO3 whiskers and their nanoscale piezoelectricity

The perovskite structured lead-free system Na_0.5Bi_0.5TiO₃ (NBT) whiskers were synthesized from whiskers of layered tunnel structured Na₂Ti₆O₁₃ (NT), using a topochemical route. Both NT and NBT whiskers show high aspect ratios with an average length of 15 µm and diameter of 1 µm. By prolonging the reaction time from 2 h to 6 h at 900 °C, NT whiskers with monoclinic phase completely transformed to NBT whiskers with pseudocubic phase. Typical strip-like nanodomains are observed in a NBT whisker, which are parallel to each other. The piezoelectric response amplitude for a NBT whisker indicates a large electric field induced strain, corresponding to a S_max/E_max value of as high as 300 pm/V. This work provides an in-depth instruction to prepare pure NBT whiskers, and gives the detailed piezoelectricity of NBT whiskers to promote their applications in energy harvesting and micro-electromechanical systems.     

Composition and microstructure of Na0.5Bi0.5TiO3 ceramics with excess Bi

In the present work, Na_0.5Bi_0.5TiO₃ (NBT) ceramics with the addition of excess Bi in two different ways – before calcination and before sintering – are considered, revealing how the excess Bi affects their microstructure and chemical content. Average grain size is seen to decrease, with the grain size distribution becoming less diffused at higher excess Bi concentrations. The reason for such a feature is the shift of the sintering temperature region where the abnormal grain growth starts to contribute towards higher temperatures. The influence of excess Bi is more pronounced in the case if it is added before calcination. It was discovered that a small amount of excess Bi helps to prevent the formation of Bi-deficient inclusions. While, high concentrations of excess Bi induce the formation of Bi-rich inclusions – most probably Na_0.5Bi_4.5Ti₄O₁₅. Possible mechanisms of formation of both types of inclusions are discussed in detail. Instead of Bi over-stoichiometry, elevated Na content and slightly lower O content were detected in the matrix grains of the sintered NBT ceramics prepared with excess Bi. These deviations increase upon increasing the added excess Bi concentration. The presence of another, Na-rich phase, is assumed, which could not be detected by X-ray diffraction or by energy-dispersive X-ray analysis.     

Enhancement of piezoelectric catalysis of Na0.5Bi0.5TiO3 with electric poling for dye decomposition

In this work, the performance of solid-phase sintered Na_0.5Bi_0.5TiO₃ ceramic powder catalyst is investigated for Rhodamine B (RhB) dye decomposition under different electric poling fields. As a result of the vibration excitation, the piezoelectric catalytic decomposition ratio of the poled Na_0.5Bi_0.5TiO₃ for RhB dye wastewater increases from 10.84% to 51.32% as the electric poling field increases from 0 to 0.5 kV/mm. The improved piezoelectric catalytic activity could be attributed to a rise in the piezoelectric performance of Na_0.5Bi_0.5TiO₃ after electric poling. The addition of the different types of radical scavengers in piezoelectric catalysis further proves that a large amount of superoxide-free radicals and a small number of hydroxyl radicals participate in the catalytic reaction. Our results demonstrate that electric poling, as a simple and effective method of improving piezoelectric catalysis, has potential applications in dye-containing wastewater treatment.     

Structure and ferroelectric behaviour of Na0.5Bi0.5TiO3-KNbO3 ceramics

Lead-free piezoelectric ceramics, (1?x)Na_0.5Bi_0.5TiO₃-xKNbO₃ (NBT-xKN), with x?=?0.02–0.08 were fabricated by solid-state reaction and sintering. The crystal structures and dielectric properties were measured for different KN contents. All compositions in the unpoled, as-sintered state were found to be single-phase pseudo-cubic. However, typical ferroelectric behaviour, with well-saturated polarisation-electric field hysteresis loops, was observed for certain compositions at high electric field levels. It is shown using high-energy synchrotron X-ray diffraction that the application of the electric field induced an irreversible structural transformation from the nano-polar pseudo-cubic phase to a ferroelectric rhombohedral phase. The changes in lattice elastic strain and crystallographic texture of a poled NBT-0.02KN specimen as a function of the grain orientation, ψ, conform well to those expected for a conventional rhombohedrally distorted perovskite ferroelectric ceramic. The dielectric permittivity-temperature relationships for all compositions exhibit two transition temperatures and a frequency-dependent behaviour that is typical of a relaxor ferroelectric. The transition temperatures and grain size decrease with the increasing KN content.     

Dielectric temperature stability of Nb-modified Bi0.5(Na0.78K0.22)0.5TiO3 lead-free ceramics

In this study, the phase structure, microstructure and dielectric properties of Bi_0.5(Na_0.78K_0.22)_0.5(Ti_1-xNb_x)O₃ lead-free ceramics prepared by traditional solid phase sintering method were studied. The second phase pyrochlore bismuth titanate (Bi₂Ti₂O₇) was produced in the system after introduction of Nb⁵⁺. The dielectric constant of the sample (x = 0.03) sintered at 1130 °C at room temperature reached a maximum of 1841, and the dielectric loss was 0.045 minimum. It had been found that the K⁺ and Nb⁵⁺ co-doped Bi_0.5Na_0.5TiO₃ (BNT) lead-free ceramics exhibited outstanding dielectric-temperature stability within 100–400 °C with T_cc ≤±15%. Result of this research provides a valuable reference for application of BNT based capacitors in high temperature field.     

Bi0.5Na0.5TiO3基无铅压电陶瓷的研究进展

随着经济的发展和人们环保意识的增强,无铅压电陶瓷的研究和开发越来越引起人们的重视.由于钛酸铋钠(Bi0.5Na0.5TiO3,简称为BNT)基无铅压电陶瓷具有良好的铁电性和高的剩余极化引起了广大学者的关注.本文分析了BNT基无铅压电陶瓷的研究进展,其中晶粒取向生长技术是提高其压电性能的一个重要途径.本文还介绍了一种溶剂热法制备织构化BNT基无铅压电陶瓷的方法.     

Enhanced optical transmittance and energy-storage performance in NaNbO3-modified Bi0.5Na0.5TiO3 ceramics

Dielectric ceramics with both excellent energy storage and optical transmittance have attracted much attention in recent years. However, the transparent Pb-free energy-storage ceramics were rare reported. In this work, we prepared transparent relaxor ferroelectric ceramics (1 − x)Bi_0.5Na_0.5TiO₃–xNaNbO₃ (BNT–xNN) by conventional solid-state reaction method. We find the NN-doping can enhance the polarization and breakdown strength of BNT by suppressing the grain growth and restrained the reduction of Ti⁴⁺ to Ti³⁺. As a result, a high recoverable energy-storage density of 5.14 J/cm³ and its energy efficiency of 79.65% are achieved in BNT–0.5NN ceramic at 286 kV/cm. Furthermore, NN-doping can promote the densification to improve the optical transmittance of BNT, rising from ∼26% (x = 0.2) to ∼32% (x = 0.5) in the visible light region. These characteristics demonstrate the potential application of BNT–xNN as transparent energy-storage dielectric ceramics.     

Effect of sintering temperature on the depolarization behavior of (Bi0.5Na0.5)TiO3-based ceramics

(Bi_0.5Na_0.5)TiO₃ (BNT)-based ferroelectric ceramics have drawn extensive attention because of their excellent electrical properties and interesting depolarization behavior. However, the poor thermal stability of electrical properties limits their practical application. In this work, the effect of sintering temperature (T_s) on the depolarization behavior of BNT-based ceramics was systematically investigated. It is found that the depolarization temperature T_d determined from pyroelectric measurement tends to decrease with increasing T_s, which indicates that lower T_s defers the ferroelectric-relaxor (FE-RE) phase transition. However, for the samples sintered at higher T_s (such as 1180°C), although the T_d is reduced, the thermal stability is better compared with the sample sintered at lower T_s (1100°C) because the diffuse behavior of the FE-RE phase transition is suppressed. According to these results, we propose that the thermal stability of electrical properties for BNT-based ceramics is not only related to high T_d, but also to the diffuse degree of phase transition.     

Investigation of the mechanism of domain switching in different Na0.5Bi0.5TiO3 microstructures

Several researches have studied the physical properties of hydrothermally-synthesized low dimensional piezoelectric nanostructures. However, the obtained piezoelectric coefficient is not high and the relationship between physical properties and microstructures is still neglected. Here we report the piezoelectric and ferroelectric properties of different lead-free sodium bismuth titanate (Na_0.5Bi_0.5TiO₃, NBT) microstructures synthesised with hydrothermal routes and give visualization of domain structures using piezoresponse force microscopy. The NBT nanowire exhibits better local piezoelectric response compared with NBT spherical aggregates and microcubes and other one-dimensional materials prepared by hydrothermal method and the large piezoelectric coefficient of nanowire was explained by observed regular stripe domain structures. Moreover, it is found that there are different domain configurations at the top and side of the nanowire under the external electrical fields, which don't change the regular stripe domain structure but lead to the movement of domain boundaries. By finite element modeling, it attributes to the different electric potential distributions from tip within the nanowire.     

Low hysteresis and temperature stable electrostrain in 0.97(0.94Na0.5Bi0.5TiO3-0.06BaTiO3)-0.03AgNbO3/xZnO composite ceramics

Na_0.5Bi_0.5TiO₃-based solid solutions are one of the most promising lead-free piezoelectric candidates since they can be easily tailored to exhibit large electrostrain. However, the large hysteresis and temperature-dependence of the electrostrain response are longstanding obstacles for their practical applications. In the present study, 0–3 type composites were developed with 0.97(0.94Na_0.5Bi_0.5TiO₃-0.06BaTiO₃)-0.03AgNbO₃ (NBT-6BT-3AN) matrix phase and ZnO inclusions. The optimum addition of 5 wt.% ZnO in the composites leads to reduction in hysteresis of electrostrain by 35% in comparison with pure NBT-6BT-3AN at room temperature. Meanwhile, electrostrain of the composites maintains superior temperature stability, with a variance of less than ±10% in the temperature range between 25 and 125 °C. The reason for the improvement of electrostrain is proposed to be attributed to the ergodic/nonergodic mixture phases induced by residual stress between the inclusion and matrix, as well as the phase evolution caused by the incorporation of Zn²⁺ into the matrix. Therefore, this work provides a new strategy to improve the electromechanical properties of Na_0.5Bi_0.5TiO₃-based ceramics.     

Construction of multi-domain coexistence enhanced piezoelectric properties of Bi0.5Na0.5TiO3-based thin films

Although the multi-phase coexistence makes Bi_0.5Na_0.5TiO₃-based piezoelectric thin films possess stronger piezoelectric properties and more spacious application prospects in electronic devices, the domain reversal mechanism of Bi_0.5Na_0.5TiO₃-based thin films cannot be accurately understood due to the size effect. In this study, the relationship between domain structure and piezoelectric properties of the (0.94-x)Bi_0.5Na_0.5TiO₃-0.06BaTiO₃-xBi(Fe_0.95Mn_0.03Ti_0.02)O₃ thin films are studied by using visualization technology PFM, structure and electrical properties characterizations. The results show that the addition of Bi(Fe_0.95Mn_0.03Ti_0.02)O₃ creates a long-range ordered/short-range disordered nanodomain coexisting structure. This kind of coexisting domain structure can realize the long-range reversal driven by disordered nanodomains under the external electric field, reduce the potential barrier and the hysteresis, and significantly enhance the piezoelectric properties of the thin films. Under the same conditions, the piezoelectric properties of the 0.94Bi_0.5Na_0.5TiO₃-0.06BaTiO₃ thin films are enhanced nearly 2.3 times. This provides a reference for exploring the physical mechanism of high performance lead-free piezoelectric thin films.     

High energy storage density realized in Bi0.5Na0.5TiO3-based relaxor ferroelectric ceramics at ultralow sintering temperature

The miniaturization and integration trend of electronic applications requires high energy storage performance, and the development of multilayer ceramic capacitors (MLCC) demands the compatibility between ceramic sintering temperature and co-firing temperature of metal electrodes. Herein, we obtained a high recoverable energy storage density and a low sintering temperature simultaneously in 0.5(Bi_0.5Na_0.5)TiO₃-0.5SrTiO₃-x mol% CuO (0.5BNT-0.5ST-x mol% CuO) via the combination of adding CuO sintering aid and citrate sol-gel synthesis method. The optimum sintering temperature decreases significantly from 1130 °C for x = 0 to 820 °C for x = 2.0. The ceramic of 0.5BNT-0.5ST-1.5 mol% CuO exhibits a large W_rec of 2.20 J/cm³ and η of 72.39% under 230 kV/cm. Furthermore, the same sample also possesses a large C_D of 1740.97 A/cm², an extremely high P_D of 139.28 MW/cm³ and an ultrafast discharge speed of 82 ns. These merits reveal that the ceramic of 0.5BNT-0.5ST-1.5 mol% CuO has great potential in practical MLCC production.     

Luminescence and electrical properties of Eu-modified Bi0.5Na0.5TiO3 multifunctional ceramics

The Eu³⁺-modified Bi_0.5Na_0.5TiO₃ (BNT) ceramics have been fabricated by the solid-state reaction method. The impact of Eu³⁺ doping on the structure, photoluminescence, and electrical properties has been studied by XRD, SEM, PL spectra, and LCR meter. X-ray diffraction analysis reveals that the crystal structure of the samples is well matched with the trigonal perovskite, and the optimal temperature of presintering is 880°C. The Eu³⁺-doped BNT ceramics show excellent red fluorescence at 614 nm corresponding to the ⁵D₀→⁷F₂ transition of Eu³⁺ under 466 nm excitation and relatively long fluorescence lifetime. The BNT-0.02Eu ceramic density is up to 5.68 g/cm³ and the relative density is up to 94.6% with sintering temperature 1075°C. The piezoelectric constant (d₃₃) of samples has been significantly improved up to 110 pC/N by Eu³⁺ doping. The BNT-0.03Eu ceramic presintered at 880°C and sintered at 1050°C has good dielectric properties and excellent luminescence properties. Eu³⁺-doped BNT ceramics make it potential applications for novel integrated electro-optical and multifunctional devices.     

Realizing excellent energy storage properties in Na0.5Bi0.5TiO3-based lead-free relaxor ferroelectrics

Development of lead-free dielectric capacitors with high recoverable energy storage density (W_rec), large energy storage efficiency (η), and wide usage temperature range are in high demanded for pulse power systems. Herein, we realized the enhancement of energy storage properties [high W_rec = 3.76 J/cm³, large η = 78.80 %, and broad operating temperature range (20?180 °C)] in lead-free Na_0.5Bi_0.5TiO₃ (BNT)-based relaxor ferroelectrics via component regulation. Excellent energy storage properties mainly originate from suppressing early polarization saturation and improving dielectric breakdown strength (E_b). Domain evolution on the nanoscale offers robust support to suppression of early polarization saturation. The enhancement of E_b can be derived from the contribution of the Mg-rich phase, which is also corroborative via first-principles calculation on basis of density functional theory (DFT). We believe that these findings in this work may provide a practicable guideline to build new lead-free ceramics for electrical energy storage applications.     

Synthesis of platelike CaTiO3 particles by a topochemical microcrystal conversion method and fabrication of textured microwave dielectric ceramics

Platelike CaTiO₃ particles with an orthorhombic perovskite structure have been synthesized by topochemical microcrystal conversion (TMC) from platelike precursor particles of the layer-structured CaBi₄Ti₄O₁₅ at 950 °C. The CaTiO₃ particles inherited and retained the shape of the precursor particles with a thickness of approximately 0.3 μm, and a width of 2–6 μm. XRD analysis showed that in the TMC reaction, the crystallographic {0 0 1} plane of CaBi₄Ti₄O₁₅ is converted into the {1 0 0} plane of CaTiO₃. Using the platelike CaTiO₃ particles as templates in the templated grain growth method, dense {1 0 0} grain-oriented CaTiO₃ ceramics having a {1 0 0} orientation could be fabricated at sintering temperatures between 1350 and 1500 °C. The maximum orientation factor reached 99.7% at 10% of template. It was found that texturing improves microwave dielectric low-loss properties, providing a 1.55 times higher Q_f value of 9310 GHz in textured ceramics compared to that of 6005 GHz in non-textured ceramics.     

Quenching-circumvented ergodicity in relaxor Na1/2Bi1/2TiO3-BaTiO3-K0.5Na0.5NbO3

Quenching alkaline bismuth titanates from sintering temperatures results in increased lattice distortion and consequently higher depolarization temperature. This work investigates the influence of quenching on the ergodicity of relaxor Na_1/2Bi_1/2TiO₃-BaTiO₃-K_0.5Na_0.5NbO₃. A distinct departure from ergodicity is evidenced from the increase in remanent polarization and the absence of frequency dispersion in the permittivity response of poled samples. Further, the samples exhibit enhanced negative strain upon application of electric field, indicating proclivity towards correlated polar nanoregions, corroborated by the enhanced tetragonal distortion. As a result, ergodic relaxor Na_1/2Bi_1/2TiO₃-6BaTiO₃-3K_0.5Na_0.5NbO₃ exhibits a depolarization temperature of 85°C with a 60% increase in remanent polarization and approximately a threefold increase in remanent strain upon quenching. Quenching-induced changes in the local environment of Na⁺ and Bi³⁺ cations hinder the development of ergodicity promoted by the A-site disorder. These results provide new insight into tailoring ergodicity of relaxor ferroelectrics.