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.     

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.     

Analysis of high temperature reduction process of Na0.5Bi0.5TiO3-based ceramics

Lead-free metamaterials with enormous effective apparent piezoelectric response has been fabricated by applying an asymmetric chemical reduction to Na_0.5Bi_0.5TiO₃ (NBT)-based ceramics. To achieve high performance, optimization of the reduction conditions is required. In this study, we analyzed the effect of reduction temperature and time on the reduction thickness of NBT-based ceramics. We found that the reduction reaction between NBT-based ceramics and graphite is an interface reaction rate-controlled process. The reduction thickness has a linear relationship with the reaction time at a fixed reduction temperature. The lower activation energy of NBT-based ceramics than that of lead-based materials indicates the lead-free ceramics are easier to be reduced. The effect of the reduction on the flexoelectric-like response was further explored, and the maximum response (?>1 mC/m) was measured in the ceramics having a reduction-thickness-to-total-thickness ratio of around 0.28. This study provides a guideline to optimize the fabrication conditions of the NBT-based metamaterials.     

The influence of Ti-nonstoichiometry in Bi0.5Na0.5TiO3

The influence of Ti-nonstoichiometry in BNT was investigated using XRD, SEM/EDX and electrical measurements. It is shown that nonstoichiometric compositions of BNT derived materials tend to maintain stoichiometry by forming a secondary phase like TiO₂ or by the evaporation of volatile compounds like Bi₂O₃ and Na₂O. Due to this ability, variations of the Ti-content can be used to control the grain size of the material with little impact on electrical properties. The data also implies that the used processing temperatures lead to evaporation approximately 2 mol% of A-site cations during preparation since the sample with 1 mol% Ti-deficiency still shows TiO₂ secondary phase.     

Nanoscale origins of small hysteresis and remnant strain in Bi0.5Na0.5TiO3-based lead-free ceramics

BiAlO₃-doped Bi_0.5Na_0.5TiO₃-Bi_0.5K_0.5TiO₃ (BA-doped BNT-BKT) ceramics are greatly concerned due to their sufficient electric-field-induced strain with small hysteresis and remnant strain for high precision positioning devices and other actuators. In this paper, the structural analysis especially the high-resolution transmission electron microscope (HRTEM) is used to reveal the origin of excellent properties obtained in 0.96(0.75BNT-0.25BKT)-0.04BA, which exhibits a large strain of 0.21% at ∼70 kV/cm, a small strain hysteresis of only 24% and a near-zero remnant strain. Using HRTEM, the antiferroelectric nano-domains composited by three variants of in-phase a⁰a⁰c⁺ octahedral tilting coexisted with the remnant ferroelectric nano-domains of anti-phase a⁻a⁻a⁻ octahedral tilting are directly identified. Then a continuous tilting model is proposed to interpret the gradually transitional tilting involving nano-domains leading to the small hysteresis and near-zero remnant strain. The findings may pave a way for further optimizing the properties through creating stable antiferroelectric nano-domains in BNT-based ceramics and the analogues.     

Nanoscale origins of small hysteresis and remnant strain in Bi0.5Na0.5TiO3-based lead-free ceramics

BiAlO₃-doped Bi_0.5Na_0.5TiO₃-Bi_0.5K_0.5TiO₃ (BA-doped BNT-BKT) ceramics are greatly concerned due to their sufficient electric-field-induced strain with small hysteresis and remnant strain for high precision positioning devices and other actuators. In this paper, the structural analysis especially the high-resolution transmission electron microscope (HRTEM) is used to reveal the origin of excellent properties obtained in 0.96(0.75BNT-0.25BKT)-0.04BA, which exhibits a large strain of 0.21% at ～70 kV/cm, a small strain hysteresis of only 24% and a near-zero remnant strain. Using HRTEM, the antiferroelectric nano-domains composited by three variants of in-phase a⁰a⁰c⁺ octahedral tilting coexisted with the remnant ferroelectric nano-domains of anti-phase a^?a^?a^? octahedral tilting are directly identified. Then a continuous tilting model is proposed to interpret the gradually transitional tilting involving nano-domains leading to the small hysteresis and near-zero remnant strain. The findings may pave a way for further optimizing the properties through creating stable antiferroelectric nano-domains in BNT-based ceramics and the analogues.     

Microstructure,dielectric, piezoelectric,and ferroelectric properties of fine-grained 0.94Na0.5Bi0.5TiO3-0.06BaTiO3 ceramics

For preparing fine-grained 0.94Na_0.5Bi_0.5TiO₃-0.06BaTiO₃ lead-free ferroelectric ceramics, the precursor powders were synthesized via sol-gel method and calcined at various temperatures. The precursor powders calcined at 520 °C, 550 °C, and 600 °C exhibit mean grain sizes of 30 ± 4 nm, 54 ± 3 nm, and 78 ± 5 nm, respectively. By optimizing the synthesis parameters, the fine-grained ceramics with high relative densities (>97%) and mean grain size around 100 nm were prepared. The ferroelectric, dielectric, and piezoelectric behavior were investigated. The ceramics prepared using the different precursor powders show different piezoelectric, ferroelectric, and dielectric behavior. The ceramic calcined at 550 °C and sintered at 900 °C exhibits the breakdown strength higher than 85 kV/cm, which exhibits the maximum polarization of 38.4 ± 0.3 μC/cm², remanent polarization of 20.6 ± 0.4 μC/cm².     

Highly-reliable dielectric capacitors with excellent comprehensive energy-storage properties using Bi0.5Na0.5TiO3-based relaxor ferroelectric ceramics

The development of capacitors with high reliability and good comprehensive performances is of great significance for practical applications. In this work, lead-free relaxor ferroelectric (FE) ceramics of (1-x)(0.5(Bi_0.5Na_0.5)TiO₃-0.5SrTiO₃)-xBi(Mg_2/3Nb_1/3)O₃ ((1-x)(BNT-ST)-xBMN) were prepared by a conventional solid-state reaction method. The introduction of BMN was found to enhance local structure disorder, leading to the significantly reduced size of FE nanodomains, which is responsible for the slim polarization-electric field hysteresis loops. A giant energy-storage density of 6.62 J/cm³ and a high efficiency of 82 % can be achieved simultaneously under a moderate electric field of 34 kV/mm at x = 0.08. It also exhibits high discharge density ～ 2.74 J/cm³, large power density ～ 248 MW/cm³ and ultrafast discharge rate ～ 28 ns at 20 kV/mm in addition to excellent temperature (10–130 °C) and frequency (1–100 Hz) stabilities. These results demonstrate that the (1-x)(BNT-ST)-xBMN ceramic system is a promising lead-free candidate for advanced pulsed power capacitor applications.     

Enhanced pyroelectric response from domain-engineered lead-free (K0.5Bi0.5TiO3-BaTiO3)-Na0.5Bi0.5TiO3 ferroelectric ceramics

Enhanced pyroelectric response is achieved via domain engineering from [001] grain-oriented, tetragonal-phase, lead-free 0.2(2/3K_0.5Bi_0.5TiO₃-1/3BaTiO₃)-0.8Na_0.5Bi_0.5TiO₃ (KBT-BT-NBT) ceramics prepared by a templated grain growth method. The [001] crystallographic orientation leads to large polarization in tetragonal symmetry; therefore, texturing along this direction is employed to enhance the pyroelectricity. X-ray diffraction analysis revealed a Lotgering factor (degree of texturing) of 93 % along the [001] crystallographic direction. The textured KBT-BT-NBT lead-free ceramics showed comparable pyroelectric figures of merit to those of lead-based ferroelectric materials at room temperature (RT). In addition to the enhanced pyroelectric response at RT, an enormous enhancement in the pyroelectric response (from 1750 to 90,900 μC m^?2 K^?1) was achieved at the depolarization temperature because of the sharp ferroelectric to antiferroelectric phase transition owing to coherent 180° domain switching. These results will motivate the development of a wide range of lead-free pyroelectric devices, such as thermal sensors and infra-red detectors.     

Structural evolution and electrical properties of Na0.5Bi0.5TiO3-CoFe2O4 ceramics with embedded structures

Lead-free 0.9Na_0.5Bi_0.5TiO₃ − 0.1CoFe₂O₄ (0.9NBT-0.1CFO) composite ceramics with novel embedded microstructures were synthesized by an in-situ sol-gel method. The structural evolution, ferroelectricities and dielectricities were studied. The embedded structures were formed around 1000 °C − 1100 °C with contributions of the strong grain boundary mobility and small size of CFO grains, and then were destroyed at 1150 °C. The 0.9NBT-0.1CFO ceramic sintered at 1100 °C showed the optimal ferroelectric hysteresis loop with a remanent polarization of ~ 52 μC/cm². Anomaly peaks in the temperature dependent permittivity curves were observed in all ceramics with embedded structures. These Debye-like type peaks generated by the interface effects of NBT and CFO appeared around ~620 °C, and could reach relatively large values of ~15000 at 100 kHz. The change rate of permittivity between zero magnetic field and 500 Oe reached 2.4%, indicating a noteworthy magnetoelectric effect.     

Improved electric-field-induced strain and strong photoluminescence properties in novel Er3+-modified 0.93Bi0.5Na0.5TiO3-0.07BaTiO3 multifunctional ceramics

Recently, the progress of electronic devices toward miniaturization has strongly promoted development of multifunctional materials possessing multiple desirable properties. In this study, we develop and fabricate 0.93Bi_0.5Na_0.5TiO₃-0.07BaTiO₃-xEr multifunctional ceramics which show simultaneously considerable electric-field-induced strain and bright green light emission properties. With the introduction of Er³⁺, the ceramics gradually transform from non-ergodic relaxor phase to ergodic relaxor phase which could reversibly transform to ferroelectric phase under the electric field. As a result, with improving Er³⁺ content, the shape of the polarization-electric field loops of the ceramics become pinched, and it is obvious that the negative strain disappears while the positive strain gradually increases and reaches a maximum value 0.46% at x = 1.2 mol%. Besides, After the ceramics are poled, the light emission peak are greatly enhanced attributed to the decreased crystal symmetry and increased domain size, and is the strongest at x = 1.2 mol%. These results indicate that 0.93Bi_0.5Na_0.5TiO₃-0.07BaTiO₃-xEr ceramics are good candidates for developing multifunctional optoelectronic devices.     

Structural,thermal, dielectric and ferroelectric properties of K0.5Bi0.5TiO3 ceramics

Dense K_0.5Bi_0.5TiO₃ (KBT) lead-free ceramics were prepared by conventional solid reaction route. Their temperature behavior (up to 600 °C) was investigated by X-ray diffraction, DSC, dielectric spectroscopy and electric field-polarization technique. The first temperature dependent Raman scattering studies were also performed. X-ray and Raman scattering results show that samples exhibit a single perovskite structure with cubic symmetry at temperatures higher than approximately 400 °C and with coexistence of the cubic and tetragonal phases below this temperature. Two structural phase transitions between tetragonal phases in temperature range 200–225 °C and between tetragonal and cubic ones near 400 °C are observed. The content of the tetragonal phase increases with decreasing temperature and at room temperature it reaches more than 70%. Temperature- dependent P-E loops and pyroelectric data revealed a polar behavior in KBT up to about 400 °C, which means that the intermediate phase (～270–380 °C) is rather ferroelectric than antiferroelectric.     

Enhanced energy storage properties of Bi0.5Na0.5TiO3-based ceramics via regulating the doping content and sintering temperature

Eco-friendly lead-free energy-storage ceramics featuring high energy storage properties and ultra-high stability have been regarded to be one of the most potential materials in the field of energy storage. In this work, a new element system, (1-x)(0.6Bi_0.5Na_0.5TiO₃-0.4SrTiO₃)-xBi[Zn_2/3(Nb_0.5Ta_0.5)_1/3]O₃ ((1-x)BNST-xBZNT) lead-free ceramics, were synthesized via a conventional solid-state sintering technology. And the phase structure, microstructure and energy storage properties of the (1-x)BNST-xBZNT ceramics were comprehensively studied. After the introduction of BZNT, the average grain size of the materials is greatly decreased, thereby enhancing the dielectric breakdown strength (DBS). Additionally, the thermal stability of the ceramics is significantly improved via regulating the doping content and sintering temperature. Furthermore, the ferroelectric long-range order of the ceramics is decomposed into randomly-oriented polar nano-domains (PNRs) after introducing BZNT, leading to strong relaxor behavior and significantly reducing remanent polarization (P_r). As a result, even under a relatively low electric field of 139 kV/cm, the 0.98BNST-0.02BZNT ceramic sintered at 1150 °C possesses high values of energy storage efficiency (η) value of 92.78% and total energy storage density (W_tot) of 1.67 J/cm³ as well as remarkable thermal stability (25–175 °C), frequency stability (20–70 Hz) and fatigue resistant stability (10⁰-10⁵ cycles). This investigation provides a useful reference for developing advanced energy storage ceramics by regulating the doping content and sintering temperature.     

Thermally-stable large strain in Bi(Mn0.5Ti0.5)O3 modified 0.8Bi0.5Na0.5TiO3-0.2Bi0.5K0.5TiO3 ceramics

(1-x)[0.8Bi_0.5Na_0.5TiO₃-0.2Bi_0.5K_0.5TiO₃]-xBi(Mn_0.5Ti_0.5)O₃ (x = 0–0.06, BNKMT100x) lead-free ferroelectric ceramics were prepared via solid state reaction method. Bi(Mn_0.5Ti_0.5)O₃ induces a structure transition from rhombohedral-tetragonal morphotropic phases to pseudo-cubic phase. Moreover, the wide range of compositions within x = 0.03–0.055 exhibit large strain of 0.31%–0.41% and electrostrictive coefficient of 0.027–0.041 m⁴/C². Especially, at x = 0.04, the large strain and electrostrictive coefficient are nearly temperature-independent in the range of 25–100 °C. The impedance analysis shows the large strain and electrostrictive coefficient originate from polar nanoregions response due to the addition of Bi(Mn_0.5Ti_0.5)O₃.     

Effect of chemical inhomogeneity on domains and ferroelectric properties of Fe‐modified 0.77Bi0.5Na0.5TiO3–0.23SrTiO3

Lead‐free 0.77(Bi_0.5Na_0.5)TiO₃–0.23Sr(Ti_1?xFe_x)O₃ (x = 0, 0.04) (BNT–23STF_x) was prepared using a conventional solid‐state reaction route. The effects of Fe‐modification on the chemical homogeneity from a μm scale perspective, the core‐shell domains structures, and the ferroelectric properties were investigated. The chemical homogeneity was analyzed using energy dispersive X‐ray mapping in scanning transmission electron microscopy mode, and the field‐dependent behaviors of strain and polarization were obtained to determine the ferroelectric properties. Substituting Fe³⁺ for Ti⁴⁺ resulted in completely different electrical behavior and properties, despite similar XRD patterns and microstructures. The Fe‐substitution promoted the mobility of Sr²⁺ ions in the BNT phase and, as a consequence, the chemical homogeneity increased and the core‐domains collapsed. Extending the ceramic processing, such as milling time and sintering time, affected domain distribution and compositional inhomogeneity, which led to a gradual transformation from ferroelectric to relaxor.     

Effect of closed pores on dielectric properties of 0.8Na0.5Bi0.5TiO3-0.2K0.5Bi0.5TiO3 porous ceramics

Porous 0.8Na_0.5Bi_0.5TiO₃-0.2K_0.5Bi_0.5TiO₃ ceramics are fabricated via the pore-forming agent method with polymethyl methacrylate (PMMA) and stearic acid (SA) as pore forming agents, and microstructure observations demonstrate that the porosity, pore shape, and pore sizes can be controlled by the synthesis technology. The dielectric properties of porous ceramics are found not only correlated to the pore-matrix composite model, but also have a significant grain-size effect. Based on the Zener Theory, pining forces exerted by pores on the grain boundary are calculated, to explain the shape effect of pores on grain boundary migration. A phase-field simulation is carried out to investigate pore shape effect on the grain size regulation in porous polycrystalline, and simulation results are in good agreements with experiential results as well as theoretical calculations. Thus, a modified equation is proposed to predict the effective permittivity of the porous piezoelectric ceramics by considering effects of porosity, pore shape and grain size.     

Thickness-dependent switching behavior of 0.8(Bi0.5Na0.5)TiO3-0.2SrTiO3 lead-free piezoelectric thin films

0.8(Bi_0.5,Na_0.5)TiO₃-0.2SrTiO₃ (BNT-0.2ST) thin films, with thicknesses ranging from 90 to 364 nm, were fabricated on platinized silicon substrates by sol-gel method. These films were investigated by switching spectroscopy piezoresponse force microscope (SS-PFM) as a function of frequency at room temperature, revealing the enhanced ferroelectric response in ∼ 210 nm film at all frequencies (0.1 Hz - 1.5 Hz). This enhancement was ascribed to the largest thermally-activated stress at such thicknesses generated during film fabrications. As the temperature of the investigated films increases from room temperature to 200 ^oC, the piezoelectric parameters were obtained from SS-PFM, such as switching polarization (R_s), coercive bias (V₀), work of switching (A_s), maximum strain (S_max), and negative strain (S_neg), indicating an occurrence of phase transition from ferroelectrics to relaxors. This work revealed that thickness plays a crucial role for ferroelectric response and temperature-dependent phase transition in BNT-0.2ST films, since it affects the stress state and switching behavior.     

Effect of cobalt doping on the sintering mechanisms of the lead-free piezoceramic (Bi0.5Na0.5)TiO3

In the search for lead-free piezoelectric ceramics, such as potassium sodium niobate, (K_0.5Na_0.5)NbO₃ (KNN), and bismuth sodium titanate (Bi_0.5Na_0.5)TiO₃ (BNT), high sintering temperatures and the associated volatilization of cations represent a major obstacle to achieve well performing materials. In this study, we investigated the effect of cobalt on the sintering behavior of BNT using in situ thermo-optical dilatometry. The addition of cobalt significantly reduced the sintering temperature at which fully dense ceramic bodies are obtained. This is accomplished by a dual effect of the dopant which facilitates oxygen diffusion: a fraction of the available Ti forms a secondary cobaltous phase. Instead of Ti, some Co is incorporated into BNT at the Ti site, causing oxygen vacancies for charge balancing. To a small degree, the dopant induces liquid phase sintering. At high sintering temperatures, swelling was observed, which was attributed to oxygen release caused by the valence transition from Co³⁺ to Co²⁺.     

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.     

Lead-free BaTiO3-Bi0.5Na0.5TiO3-Na0.73Bi0.09NbO3 relaxor ferroelectric ceramics for high energy storage

A series of (1-x)(0.65BaTiO₃-0.35Bi_0.5Na_0.5TiO₃)-xNa_0.73Bi_0.09NbO₃ ((1-x)BBNT-xNBN) (x = 0–0.14) ceramics were designed and fabricated using the conventional solid-state sintering method. The microstructure, dielectric property, relaxor behavior and energy storage property were systematically investigated. X-ray diffraction results reveal a pure perovskite structure and dielectric measurements exhibit a relaxor behavior for the (1-x)BBNT-xNBN ceramics. The slim polarization electric field (P-E) loops were observed in the samples with x ≥ 0.02 and the addition of Na_0.73Bi_0.09NbO₃ (NBN) could decrease the remnant polarization (P_r) of the (1-x)BBNT-xNBN ceramics obviously. The sample with x = 0.08 exhibits the highest energy storage density of 1.70 J/cm³ and the energy storage efficiency of 82% at 172 kV/cm owing to its submicron grain size and high relative density. These results show that the (1-x)BBNT-xNBN ceramics may be promising lead-free materials for high energy storage density capacitors.