Enhanced piezoelectric properties of sodium bismuth titanate (Na0.5Bi4.5Ti4O15) ceramics with B‐site cobalt modification

The piezoelectric properties of the cobalt‐modified sodium bismuth titanate (Na_0.5Bi_4.5Ti₄O₁₅, NBT) piezoelectric ceramics were investigated. The piezoelectric properties of NBT ceramics were significantly enhanced by cobalt modification. The Curie temperature T_C and piezoelectric constant d₃₃ for the 0.3 wt% cobalt‐modified NBT ceramics (NBT‐C3) were found to be 663 °C and 30 pC/N, respectively. Thermal annealing studies presented that the cobalt‐modified NBT ceramics possess stable piezoelectric properties, demonstrating that the cobalt‐modified NBT‐based ceramics are promising candidates for high temperature piezoelectric applications. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Dielectric and Piezoelectric Properties of Sodium Bismuth Titanate Ceramics with KCe Substitution

The piezoelectric properties of the (KCe)-substituted sodium bismuth titanate (Na_0.5Bi_4.5Ti₄O₁₅, NBT) piezoelectric ceramics are investigated. The piezoelectric properties of NBT ceramics are significantly enhanced by (KCe) substitution. The Curie temperature Tc, and piezoelectric coefficient d₃₃ for the (KCe)-substituted NBT are found to be 663ºC, and 27pC/N, respectively. Dielectric and annealing spectroscopy resent that the (KCe) co-substituted NBT piezoelectric ceramics possess stable piezoelectric properties.     

Microstructure,dielectric, and piezoelectric properties of 0.38Bi(Gax Sc1–x )O3–0.62PbTiO3 high temperature piezoelectric ceramics

0.38Bi(Ga_x Sc_1–x )O₃–0.62PbTiO₃ (BGSPTx) ceramics have been prepared by using the conventional mixed oxide method. X‐ray diffraction analysis revealed that BGSPTx has a pure perovskite structure, and the crystal symmetry of BGSPTx changed from rhombohedral to tetragonal with increasing Ga content (x). The Curie temperature (T_C) of BGSPTx ceramics is in the range of 448–467 °C for different x. The ferroelectric phase transition of BGSPTx was found to be of the first order type according to the Curie–Weiss law. For x = 0.125, BGSPTx ceramics show enhanced piezoelectric properties: piezoelectric constant d₃₃ = 420 pC/N and d₃₁ = –142 pC/N, planar and thickness electromechanical coupling factors k_p = 56.27% and k_t = 56.00%, respectively. The high‐T_C of BGSPTx coupled with its excellent piezoelectric properties suggests those future high‐temperature applications. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Piezoelectric and ferroelectric properties of [(K0.4725Na0.4725)Li0.055]NbO3–(Ag0.5Li0.5)TaO3 lead‐free ceramics

New lead‐free piezoelectric (1 – x)[(K_0.4725Na_0.4725)Li_0.055]NbO₃– x (Ag_0.5Li_0.5)TaO₃ [(1 – x)KNNL–x ALT] ceramics were prepared by conventional sintering. Piezoelectric and ferroelectric properties and Curie temperature of the ceramics were studied. The (1 – x)KNNL–x ALT (x = 0.04) ceramics exhibit good properties (d₃₃ ～ 252 pC/N, k_p ～ 41%, T_C ～ 471 °C, T_o–t = 47 °C, P_r = 33.1 μC/cm², E_c = 10.6 kV/cm). These results show that (1 – x)KNNL–x ALT (x = 0.04) ceramic is a promising lead‐free piezoelectric material for high temperature application. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Growth and properties of Li,Ta modified (K,Na)NbO3 lead‐free piezoelectric single crystals

Li, Ta modified (K,Na)NbO₃ single crystals with the size of 18 mm × 18 mm × 10 mm were successfully grown by top‐seeded solution growth method, with orthorhombic–tetra‐gonal phase transition temperature ～79 °C and Curie temperature ～276 °C. The electromechanical coupling factors k₃₃ and k_t were found to be ～88% and ～65%, respectively. The piezoelectric coefficient d₃₃ for the [001]_c poled crystals reached 255 pC/N. In addition, the electromechanical coupling factor exhibited high stability over the temperature range of –50 °C to 70 °C, making these lead free crystals good candidates for electromechanical applications. (© 2014 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Dielectric and piezoelectric properties of barium-modified Aurivillius-type Na0.5Bi4.5Ti4O15

In this study, monophasic Ba_x(Na_0.5Bi_0.5)_1−xBi₄Ti₄O₁₅ (x=0.03, 0.06, 0.09 and 0.12) ceramics fabricated from the powders synthesized via the solid-state reaction route exhibited relaxor behavior. X-ray diffraction analysis revealed that the barium-modified Na_0.5Bi_4.5Ti₄O₁₅ ceramics have a pure four-layer Aurivillius phase structure. Dielectric properties and phase transitions were studied and are explained in terms of lattice response of these ceramics. A shift in ferroelectric–paraelectric phase transition (T_c) to lower temperatures and a corresponding increase in permittivity peak with increasing concentration of Ba²⁺ are also observed. The decrease of orthorhombicity in the lattice structure by the larger Ba²⁺ ion incorporation, indicating an approach of a and b parameters, results in lower Curie temperature. The piezoelectric activity of Na_0.5Bi_4.5Ti₄O₁₅ (NBT) ceramics was significantly improved by the modification of barium. The Curie temperature T_c and piezoelectric coefficient d₃₃ for the composition with x=0.12 were found to be 635 °C and 21 pC/N, respectively. The relationship of polarization with lattice response is discussed.     

The effect of CuO and NiO doping on dielectric and ferroelectric properties of Na0.5Bi0.5TiO3 lead-free ceramics

In the present work, lead-free piezoelectric ceramics (Na_0.5Bi_0.5)TiO₃ –xCuO–yNiO (for x = 0.0, 0.02, 0.04 and 0.06) have been prepared by a conventional solid-state reaction method. An investigation of CuO and NiO doping in bismuth sodium titanate (BNT) and a study of the structure, morphology, and dielectric and ferroelectric properties of the NBT–CuNi system have been conducted. Phase and microstructural analysis of the (Na_0.5Bi_0.5)TiO₃ (NBT) based ceramics has been carried out using X-ray diffraction and scanning electron microscopy (SEM) techniques. Field emission scanning electron microscopy (FE-SEM) images showed that inhibition of grain growth takes place with increasing Cu and Ni concentration. The results indicate that the co-doping of NiO and CuO is effective in improving the dielectric and ferroelectric properties of NBT ceramics. Temperature-dependent dielectric studies have also been carried out at room temperature to 400 °C at different frequencies. The NBT ceramics co-doped with x = 0.06 and y = 0.06 exhibited an excellent dielectric constant ?_r = 1514. The study suggests that there is enormous scope of application of such materials in the future for actuators, ultrasonic transducers and high-frequency piezoelectric devices.     

Lead‐free piezoelectric (Na0.5Bi0.5)0.94TiO3–Ba0.06TiO3 nanofiber by electrospinning

Lead‐free (Na_0.5Bi_0.5)_0.94TiO₃–Ba_0.06TiO₃ (NBT‐BT6) nanofibers were synthesized by the sol–gel process and electrospinning, and a butterfly‐shaped piezoelectric response was measured by scanning force microscopy. NBT‐BT6 nanofibers with perovskite phase were formed, after being cleaned at 700 °C for 1 hour, and the diameters are in the range of 150 nm to 300 nm. The average value of the effective piezoelectric coefficient d₃₃ is 102 pm/V. The high piezoelectricity may be attributed to the easiness for the electric field to tilt the polar vector of the domain and to the increase of the possible spontaneous polarization direction. There is a potential for the application of NBT‐BT6 nanofibers in nanoscale piezoelectric devices. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Piezoelectric properties of PbHfO3–PbTiO3–Pb(Mg1/3Nb2/3)O3 ternary ceramics

(1 – x)Pb(Hf_1–yTi_y)O₃–x Pb(Mg_1/3Nb_2/3)O₃ (x = 0.1 ～ 0.25, y = 0.555) ternary piezoelectric ceramics were prepared using the two‐step precursor method. Morphotropic phase boundary (MPB) compositions, located at x = 0.18 ～ 0.22, were confirmed using X‐ray diffraction and by their dielectric, piezoelectric and ferroelectric properties. The optimum dielectric and piezoelectric properties were achieved for the MPB composition 0.8Pb(Hf_0.445Ti_0.555)O₃–0.2Pb(Mg_1/3Nb_2/3)O₃, with dielectric permittivity ε_r, piezoelectric coefficient d₃₃, planar electromechanical coupling k_p and Curie temperature T_C being on the order of 2800, 680 pC/N, 70% and 276 °C, respectively. Of particular significance is that the new ternary ceramics exhibit comparable piezoelectric and electromechanical properties to commercial PZT5H ceramics, but with much improved T_C, showing a potential for applications at elevated temperature. (© 2012 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Effect of Cu-stoichiometry on the dielectric and electric properties in CaCu3Ti4O12 ceramics

CaCu_3+yTi₄O₁₂ (y=0, ±0.025, ±0.05, ±0.1 and −0.15) ceramics are prepared by the conventional solid-state reaction technique under sintering condition of 1050 ^°C, 10 h. X-ray diffraction shows that they all have the good crystalline structure. Cu-deficient ceramics exhibit the microstructures of uniform grain size distribution, whereas both Cu-stoichiometric and Cu-rich ceramics display microstructures of bimodal grain size distribution. The largeness of low-frequency dielectric permittivity at room temperature is found to be very sensitive to the Cu-stoichiometry. Upon raising the measuring temperature, all of the ceramics present commonly three semicircles in the complex impedance plane. It indicates that there exist three distinct contributions, which are ascribed to arising from domains, grain boundaries and domain boundaries. In addition, the influence of CuO segregation on the dielectric and electrical properties is also discussed.     

Enhanced depolarization temperature in 0.90NBT–0.05KBT–0.05BT ceramics induced by BT nanowires

The depolarization temperature (T_d) of piezoelectric materials is an important figure of merit for their application at elevated temperatures. This study focuses on the effect of BaTiO₃ (BT) nanowires on T_d and piezoelectric properties of morphotropic-phase-boundary 0.90NBT–0.05KBT–0.05BT ceramics. The results reveal that BaTiO₃ nanowires can pin the domain wall, leading to the increase of coercive field (E_c) from 21.06 kV/cm to 34.99 kV/cm. The T_d value of 0.90NBT–0.05KBT–0.05BT ceramics can be enhanced approximately 20 °C when using BT nanowires instead of BT solution as the raw material. Meanwhile, at the same polarization conditions, the piezoelectric constant of the ceramic added BT nanowires (172 pC/N) is decreased but still remains a larger value compared with those of other lead-free ceramics. The results imply that the addition of BT nanowires into NBT–KBT is a very effective route to improve T_d.     

Characterization of lead free (K0.5Na0.5)NbO3-LiSbO3 piezoceramic

(K_0.5Na_0.5)NbO₃ (KNN) based lead free ceramics have been fabricated by a solid state reaction. In this work, LiSbO₃ (LS) modified KNN based ceramics were sintered at atmospheric pressure and high density (>96% theoretical) was obtained. The detailed elastic, dielectric, piezoelectric and electromechanical properties were characterized by using the resonance technique combined with the ultrasonic method. The full set of material constants for the obtained polycrystalline ceramics were determined and compared to the pure hot pressed KNN counterpart. KNN-LS polycrystalline ceramic was found to have higher elastic compliance, dielectric permittivity and piezoelectric strain coefficients, but lower mechanical quality factor, when compared to pure KNN, exhibiting a “softening” behavior. However, a high coercive field (∼17 kV/cm) was found for the LS modified KNN material. The properties as a function of temperature were determined in the range of −50-250 ^°C, showing a polymorphic phase transition near room temperature, giving rise to improved piezoelectric behavior.     

Effect of SrTiO3 on dielectric and piezoelectric properties of NBT

Composites of (1 ? x)Na_0.5Bi_0.5TiO₃-(x)SrTiO₃, where x = 0.05, 0.10, 0.15, 0.2, 0.3 and 0.9 are studied. Individual compounds are synthesized by sol gel, and composites are prepared by solid-state sintering process. Through the analysis of X-ray diffraction, lattice parameters are obtained and, from scanning electron microscope (SEM), micro-structure of the samples is observed. The depolarization temperature (T_d) and the Curie temperature (T_c) are determined from dielectric studies. Relaxor behavior of the samples is interpreted using modified Curie Weiss law. Control of polarization in sodium bismuth titanate (NBT) is achieved using strontium titanate (SrTiO₃-ST) and studied through polarization vs. electric field (PE) loops and piezoelectric measurements. The intra-granual and inter-granual effects on the electrical properties of the ceramics are studied from impedance analysis.     

Orientation dependence of electrical properties of 0.96Na<Subscript>0.5</Subscript>Bi<Subscript>0.5</Subscript>TiO<Subscript>3</Subscript>-0.04BaTiO<Subscript>3</Subscript> lead-free piezoelectric single crystal

In this paper, a single crystal of 0.96Na_0.5Bi_0.5TiO₃-0.04BaTiO₃ with dimensions of Φ 30×10 mm was grown by the top-seeded-solution growth method. X-ray powder diffraction results show that the as-grown crystal possesses the rhombohedral perovskite-type structure. The dielectric, piezoelectric and electrical conductivity properties were systematically investigated with 〈001〉, 〈110〉 and 〈111〉 oriented crystal samples. The room-temperature dielectric constants for the 〈001〉, 〈110〉 and 〈111〉 oriented crystal samples are found to be 650, 740 and 400 at 1 kHz. The (T _m, ε _m) values of the dielectric temperature spectra are almost independent of the crystal orientations; they are (306°C, 3718), (305°C, 3613) and (307°C, 3600) at 1 kHz for the 〈001〉, 〈110〉 and 〈111〉 oriented crystal. The optimum poling conditions were obtained by investigating the piezoelectric constants d ₃₃ as a function of poling temperature and poling electric field. For the 〈001〉 and 〈110〉 crystal samples, the maximum d ₃₃ values of 146 and 117 pC/N are obtained when a poling electric field of 3.5 kV/mm and a poling temperature of 80°C were applied during the poling process. The as-grown 0.96Na_0.5Bi_0.5TiO₃-0.04BaTiO₃ crystal possesses a relatively large dc electrical conductivity, especially at higher temperature, having a value of 1.98×10⁻¹¹ Ω⁻¹⋅m⁻¹ and 3.95×10⁻⁹ Ω⁻¹⋅m⁻¹ at 25°C and 150°C for the 〈001〉 oriented crystal sample.     

Effects of (LiCe) co-substitution on the structural and electrical properties of CaBi2Nb2O9 ceramics

The piezoelectric, dielectric, and ferroelectric properties of the (LiCe) co-substituted calcium bismuth niobate (CaBi₂Nb₂O₉, CBNO) are investigated. The piezoelectric properties of CBNO ceramics are significantly enhanced and the dielectric loss tanδ decreased. This makes poling using (LiCe) co-substitution easier. The ceramics (where □ represents A-site Ca²⁺ vacancies, possess a pure layered structure phase and no other phases can be found. The Ca_0.88(LiCe)_0.04□_0.04Bi₂Nb₂O₉ ceramics possess optimal piezoelectric properties, with piezoelectric coefficient (d₃₃) and Curie temperature (T_C) found to be 13.3 pC/N and 960 ℃, respectively. The dielectric and piezoelectric properties of the (LiCe) co-substituted CBNO ceramics exhibit very stable temperature behaviours. This demonstrates that the CBNO ceramics are a promising candidate for ultrahigh temperature applications.     

Substitution and proton doping effect on SrZrO3 behaviour: high‐pressure Raman study

The high‐pressure Raman studies of pure, Yb‐modified, protonated and non‐protonated SrZrO₃ dense ceramics were performed between 0.1 and 40 GPa using a diamond anvil cell. Lanthanide‐modified, protonated SrZrO₃ perovskites are potential materials for electrolytic membrane in fuel cells and electrolysers working at medium temperature. The comparison of the Raman spectra shows important differences in the pressure behaviour between the pure and Yb‐modified SrZrO₃ ceramics. SrZrO₃ exhibits a rigid structure without any structural modification, whereas for both SrZr_0.93 Yb_0.07 O_2.965 and SrZr_0.93 Yb_0.07 O_2.962 H_0.003 a sequence of structural modifications at 10, 20 and 35 GPa is revealed. The character of these structural modifications is very similar to that observed as a function of the temperature (orthorhombic Pnma 750 °C → pseudo‐tetragonal Imma 840 °C → tetragonal I4/mcm 1070 °C → cubic Pm3m), which suggests that they can be considered as the phase transitions. Despite the low level of proton content (0.3% mole/mole), significant difference between protonated and non‐protonated compounds is observed for the 700–750 cm⁻¹ doublet assigned to the Zr O octahedron stretching mode, perturbed by an oxygen atom vacancy and/or neighbouring Yb ion. The location of proton is discussed. Copyright © 2011 John Wiley & Sons, Ltd.     

Microwave dielectric properties of the 5.5Li<Subscript>2</Subscript>O–Nb<Subscript>2</Subscript>O<Subscript>5</Subscript>–7TiO<Subscript>2</Subscript> ceramics

A new Li₂O–Nb₂O₅–TiO₂ (LNT) ceramic with the Li₂O:Nb₂O₅:TiO₂ mole ratio of 5.5:1:7 was prepared by solid state reaction route. The phase and structure of the ceramic were characterized by X-ray diffraction and scanning electron microscopy (SEM). The microwave dielectric properties of the ceramics were studied using a network analyzer. The microwave dielectric ceramic has low sintering temperature (∼1075°C) and good microwave dielectric properties of ε _r=42, Q×f=16900 GHz (5.75 GHz), and τ _f =63.7 ppm/°C. The addition of B₂O₃ can effectively lower the sintering temperature from 1075 to 875°C and does not induce degradation of the microwave dielectric properties. Obviously, the LNT ceramics can be applied to microwave low temperature-cofired ceramics (LTCC) devices.     

Combined effects of Li content and sintering temperature on?polymorphic phase boundary and electrical properties of Li/Ta co-doped (Na, K)NbO3 lead-free piezoceramics

Crystallographic structure, phase transition and electrical properties of lead-free (Na_0.535K_0.485)_1−x Li _x (Nb_0.942Ta_0.058)O₃ (x=0.042–0.098) (NKL _x NT) piezoelectric ceramics were investigated. The experimental results show that both Li content and sintering temperature strongly affect the orthorhombic–tetragonal polymorphic phase boundary (PPB), which results in remarkable differences of the piezoelectric property and its temperature stability in the NKL _x NT ceramics. Chemical analysis indicates that sodium volatilizes more seriously than potassium and lithium with increasing sintering temperature. Due to the comprehensively optimized effects of Li content and sintering temperature, an enhanced piezoelectric constant d ₃₃ (276 pC/N) was obtained at room temperature in the ceramics with x=0.074 sintered at 1000°C. In the same composition, a further high d ₃₃ up to 354 pC/N was obtained at 43°C, which is close to its T _o−t temperature. Furthermore, better temperature stability can be obtained when x=0.082 sintered at 1000°C, whose piezoelectric constant d ₃₃ (236 pC/N) keeps almost constant from room temperature to 100°C. Such a temperature-independent piezoelectric property is available in the NKL _x NT ceramics with high Li content because its T _o−t was moved below room temperature.     

Pyroelectric properties of BiFeO3 ceramics prepared by a modified solid-state-reaction method

BiFeO₃ (BFO) ceramics were prepared by a modified solid-state-reaction method which adopts a higher heating/cooling rate during the sintering process than usually used. It was found that the calcination temperature T _cal (from 400 to 750°C) does not influence the BFO phase formation, while the sintering temperature T _sin (from 815 to 845°C) dominates the phase purity. The optimum sintering temperature was in the range from 825 to 835°C. The optimized samples exhibit saturated ferroelectric hysteresis loops with a remnant polarization of 13.2 μC/cm². The measured piezoelectric coefficient d ₃₃ was 45 pC/N. No remnant magnetization was observed in all of the samples. The pyroelectric properties were studied as a function of temperature and frequency. A pyroelectric coefficient as high as 90 μC/m² K was obtained at room temperature in the optimized sample. An abrupt decrease of the pyroelectric coefficient was observed at temperatures between 70 and 80°C. On the basis of our results, BFO may have the potential for pyroelectric applications.     

Nanocrystalline CaCu<Subscript>3</Subscript>Ti<Subscript>4</Subscript>O<Subscript>12</Subscript> powder by PVA sol–gel route: synthesis,characterization and its giant dielectric constant

Nanocrystalline CaCu₃Ti₄O₁₂ powders were synthesized by a simple PVA sol–gel route and calcined at 700 and 800°C in air for 8 h. The diameter of the powders ranges from 40–100 nm. The calcined CaCu₃Ti₄O₁₂ powders were characterized by TG-DTA, XRD, FTIR, SEM, and TEM. Sintering of the powders was conducted in air at 1100°C for 16 h. The XRD results indicated that all sintered samples had a typical perovskite CaCu₃Ti₄O₁₂ structure although the sintered samples contained some amount of CaTiO₃. SEM of the sintered CaCu₃Ti₄O₁₂ ceramics showed the average grain sizes of 13–15 μm. The samples exhibit a giant dielectric constant, ε′∼10⁵ at 150 to 200°C with weak temperature dependence below 1 kHz in the sample sintered using the powders calcined at 700°C. The Maxwell–Wagner polarization mechanism is used to explain the high permittivity in these ceramics. It is also found that all sintered samples have the same activation energy of grains, which is ∼0.122 eV.