Effect of Nb-doping on dielectric, ferroelectric and conduction behaviour of lead free Bi0.5(Na0.5K0.5)0.5TiO3 ceramic

Bi_0.5(Na_0.5K_0.5)_0.5TiO₃ + y wt.% Nb (y = 0-1) piezoelectric ceramics were synthesized by solid state reaction. The effect of varying Nb concentration on various properties of BNKT ceramic has been investigated in detail. The effect of Nb-doping on dielectric and ferroelectric property has been presented. An increase in its depolarization temperature and Curie temperature with Nb concentration was observed. The electrical properties of pure and Nb-doped BNKT ceramic over a wide range of frequencies (20 Hz to 2 MHz) and temperature (30-430 °C) were studied using impedance spectroscopic technique.     

Large strain response in Li/Nb co-doped Bi0.5(Na0.8K0.2)0.5TiO3 lead-free piezoceramics

A series of (Bi_0.5Na_0.4K_0.1)Ti_0.98Nb_0.02O₃-xLi lead-free ceramics were fabricated using the solid-state reaction technique. The effects of Li/Nb cations on the structural and electrical properties of the ceramics were investigated. All the sintered ceramics exhibited pure perovskite structure and the average grain size increased slightly with increasing the Li content. Shape of the P-E loops illustrated the relaxor characteristic of all the samples. A giant strain of 0.4% was obtained at 60 kV/cm at x = 0.01 and the corresponding normalized strain was up to 683 pm/V, moreover, the strain exhibits excellent fatigue-resistance behavior. The giant strain can be attributed to the ferroelectric-relaxor phase transition under external driving electric field. These results indicate the sintered Li/Nb co-doped lead-free ceramics can be promising candidate for actuator applications.     

Fabrication and characterization of (Pb(Mg1/3Nb2/3)O3, Pb(Yb1/2Nb1/2)O3, PbTiO3) ternary system ceramics

New ternary compositions in the Pb(Mg_1/3Nb_2/3)O₃-Pb(Yb_1/2Nb_1/2)O₃–PbTiO₃ (PMN-PYbN-PT) system were prepared using 0.5Pb(Yb_1/2Nb_1/2)O₃-0.5PbTiO₃ (PYbNT) and (1-x)Pb(Mg_1/3Nb_2/3)O₃–xPbTiO₃ (x = 0.26; PMNT26 or x = 0.325; PMNT32.5) powders synthesized via the columbite method. Dense (≥ 96% of theoretical density) ceramics with PMN/PYbN mole ratios of 25/75 (R-25), 50/50 (R-50) and 75/25 (R-75T and R-75R) were fabricated by reactive sintering at 1000 °C for 4 h. Therefore, incorporation of PYbNT to PMNT successfully decreased sintering temperature of PMNT from 1200 °C-1250 °C to 1000 °C. Samples with higher density and perovskite ratio together with lower weight loss possessed higher dielectric and piezoelectric values in each composition. The R-75 samples had remanent polarization (P_r) values of 34-36 μC/cm² and piezoelectric charge coefficient (d₃₃) of 560 pC/N. The sharp phase transition PMNT as a function of temperature became broader or more diffuse with increasing PYbNT content. However, PYbNT addition to PMNT increased Curie temperature (T_c) from 183 °C (for PMNT32.5) to 220-242 °C (for R-75T and R-75R) to 336 °C (for R-25). Therefore, these ternary compositions can be tailored for various high temperature applications due to the relatively higher T_c with enhanced piezoelectric and dielectric properties as compared to PMNT.     

Enhanced energy-storage properties of (1-x)(0.7Bi0.5Na0.5TiO3-0.3Bi0.2Sr0.7TiO3)-xNaNbO3 lead-free ceramics

A series of (1-x)(0.7Bi_0.5Na_0.5TiO₃-0.3Bi_0.2Sr_0.7TiO₃)-xNaNbO₃ (BNT-BST-100xNN) lead-free ceramics were fabricated using conventional solid-state reaction technique. The phase behavior, microstructure, dielectric, ac impedance and energy-storage properties of the sintered ceramics were systematically investigated. XRD patterns and surface SEM micrographs revealed the introduction of NaNbO₃ didn't change the perovskite structure of BNT-BST at low doping level. The NaNbO₃ doping gave rise to slimmer P-E loops and thus gained enhanced energy storage properties. Therefore, a maximum energy storage density of 1.03 J/cm³ was achieved at 85 kV/cm at x = 0.01 via increasing the dielectric breakdown strength (DBS). Temperature-dependent dielectric permittivity illustrated the enhanced relaxor characteristics, implying the long-rang ferroelectric order was further damaged due to the introduction of NaNbO₃. The results above indicate the sintered ternary ceramics can be a promising lead-free candidate for energy storage capacitors.     

Rheology and physical properties of Bi0.5(Na0.82K0.18)0.5TiO3 piezoelectric thick films by aqueous gel-tape casting process

Piezoelectric Bi_0.5(Na_0.82K_0.18)_0.5TiO₃ thick films were prepared by aqueous gel-tape casting. Bi_0.5(Na_0.82K_0.18)_0.5TiO₃ nano-powder with perovskite structure prepared by sol–gel process was obtained. The average particle size was 200 nm. A stable Bi_0.5(Na_0.82K_0.18)_0.5TiO₃ suspension with 46 vol% solid loading and <1 Pa s viscosity was prepared when 0.8 wt% of ammonium polyacrylate was added with the pH value controlled in the range 7–9. The plasticizer glycerol had a positive effect on the fluidity of the suspensions. The tensile strength and strain to failure of the green tape were 0.42 MPa and 0.04 mm/mm when the addition of glycerol was 50 wt% of the premix solvent. The resulting about 100 μm thick films had relative permittivity of 910, dielectric loss of 4.9% at 10 kHz, remanent polarization of 24 μC/cm², coercive field of 56 kV/cm, and longitudinal effective piezoelectric coefficient d₃₃eff of 102 pC/N. The good performance illustrated that gel-tape casting was the effective way to prepare Bi_0.5(Na_0.82K_0.18)_0.5TiO₃ thick film.     

Effect of Eu doping on structure and electrical properties of lead-free (Bi0.5Na0.5)0.94Ba0.06TiO3 ceramics

Eu-doped (Bi_0.5Na_0.5)_0.94Ba_0.06TiO₃ (BNBT6-xEu, x=0.00–2.00 at%) lead-free piezoelectric ceramics have been synthesized by the solution combustion method. The effect of Eu doping concentration on the phase structure, microstructure and electrical properties of BNBT6 ceramics has been investigated. The XRD analysis confirms that the europium additive incorporates into the BNBT6 lattice and results in a phase transition from the coexistence of rhombohedral and tetragonal phases to a more symmetric pseudocubic phase. The SEM images indicate that the europium additive has little effect on the ceramic microstructure and the average grain size is about 2.0 μm. The electrical properties of BNBT6 ceramics can be improved by appropriate Eu doping. The 0.25 at% Eu doped BNBT6 ceramic presents excellent electrical properties: piezoelectric constant d₃₃=149 pC/N, remnant polarization P_r=40.27 μC/cm², coercive field E_c=2.95 kV/mm, dielectric constant ε_r=1658 and dissipation factor tan δ=0.0557 (10 kHz).     

Effect of Bi2O3 additives on sintering and microwave dielectric behavior of La(Mg0.5Ti0.5)O3 ceramics

Bi₂O₃ was selected as liquid phase sintering aid to lower the sintering temperature of La(Mg_0.5Ti_0.5)O₃ ceramics. The sintering temperature of La(Mg_0.5Ti_0.5)O₃ ceramics is generally high, about 1600 °C. However, the sintering temperature was significantly lowered about 275 °C from 1600 °C to 1325 °C by incorporating in 15 mol% Bi₂O₃ and revealed the optimum microwave dielectric properties of dielectric constant (?_r) value of 40.1, a quality factor (Q × f) value of 60,231 GHz, and the temperature coefficient (τ_f) value of 70.1 ppm/°C. During all addition ranges, the relative dielectric constants (?_r) were different and ranged from 32.0 to 41.9, the quality factors (Q × f) were distributed in the range of 928–60,231 GHz, and the temperature coefficient (τ_f) varies from 0.3 ppm/°C to 70.3 ppm/°C. Noticeably, a nearly zero τ_f can be found for doping 5 mol% Bi₂O₃ sintering at 1325 °C. It implies that nearly zero τ_f can be achieved by appropriately adjusting the amount of Bi₂O₃ additions and sintering temperature for La(Mg_0.5Ti_0.5)O₃ ceramics.     

Effect of Li addition on phase formation behavior and electrical properties of (K0.5Na0.5)NbO3 lead free ceramics

In this work, Li-modified KNN ceramic compositions ((K_0.5Na_0.5)_1−xLi_x)NbO₃ with x = 0.03, 0.04, 0.05, 0.06, 0.65 and 0.07 were prepared by a conventional solid-state mixed-oxide method. The structural phase formation and microstructure were characterized by X-ray diffraction technique (XRD) and scanning electron microscopy (SEM). It has been found that a morphotropic phase boundary (MPB) between orthorhombic phase and tetragonal phases should exist between compositions with Li contents of 6-6.5%. The Curie temperature (T_c) of the ceramics shifted to higher temperature with increasing Li content. The room temperature dielectric constant was also seen to be higher than the pure KNN ceramics. In addition, the ferroelectric properties were found to enhance at near MPB compositions. This study clearly showed that the addition of Li could improve the dielectric and ferroelectric properties in (K_0.5Na_0.5)NbO₃ ceramics.     

The influence of sintering aids for Nd(Mg0.5Ti0.5)O3 microwave dielectric ceramics properties

The influence of various sintering aids on the microwave dielectric properties and the structure of Nd(Mg_0.5Ti_0.5)O₃ ceramics were investigated systematically. B₂O₃, Bi₂O₃, and V₂O₅ were selected as liquid-phase sintering aids to lower the sintering temperature. The sintered Nd(Mg_0.5Ti_0.5)O₃ ceramics are characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), and microwave dielectric properties. The sintering temperature of Nd(Mg_0.5Ti_0.5)O₃ microwave dielectric ceramics is generally high, about 1500 °C. However, the sintering temperature was significantly lowered about 175 °C from 1500 °C to 1325 °C by incorporating in 10 mol% B₂O₃ and revealed the optimum microwave dielectric properties of dielectric constant (_r) value of 26.2, a quality factor (Q × f) value of 61,307 (at 9.63 GHz), and τ_f value of −45.5 ppm/°C. NdVO₄ secondary phase was observed at 10 mol% V₂O₅ addition in the sintering temperature range of 1300–1325 °C, which led the degradation in microwave dielectric properties. The microwave dielectric properties as well as grain sizes, grain morphology, and bulk density were greatly dependent on sintering temperature and various sintering aids. In this study, it is found that Nd(Mg_0.5Ti_0.5)O₃ incorporated with 10 mol% B₂O₃ with lower sintering temperature and excellent dielectric microwave properties may be suggested for application in microwave communication devices. The use of liquid-phase sintering, the liquid formed during firing normally remains as a grain boundary phase on cooling. This grain boundary phase can cause a deterioration of the microwave properties. Therefore, the selection of a suitable sintering aid is extremely important.     

Enhanced ferroelectric properties in (Ba1−xCax)(Ti0.94Sn0.06)O3 lead-free ceramics

Lead-free (Ba_1−xCa_x)(Ti_0.94Sn_0.06)O₃ (BCST) (x = 0.01-0.04) ceramics were prepared using a solid-state reaction technique. The effects of Ca content on the phase structure and electrical properties of the BCST ceramics were investigated. High piezoelectric coefficient of d₃₃ = 440 pC/N, planar electromechanical coupling factor of k_p = 45% and dielectric constant ?_r = 6900 were obtained for the samples at x = 0.03. At room temperature, a polymorphic phase transition (PPT) from orthorhombic phase to tetragonal phase was identified in the composition range of 0.02 < x < 0.04.     

Structure and electrical properties of Ca2+-doped (Na0.47Bi0.47Ba0.06)TiO3 lead-free piezoelectric ceramics

The lead-free piezoelectric ceramics (Na_.47Bi_.47Ba_.06)_1-xCa_xTiO₃ (x?=?0, 0.01, 0.02, 0.03, 0.05, and 0.08, abbreviated as BNBTC/0, BNBTC/1, BNBTC/2, BNBTC/3, BNBTC/5, and BNBTC/8, respectively) were obtained using the solid-state reaction method. The structure, electric conductivity, and dielectric, ferroelectric, and piezoelectric properties of the Ca²⁺-doped (Na_.47Bi_.47Ba_.06)TiO₃ ceramics were thoroughly investigated. The ceramics sintered at 1200?°C exhibit dense microstructures, having relative densities higher than 96%. The X-ray diffraction results demonstrate that all ceramics have a pure perovskite structure. The mean grain sizes of the ceramics are related to the Ca²⁺ quantity. A small quantity of Ca²⁺ ions (x?≤?0.03) improves the piezoelectric and ferroelectric properties of the samples. The dielectric behavior of the samples is sensitive to the Ca²⁺ content and electric poling. The results demonstrate that the electrical properties of the (Na_.47Bi_.47Ba_.06)TiO₃ lead-free ceramics can be well tuned by varying the Ca²⁺ quantity.     

Effect of Bi2O3 and B2O3 additives on the sintering temperature, microstructure, and microwave dielectric properties for Sm(Mg0.5Ti0.5)O3 ceramics

The microwave dielectric properties of Sm(Mg_0.5Ti_0.5)O₃ incorporated with various amount of Bi₂O₃ and B₂O₃ additives have been investigated systematically. In this study, both Bi₂O₃ and B₂O₃ additives acting as a sintering aid can effectively lower the sintering temperature from 1550 °C to 1300 °C. The ionic radius of Bi³⁺ for a coordination number of 6 is 0.103 nm, whereas the ionic radius of B³⁺ is 0.027 nm. Clearly, the ionic radius of Bi³⁺ is greatly larger than one of B³⁺, which resulted in the specimens incorporated with Bi₂O₃ having larger lattice parameters and cell volume than those incorporated with B₂O₃. The experimental results show that no second phase was observed throughout the entire experiments. Depending on the interfacial tension, the liquid phase may penetrate the grain boundaries completely, in which case the grains will be separated from one another by a thin layer as shown in Sm(Mg_0.5Ti_0.5)O₃ ceramics incorporated with Bi₂O₃. Whereas, in Sm(Mg_0.5Ti_0.5)O₃ ceramics incorporated with B₂O₃, the volume fraction of liquid is high, the grains may dissolve into the liquid phase, and rapidly rearrange, in which case contact points between agglomerates will be dissolved due to their higher solubility in the liquid, leading plate-like shape microstructure.A dielectric constant (?_r) of 29.3, a high Q × f value of 26,335 GHz (at 8.84 GHz), and a τ_f of −32.5 ppm/°C can be obtained for Sm(Mg_0.5Ti_0.5)O₃ ceramics incorporated with 10 mol% Bi₂O₃ sintered at 1300 °C. While Sm(Mg_0.5Ti_0.5)O₃ ceramics incorporated with 5 mol% B₂O₃ can effectively lower temperature coefficient of resonant frequency, which value is −21.6 ppm/°C. The Sm(Mg_0.5Ti_0.5)O₃ ceramic incorporated with heavily Bi₂O₃ and B₂O₃ additives exhibits a substantial reduction in temperature (∼250 °C) and compatible dielectric properties in comparison with that of an un-doped one. This implied that this ceramic is suitable for miniaturization in the application of dielectric resonators and filters by being appropriately incorporated with a sintering aid.     

Low-temperature preparation and microwave dielectric properties of cold sintered Li2Mg3TiO6 nanocrystalline ceramics

This study aims to fabricate Li₂Mg₃TiO₆ ceramics with ultrafine grains using a novel cold sintering process combined with a post-annealing treatment at a temperature <?950?°C. In this study, phase composition, sintering behavior, microstructure evolution, and microwave dielectric properties of the resultant nanocrystalline ceramics were investigated for the first time. The as-compacted green pellets at 180?°C yielded a high relative density of ~ 90% and the ceramics that were post-sintered over a broad temperature range (800–950?°C) possessed highly dense microstructure with a relative density of ~ 96%. The average grain size varied from 100 to 1200?nm for the samples sintered at 800–950?°C. Furthermore, the quality (Q × f) values of the obtained specimens exhibited a strong positive dependency on the grain size, which increased from 17,790 to 47,960?GHz for grain sizes ranging between 100 and 1200?nm, while the dielectric permittivity (ε_r) and temperature coefficient of the resonant frequency (τ_f) values did not undergo any significant changes over this range of grain size.     

Enhancement of piezoelectric and ferroelectric properties of BaTiO3 ceramics by aluminum doping

Ferroelectric and piezoelectric properties of BaTiO₃ and Al-doped BaTiO₃ ceramics were investigated. The ferroelectric study demonstrated that, by doping Al³⁺ ions in the A-site of BaTiO₃, the polarization–electric field loop exhibited enhanced remnant polarization (from 12 to 17.5  μC/cm²), saturation and switching. In addition, the piezoelectric constant (d₃₃) increased with Al-doping for both static and dynamic strain values (from 75 to 135 and from 29.2 to 57.9 pC/N, respectively, at a maximum applied electric field of 16 kV/cm). Furthermore, the dielectric constant values increased and both the dielectric loss factor and leakage current decreased, even though the transition temperature shifted to lower temperature (from 121 to 113 °C) for the Al-doped sample. Therefore, the Al-doped BaTiO₃ has adjustable piezoelectric and ferroelectric properties.     

Dielectric properties of CuO-doped La2.98/3Ba0.01(Mg0.5Sn0.5)O3 ceramics at microwave frequency

The microwave dielectric properties of La_2.98/3Ba_0.01(Mg_0.5Sn_0.5)O₃ ceramics prepared by the conventional solid-state method were investigated for application in mobile communication. A 100 °C reduction of the sintering temperature was obtained by using CuO as a sintering aid. A dielectric constant of 20.0, a quality factor (Q × f) of 50,100 GHz and a temperature coefficient of resonant frequency τ_f of −78.3 ppm/°C were obtained when La_2.98/3Ba_0.01(Mg_0.5Sn_0.5)O₃ ceramics with 0.25 wt.% CuO were sintered at 1500 °C for 4 h.     

Investigation on the anti-reduction mechanism of Ti4+ in high dielectric constant system Ca0.9La0.067TiO3 by doping with Al2O3

Ca_0.9La_0.067TiO₃ (abbreviated as CLT) ceramics doped with different amount of Al₂O₃ were prepared via the solid state reaction method. The anti-reduction mechanism of Ti⁴⁺ in CLT ceramics was carefully investigated. X-ray diffraction (XRD) was used to analyze the phase composition and lattice structure. Meanwhile, the Rietveld method was taken to calculate the lattice parameters. X-ray photoelectron spectroscopy (XPS) was employed to study the valence variation of Ti ions in CLT ceramics without and with Al₂O₃. The results showed that Al³⁺ substituted for Ti⁴⁺ to form solid solution and the solid solubility limit of Al³⁺ is near 1.11 mol%. Furthermore, the reduction of Ti⁴⁺ in CLT ceramics was restrained by acceptor doping process and the Q × f values of CLT ceramics were improved significantly. The CLT ceramic doped with 1.11 mol% Al₂O₃ exhibited good microwave dielectric properties: ε_r = 141, Q × f = 6848 GHz, τ_f = 576 ppm/°C.     

Synthesis,structural analysis and dielectric properties of Ba8(Mg1−xZnx)Nb6O24 hexagonal perovskites

Ba₈(Mg_1−xZn_x)Nb₆O₂₄ (x=0, 0.2, 0.4, 0.6, 0.8 and 1) ceramics were prepared through the conventional solid-state route. The materials were calcined at 1250 °C and sintered at 1375–1425 °C. The structure of the system was analyzed using X-ray diffraction and vibrational spectroscopic studies. The microstructure of the sintered pellet was analyzed using scanning electron microscopy. The dielectric constant (ε_r), temperature coefficient of resonant frequency (τ_f) and the unloaded quality factor (Q_u) were measured in the microwave frequency region. The τ_f values of the compositions were reduced by varying the value of x from 0 to 1. The dielectric responses to frequency were also studied in the radio frequency region. The compositions have good microwave dielectric properties and hence are suitable for dielectric resonator applications.     

An investigation of (Na0.5K0.5)NbO3–CaTiO3 based lead-free ceramics and surface acoustic wave devices

Lead-free (Na_0.5K_0.5)NbO₃ ceramics doped with CaTiO₃ (0–3 mol%) have been prepared by the conventional mixed oxide method in this paper. All of the CaTiO₃ doped (Na_0.5K_0.5)NbO₃ specimens do not deliquesce as exposed to water for a long time. The samples are characterized by X-ray diffraction analysis, Raman scattering spectra, scanning electron microscopy, and atomic force microscopy. The dielectric, piezoelectric and ferroelectric properties are also investigated. The results show that the addition of CaTiO₃ is very effective in preventing the deliquescence and in improving the electric properties of (Na_0.5K_0.5)NbO₃ ceramics. Finally, surface acoustic wave devices based on lead-free ceramics have been successfully fabricated and their characterization is presented.     

Electric-field-induced strain in Mn-doped KNbO3 ferroelectric ceramics

Potassium niobate, KNbO₃ (KN), ceramics doped with manganese (Mn) were prepared by a modified conventional ceramic fabrication process to characterize their dielectric, ferroelectric and electrostrain properties. In this study, 0.22% of a large electric-field-induced strain was obtained at 80 kV/cm under unipolar driving for 1.2 wt% MnCO₃-doped KN ceramics. Basically, it is difficult to obtain dense and nondeliquescent KN ceramics by the conventional method because of potassium ions. The key factor in obtaining dense and nondeliquescent KN ceramics is the calcination process control. Thus, the two-step calcination pattern is proposed for this purpose. Dense, nondeliquescent and high-resistivity Mn-doped KN ceramics were obtained, resulting in a large electric-field-induced strain under a high electric field.