Characterization of sol-gel synthesised lead-free (1 − x)Na0.5Bi0.5TiO3-xBaTiO3-based ceramics

The crystal structure, microstructure, dielectric and ferroelectric properties of (1 − x)Na_0.5Bi_0.5TiO₃-xBaTiO₃ ceramics with x = 0, 0.03, 0.05, 0.07 and 0.1 are investigated. A structural variation according to the system composition was investigated by X-ray diffraction (XRD) analyses. The results revealed that the synthesis temperature for pure perovskite phase powder prepared by the present sol-gel process is much lower (800 °C), and a rhombohedral-tetragonal morphotropic phase boundary (MPB) is found for x = 0.07 composition which showing the highest remanent polarization value and the smallest coercive field. The optimum dielectric and piezoelectric properties were found with the 0.93Na_0.5Bi_0.5TiO₃-0.07BaTiO₃ composition. The piezoelectric constant d₃₃ is 120 pC/N and good polarization behaviour was observed with remanent polarization (P_r) of 12.18 pC/cm², coercive field (E_c) of 2.11 kV/mm, and enhanced dielectric properties ?_r > 1500 at room temperature. The 0.93Na_0.5Bi_0.5TiO₃-0.07BaTiO₃-based ceramic is a promising lead-free piezoelectric candidate for applications in different devices.     

Phase structure and electrical properties of (0.8 − x) BaTiO3-0.2Bi0.5Na0.5TiO3-xBaZrO3 lead-free piezoceramics

Lead-free piezoelectric ceramics (0.8 − x)BaTiO₃-0.2Bi_0.5Na_0.5TiO₃-xBaZrO₃ (BT-BNT-xBZ, 0 ≤ x ≤ 0.08) doped with 0.3 wt% Li₂CO₃ were prepared by conventional solid-state reaction method. With the Li₂CO₃ doping, all the ceramics can be well sintered at 1170-1210 °C. The phase structure, dielectric, ferroelectric and piezoelectric properties of the ceramics were investigated. Results show that a morphotropic phase boundary (MPB) between tetragonal and pseudocubic phases exists at x = 0.03-0.04. The addition of Zr can improve the piezoelectric properties of BT-BNT ceramics. Furthermore, a relaxor behavior is induced and the tetragonal-cubic phase transition shifts towards lower temperatures after the addition of Zr. The ceramics with x = 0.03 possess the optimum electrical properties: d₃₃ = 72 pC/N, k_p = 15.4%, ?_r = 661, P_r = 18.5 μC/cm², E_c = 34.1 kV/cm, T_c = 150 °C.     

Preparation and electrical properties of Bi0.5Na0.5TiO3-BaTiO3-KNbO3 lead-free piezoelectric ceramics

Lead-free (1 − x)Bi_0.47Na_0.47Ba_0.06TiO₃-xKNbO₃ (BNBT-xKN, x = 0-0.08) ceramics were prepared by ordinary ceramic sintering technique. The piezoelectric, dielectric and ferroelectric properties of the ceramics are investigated and discussed. The results of X-ray diffraction (XRD) indicate that KNbO₃ (KN) has diffused into Bi_0.47Na_0.47Ba_0.06TiO₃ (BNBT) lattices to form a solid solution with a pure perovskite structure. Moderate additive of KN (x ≤ 0.02) in BNBT-xKN ceramics enhance their piezoelectric and ferroelectric properties. Three dielectric anomaly peaks are observed in BNBT-0.00KN, BNBT-0.01KN and BNBT-0.02KN ceramics. With the increment of KN in BNBT-xKN ceramics, the dielectric anomaly peaks shift to lower temperature. BNBT-0.01KN ceramic exhibits excellent piezoelectric properties and strong ferroelectricity: piezoelectric coefficient, d₃₃ = 195 pC/N; electromechanical coupling factor, k_t = 58.9 and k_p = 29.3%; mechanical quality factor, Q_m = 113; remnant polarization, P_r = 41.8 μC/cm²; coercive field, E_c = 19.5 kV/cm.     

Piezoelectric and dielectric properties of Dy2O3-doped (Bi0.5Na0.5)0.94Ba0.06TiO3 lead-free ceramics

(Bi_0.5Na_0.5)_0.94Ba_0.06TiO₃ + x wt% Dy₂O₃ with x = 0-0.3 ceramics were synthesized by conventional solid-state processes. The effects of Dy₂O₃ on the microstructure, the piezoelectric and dielectric properties were investigated. X-ray diffraction pattern confirmed that the coexistence of tetragonal and rhombohedral phases in the (Bi_0.5Na_0.5)_0.94Ba_0.06TiO₃ composition was not changed by adding 0.05-0.3 wt% Dy₂O₃. SEM images indicate that all the ceramics have pore-free microstructures with high density, and that doping of Dy₂O₃ inhibits the grain growth of the ceramics. The addition of Dy₂O₃ shows the double effects on decreasing the piezoelectric and dielectric properties for 0 < x < 0.15 when Dy³⁺ ions substitute B-site Ti⁴⁺ ions, and increasing the properties for 0.15 < x < 0.3 when Dy³⁺ ions enters into A-site of the perovskite structure. The optimum electric properties of piezoelectric constant d₃₃ = 170 pC/N and the dielectric constant ?_r = 1900 (at a frequency of 1 kHz) are obtained at x = 0.3.     

Structure, microstructure and electrical properties of (1 − x − y)Bi0.5Na0.5TiO3–xBi0.5K0.5TiO3–yBi0.5Li0.5TiO3 lead-free piezoelectric ceramics

The ternary system (1 − x − y)Bi_0.5Na_0.5TiO₃–xBi_0.5K_0.5TiO₃–yBi_0.5Li_0.5TiO₃ (abbreviated to BNKLT-x/y) was synthesized by conventional oxide-mixed method. The phase structure, microstructure, and dielectric, ferroelectric and piezoelectric properties of the ceramics were investigated. The X-ray diffraction patterns showed that pure perovskite phase with rhombohedral structure can be obtained in all the ceramics. The grain size varied with x and y. The temperature dependence of dielectric constant and dielectric loss revealed there were two phase transitions which were from ferroelectric (tetragonal) to anti-ferroelectric (rhombohedral) and anti-ferroelectric to paraelectric (cubic). Either increasing x or y content can make T_m (the temperature at which dielectric constant _r reaches the maximum) increase. With the addition of Bi_0.5K_0.5TiO₃, the remanent polarization P_r increased but the coercive field E_c decreased. With the addition of Bi_0.5Li_0.5TiO₃, P_r increased obviously and E_c increased slightly. Due to the stronger ferroelectricity by modifying Bi_0.5K_0.5TiO₃ and Bi_0.5Li_0.5TiO₃, the piezoelectric properties were enhanced at x = 0.22 and y = 0.10, which were as follows: P_r = 31.92 μC/cm², E_c = 32.40 kV/cm, _r = 1118, tan δ = 0.041, d₃₃ = 203 pC/N and K_p = 0.31. The results show that the BNKLT-x/y ceramics are promising candidates for the lead-free materials.     

The temperature-dependent electrical properties of Bi0.5Na0.5TiO3-BaTiO3-Bi0.5K0.5TiO3 near the morphotropic phase boundary

Bi_0.5Na_0.5TiO₃-BaTiO₃-Bi_0.5K_0.5TiO₃ (BNT-BT-BKT) lead-free piezoceramics with compositions near the rhombohedral-tetragonal morphotropic phase boundary (MPB) were prepared and investigated. At room temperature, all ceramics show excellent electrical properties. In this study, the best properties were observed in 0.884BNT-0.036BT-0.08BKT, with the remnant polarization, bipolar total strain, unipolar strain, piezoelectric constant, and planar electromechanical coupling factor being 34.4 μC cm⁻², 0.25%, 0.15%, 122 pC N⁻¹, and 0.30, respectively. Detailed analysis of the temperature dependence of polarization-electric field (P-E) loops and bipolar/unipolar strain-electric field (S-E) curves of this composition revealed a ferroelectric-antiferroelectric phase transition around 100 °C. Around this temperature, there is a significant shape change in both P-E and S-E curves, accompanied by enhanced strain and decreased polarization; the largest recoverable strain reaches 0.42%. These results can be explained by the formation of antiferroelectric order and the contribution of field-induced antiferroelectric-ferroelectric phase transition to piezoelectric response. Our results indicate that BNT-BT-BKT lead-free piezoceramics can have excellent electrical properties in compositions near the MPB and also reveal some insight into the temperature dependence of the electrical performance with the MPB composition.     

Properties of praseodymium-doped bismuth potassium titanate (Bi0.5K0.5TiO3) synthesised using the soft combustion technique

Bismuth potassium titanate (Bi_0.5K_0.5TiO₃; BKT) and praseodymium-doped BKT (Bi_0.5(1−x)Pr_xK_0.5TiO₃; BPKT) powders were synthesised using the soft combustion technique. Fine particles of 10-100 nm of BKT and BPKT were produced. A single phase BKT was obtained with a minimum of 0.5 mol of glycine. Various compounds of Bi_0.5(1−x)Pr_xK_0.5TiO₃ where x = 0.01, 0.03, 0.05, 0.10, 0.15 and 0.20 were prepared. Pure BKT and BPKT powders were obtained after calcination at 800 °C for 3 h. After sintering at 1050 °C for 5 h, pure BKT and BPKT pellets were obtained for x = 0 and 0.01. However, for BPKT with x = 0.03, 0.05, 0.10, 0.15 and 0.20, a minor amount of Bi₄Ti₃O₁₂ (BIT) secondary phase was present after sintering at 1050 °C for 5 h. The crystallite size and grain size of all the samples followed similar trends, first increasing from x = 0 (undoped BKT) to x = 0.05 and then decreasing above x = 0.05. Among the undoped and doped samples, BPKT with x = 0.05 had the highest dielectric properties (?_r = 713.87) due to its large crystallite size (68.66 nm), large grain size (∼435 nm) and high relative density (93.39%).     

Improving the piezoelectric thermal stability by tailoring phase transition behavior in the new (1 − x)[0.65PbMg1/3Nb2/3O3-0.35PbTiO3]-xBiZn1/2Ti1/2O3 perovskite solid solutions

The phase transition behavior and its effect on thermal stability of the piezoelectric properties of the (1 − x)[0.65PbMg_1/3Nb_2/3O₃-0.35PbTiO₃]-xBiZn_1/2Ti_1/2O₃ ceramics with 0 ≤ x ≤ 0.06 were investigated. The phase transition from the monoclinic to tetragonal phase was determined by the dielectric constant and elastic constant measurements. The temperature independent piezoelectric response with −d₃₁ = 188 pC/N was obtained from 175 to 337 K for the composition with x = 0.02. The enhanced thermal stability of piezoelectric response was achieved by shifting the monoclinic-tetragonal phase transition to the lower temperature.     

Phase transition and electrical properties of (1 − x)K0.02Na0.98NbO3-xBaTiO3 ceramics

(1 − x)K_0.02Na_0.98NbO₃-xBaTiO₃ ceramics were prepared by the solid state reaction method, and their electrical properties were investigated. The samples showed crystal structure changing from monoclinic to orthorhombic, and then to tetragonal, with an increase in BaTiO₃ content. The addition of BaTiO₃ markedly enhanced ferroelectric and piezoelectric properties of K_0.02Na_0.98NbO₃ ceramics. Remnant polarization increased and coercive field decreased only in the samples with small amount of BaTiO₃. Piezoelectric properties were improved with the addition of BaTiO₃. The 0.9K_0.02Na_0.98NbO₃-0.1BaTiO₃ ceramics showed maximum piezoelectric constant (d₃₃ = 160 pC/N), which was even comparable with that of (1 − x)K_0.5Na_0.5NbO₃-xBaTiO₃ ceramics. Their good piezoelectric properties, along with a low ferroelectric-ferroelectric transition temperature (T_F-F), made the 0.9K_0.02Na_0.98NbO₃-0.1BaTiO₃ ceramics a potential candidate for lead-free piezoelectric applications.     

Structure and electrical properties of MnO2-doped Sr2−xCaxNaNb5O15 lead-free piezoelectric ceramics

Lead-free piezoelectric ceramics Sr_2−xCa_xNaNb₅O₁₅ + y wt% MnO₂have been prepared by the conventional solid state reaction method. Our results reveal that Ca²⁺and Mn ions have entered into the Sr₂NaNb₅O₁₅ lattices to form a solid solution with tungsten-bronze structure. The substitution of Ca²⁺ induces a decrease in piezoelectric coefficient d₃₃, electromechanical coupling factors k_p and k_t, while, the addition of Mn ions decreases the sintering temperature and effectively promotes the densification of the ceramics. The effect of substitution of Ca²⁺and Mn ions on the structure, electrical properties and diffused phase changing were investigated systematically. For the ceramic with x = 0.05 and y = 0.5, the piezoelectric, dielectric and ferroelectric properties become optimum, giving a piezoelectric coefficient d₃₃ = 190 pC/N, electromechanical coupling factors k_p = 13.4% and k_t = 36.5%, ?_r = 2123, loss tangent tan δ = 0.038, remanent polarization P_r = 4.76 μC/cm², coercive field E_c = 12.68 kV/cm, and Curie temperature T_c = 260 °C.     

Coexistence of room temperature ferroelectricity and ferrimagnetism in multiferroic BiFeO3-Bi0.5Na0.5TiO3 solid solution

The structure, ferroelectric and magnetic properties of (1 − x)BiFeO₃-xBi_0.5Na_0.5TiO₃ (x = 0.37) solid solution fabricated by a sol-gel method have been investigated. X-ray diffraction and Raman spectroscopy measurements show a single-phase perovskite structure with no impurities identified. Compared with pure BiFeO₃, the coexistence of ferroelectricity and ferrimagnetism have been observed at room temperature for the solution with remnant polarization P_r = 1.41 μC/cm² and remnant magnetization M_r = 0.054 emu/g. Importantly, a magnetic transition from ferrimagnetic (FM) ordering to paramagnetic (PM) state is observed, with Curie temperature T_C ∼ 330 K, being explained in terms of the suppression of cycloid spin configuration by the structural distortion.     

The structural and electric properties of Li- and K-substituted Bi0.5Na0.5TiO3 ferroelectric ceramics

The structure, dielectric properties and phase transition of lithium and potassium modified Bi_0.5Na_0.5TiO₃ ceramics were investigated widely. The phase transition behavior with respect to changes in composition and temperature was investigated using X-ray diffraction analysis, dielectric and ferroelectric characterizations. The experimental results show that there is a diffusion phase transition in (Na_1−xK_x)_0.5Bi_0.5TiO₃ ceramics at T_m and the diffuseness of the phase transition is more obvious for the samples near the morphotropic phase boundary. In (Na_1−xLi_x)_0.5Bi_0.5TiO₃ system, due to the space charge polarization induced by ions conductivity, the low frequency permittivity increases so remarkably at high temperature that the peak of maximum permittivity vanishes. The hysteresis loops at different temperatures indicate that there is no existence of anti-ferroelectrics in lithium and potassium modified Bi_0.5Na_0.5TiO₃ ceramics above the depolarization temperature T_d. The depolarization reason is that the tetragonal nonpolar phase occurs and leads to the macro-micro domain transformation at about T_d.     

High-dielectric-constant and low-loss microwave dielectric in the (1 − x)La(Mg0.5Ti0.5)O3-x(Ca0.8Sr0.2)TiO3 solid solution system

The microwave dielectric properties and microstructures of (1 − x)La(Mg_0.5Ti_0.5)O₃-x(Ca_0.8Sr_0.2)TiO₃ ceramics, prepared by a mixed oxide route, have been investigated. The forming of solid solutions was confirmed by the XRD patterns and the measured lattice parameters for all compositions. A near zero τ_f was achieved for samples with x = 0.5, although the dielectric properties varied with sintering temperature. The Q × f value of 0.5La(Mg_0.5Ti_0.5)O₃-0.5(Ca_0.8Sr_0.2)TiO₃ increased up to 1475 °C, after which it decreased. The decrease in dielectric properties was coincident with the onset of rapid grain growth. The optimum combination of microwave dielectric properties was achieved at 1475 °C for samples where x = 0.5 with a dielectric constant ?_r of 47.12, a Q × f value of 35,000 GHz (measured at 6.2 GHz) and a τ_f value of −4.7 ppm/°C.     

Structure and dielectric characterization of xNd(Mg1/2Ti1/2)O3-(1 − x)Ca0.6La0.8/3TiO3 in the microwave frequency range

The crystal structures, phase compositions and the microwave dielectric properties of the xLa(Mg_1/2Ti_1/2)O₃-(1 − x)Ca_0.8Sr_0.2TiO₃ composites prepared by the conventional solid state route have been investigated. The formation of solid solution is confirmed by the XRD patterns. Doping with B₂O₃ (0.5 wt.%) can effectively promote the densification and the dielectric properties of xNd(Mg_1/2Ti_1/2)O₃-(1 − x)Ca_0.6La_0.8/3TiO₃ ceramics. It is found that xNd(Mg_1/2Ti_1/2)O₃-(1 − x)Ca_0.6La_0.8/3TiO₃ ceramics can be sintered at 1375 °C, due to the liquid phase effect of B₂O₃ addition observed by Scanning Electronic Microscopy. At 1375 °C, 0.4Nd(Mg_1/2Ti_1/2)O₃-0.6Ca_0.6La_0.8/3TiO₃ ceramics with 1 wt.% B₂O₃ addition possesses a dielectric constant (?_r) of 49, a Q × f value of 13,000 (at 8 GHz) and a temperature coefficients of resonant frequency (τ_f) of 1 ppm/°C. As the content of Nd(Mg_1/2Ti_1/2)O₃ increases, the highest Q × f value of 20,000 GHz for x = 0.9 is achieved at the sintering temperature 1400 °C.     

Microwave dielectric properties of (1 − x)ZnMoO4-xTiO2 composite ceramics

(1 − x)ZnMoO₄-xTiO₂ (x = 0.0, 0.05, 0.158, 0.25, and 0.35) composite ceramics were synthesized by the conventional solid state reaction process. The sintering behavior, phase composition, chemical compatibility with silver, and microwave dielectric properties were investigated. All the specimens can be well densified below 950 °C. From the X-ray diffraction analysis, it indicates that the triclinic wolframite ZnMoO₄ phase coexists with the tetragonal rutile TiO₂ phase, and it is easy for silver to react with ZnMoO₄ to form Ag₂Zn₂(MoO₄)₃ phase and hard to react with TiO₂. When the volume fraction of TiO₂ (x value) increasing from 0 to 0.35, the microwave dielectric permittivity of the (1 − x)ZnMoO₄-xTiO₂ composite ceramics increases from 8.0 to 25.2, the Q_f value changes in the range of 32,300-43,300 GHz, and the temperature coefficient τ_f value varies from −128.9 to 157.4 ppm/°C. At x = 0.158, the mixture exhibits good microwave dielectric properties with a ?_r = 13.9, a Q_f = 40,400 GHz, and a τ_f = +2.0 ppm/°C.     

Phase transition and piezoelectric properties of K0.48Na0.52NbO3-LiTa0.5Nb0.5O3-NaNbO3 lead-free ceramics

Plate-like NaNbO₃ (NN) particles were used as the raw material to fabricate (1 − x)[0.93 K_0.48Na_0.52Nb O₃-0.07Li(Ta_0.5Nb_0.5)O₃]-xNaNbO₃ lead-free piezoelectric ceramics using a conventional ceramic process. The effects of NN on the crystal structure and piezoelectric properties of the ceramics were investigated. The results of X-ray diffraction suggest that the perovskite phase coexists with the K₃Li₂Nb₅O₁₅ phase, and the tilting of the oxygen octahedron is probably responsible for the evolution of the tungsten-bronze-typed K₃Li₂Nb₅O₁₅ phase. The Curie temperature (T_C) is shifted to lower temperature with increasing NN content. (1 − x)[0.93 K_0.48Na_0.52NbO₃-0.07Li(Ta_0.5Nb_0.5)O₃]-xNaNbO₃ ceramics show obvious dielectric relaxor characteristics for x > 0.03, and the relaxor behavior of ceramics is strengthened by increasing NN content. Both the electromechanical coupling factor (k_p) and the piezoelectric constant (d₃₃) decrease with increasing amounts of NN. 0.01-0.03 mol of plate-like NaNbO₃ in 0.93 K_0.48Na_0.52NbO₃-0.07Li(Ta_0.5Nb_0.5)O₃ gives the optimum content for preparing textured ceramics by the RTGG method.     

Phase evolution, crystal structure and dielectric behavior of (1 − x)Nd(Zn0.5Ti0.5)O3 + xBi(Zn0.5Ti0.5)O3 compound ceramics

The phase evolution, crystal structure and dielectric properties of (1 − x)Nd(Zn_0.5Ti_0.5)O₃ + xBi(Zn_0.5Ti_0.5)O₃ compound ceramics (0 ≤ x ≤ 1.0, abbreviated as (1 − x)NZT-xBZT hereafter) were investigated. A pure perovskite phase was formed in the composition range of 0 ≤ x ≤ 0.05. The B-site Zn²⁺/Ti⁴⁺ 1:1 long range ordering (LRO) structure was detected by both XRD and Raman spectra in x ≤ 0.05 samples. However, this LRO structure became gradually degraded with an increase in x. The dielectric behaviors of the compound ceramic at various frequencies were investigated and correlated to its chemical composition and crystal structure. A gradually compensated τ_f value was obtained in (1 − x)NZT-xBZT microwave dielectrics at x = 0.03, which was mainly due to the dilution of dielectric constant in terms of Claussius-Mossotti differential equation.     

Study of structural, dielectric and electrical behavior of (1 − x)Ba(Fe0.5Nb0.5)O3-xSrTiO3 ceramics

Polycrystalline samples of BaFe_0.5Nb_0.5O₃ and (1 − x)Ba(Fe_0.5Nb_0.5)O₃-xSrTiO₃ [referred as BFN and BFN-ST respectively] (x = 0.00, 0.15 and 0.20) have been synthesized by a high-temperature solid-state reaction technique. The XRD patterns of the BFN and BFN-ST at room temperature show a monoclinic phase. The microstructure of the ceramics was examined by the scanning electron microscopy (SEM) and shows the polycrystalline nature of the samples with different grain sizes, which are inhomogeneously distributed through the sample surface. Detailed studies of dielectric and impedance properties of the materials in a wide range of frequency (100 Hz-5 MHz) and temperatures (30-270 °C) showed that properties are strongly temperature and frequency dependent. Complex Argand plane plot of ?″ against ?′, usually called Cole-Cole plots is used to check the polydispersive nature of relaxation phenomena in above mentioned compounds. Relaxation phenomena of non-Debye type have been observed in the BFN and BFN-ST ceramics, as confirmed by the Cole-Cole plots.     

Relationship between structure and properties in high-temperature Bi(Al0.5Fe0.5)O3-PbTiO3 piezoelectric ceramics

Ceramic samples of xBi(Al_0.5Fe_0.5)O₃-(1 − x)PbTiO₃ (BAF-PT, x = 0.05-0.5) solid solutions were fabricated using the conventional solid state reaction method. X-ray diffraction analysis revealed that all compositions can form single perovskite phase with tetragonal symmetry. The relationship between the tetragonal lattice parameters, tetragonality c/a, cell volume, and ferro-piezoelectric characterization as a function of x was systematically investigated. The BAF modification can effectively improve the poling condition at a proper BAF content. A combination of piezoelectric constant of d₃₃ (50-60 pC/N), electromechanical planar coupling coefficients of k_p (20.3-22.5%), and high Curie temperature T_c (>478 °C) suggested that BAF-PT could be a good candidate for high-temperature piezoelectric applications.