Influences of poling condition and sintering temperature on piezoelectric properties of (Na0.5Bi0.5)1 − xBaxTiO3 ceramics

The structure, ferroelectric characteristics and piezoelectric properties of (Na_0.5Bi_0.5)_1 − xBa_xTiO₃ (x = 0.04, 0.06, 0.10) ceramics prepared by conventional solid state method were investigated. The influences of poling condition and sintering temperature on the piezoelectric properties of the ceramics were examined. The piezoelectric properties of the ceramics highly depend on poling field and temperature, while no remarkable effect of poling time on the piezoelectric properties was found in the range of 5-25 min. Compared with (Na_0.5Bi_0.5)_0.96Ba_0.04TiO₃ and (Na_0.5Bi_0.5)_0.90Ba_0.10TiO₃, the piezoelectric properties of (Na_0.5Bi_0.5)_0.94Ba_0.06TiO₃ are more sensitive to poling temperature due to the relatively low depolarization temperature. Moderate increase of sintering temperature improved the poling process and piezoelectric properties due to the development of microstructural densification and crystal structure. With respect to sintering behavior and piezoelectric properties, a sintering temperature range of 1130-1160 °C was ascertained for (Na_0.5Bi_0.5)_0.90Ba_0.10TiO₃.     

Influence of sintering temperature on piezoelectric properties of (K0.5Na0.5)NbO3-LiNbO3 lead-free piezoelectric ceramics

Lead-free piezoelectric ceramics (1 − x)(K_0.5Na_0.5)NbO₃-xLiNbO₃ have been synthesized by traditional ceramics process without cold-isostatic pressing. The effect of the content of LiNbO₃ and the sintering temperature on the phase structure, the microstructure and piezoelectric properties of (1 − x)(K_0.5Na_0.5)NbO₃-xLiNbO₃ ceramics were investigated. The result shows that the phase structure transforms from the orthorhombic phase to tetragonal phase with the increase of the content of LiNbO₃, and the orthorhombic and tetragonal phase co-exist in (K_0.5Na_0.5)NbO₃-LiNbO₃ ceramics when the content of LiNbO₃ is about 0.06 mol. The sintering temperature of (1 − x)(K_0.5Na_0.5)NbO₃-xLiNbO₃ decreases with the increase of the content of LiNbO₃. The optimum composition for (1 − x)(K_0.5Na_0.5)NbO₃-xLiNbO₃ ceramics is 0.94(K_0.5Na_0.5)NbO₃-0.06LiNbO₃. The optimum sintering temperature of 0.94(K_0.5Na_0.5)NbO₃-0.06LiNbO₃ ceramics is 1080 °C. Piezoelectric properties of 0.94 (K_0.5Na_0.5)NbO₃-0.06LiNbO₃ ceramics under the optimum sintering temperature are piezoelectric constant d₃₃ of 215 pC/N, planar electromechanical coupling factor k_p of 0.41, thickness electromechanical coupling factor k_t of 0.48, the mechanical quality factor Q_m of 80, the dielectric constant of 530 and the Curie temperature T_c = 450 °C, respectively. The results indicate that 0.94(K_0.5Na_0.5)NbO₃-0.06LiNbO₃ piezoelectric ceramics is a promising candidate for lead-free piezoelectric ceramics.     

Ferroelectric and pyroelectric properties of (Na0.5Bi0.5)TiO3-BaTiO3 based trilayered thin films

Trilayered Bi_3.25La_0.75Ti₃O₁₂ (25 nm)/(Na_0.5Bi_0.5)_0.94Ba_0.06TiO₃ (300 nm)/Bi_3.25La_0.75Ti₃O₁₂ (25 nm) and Pb(Zr_0.4Ti_0.6)O₃ (25 nm)/(Na_0.5Bi_0.5)_0.94Ba_0.06TiO₃ (300 nm)/Pb(Zr_0.4Ti_0.6)O₃ (25 nm) thin films without undesirable phases have been deposited on Pt/Ti/SiO₂/Si substrates. It was found that the Bi_3.25La_0.75Ti₃O₁₂ and Pb(Zr_0.4Ti_0.6)O₃ layers are very effective to inhibit the charge transport in the trilayered films. Much better insulating properties than those of (Na_0.5Bi_0.5)_0.94Ba_0.06TiO₃ films have been achieved in the trilayered films. The trilayered films show good dielectric, ferroelectric and pyroelectric properties. Remnant polarizations 2P_r of 16 µC/cm² and 34 µC/cm², pyroelectric coefficients of 4.8 × 10^− 4 C m^− 2 K^− 1 and 7.0 × 10^− 4 C m^− 2 K^− 1 have been obtained for the Bi_3.25La_0.75Ti₃O₁₂/(Na_0.5Bi_0.5)_0.94Ba_0.06TiO₃/Bi_3.25La_0.75Ti₃O₁₂ and Pb(Zr_0.4Ti_0.6)O₃/(Na_0.5Bi_0.5)_0.94Ba_0.06TiO₃/Pb(Zr_0.4Ti_0.6)O₃ thin films, respectively. The trilayered films are promising candidates for sensor and actuator applications.     

Structure and electrical properties of (1 − x)Bi0.5Na0.5TiO3-xBi0.5K0.5TiO3 ceramics near morphotropic phase boundary

The binary lead-free piezoelectric ceramics with the composition of (1 − x)Bi_0.5Na_0.5TiO₃-xBi_0.5K_0.5TiO₃ were synthesized by conventional mixed-oxide method. The phase structure transformed from rhombohedral to tetragonal phase in the range of 0.16 ≤ x ≤ 0.20. The grain sizes varied with increasing the Bi_0.5K_0.5TiO₃ content. Electrical properties of ceramics are significantly influenced by the Bi_0.5K_0.5TiO₃ content. Two phase transitions at T_t (the temperature at which the phase transition from rhombohedral to tetragonal occurs) and T_c (the Curie temperature) were observed in all the ceramics. Adding Bi_0.5K_0.5TiO₃ content caused the variations of T_t and T_c. A diffuse character was proved by the linear fitting of the modified Curie-Weiss law. Besides, the ceramics with homogeneous microstructure and excellent electrical properties were obtained at x = 0.18 and sintered at 1170 °C. The piezoelectric constant d₃₃, the electromechanical coupling factor K_p and the dielectric constant ?_r reached 144 pC/N, 0.29 and 893, respectively. The dissipation factor tan δ was 0.037.     

Fabrication of lead-free (Na0.82K0.18)0.5Bi0.5TiO3 piezoelectric nanofiber by electrospinning

(Na_0.82K_0.18)_0.5Bi_0.5TiO₃ nanofibers were synthesized by sol-gel process and electrospinning. Scanning electron microscopy was used to verify that the diameters and lengths are in the range of 150-600 nm and several hundreds of micrometer. Perovskite structure and grain size (20-70 nm) were verified by X-ray diffraction and transmission electron microscopy. The high effective piezoelectric coefficient d₃₃ (96 pm/V) was measured by scanning force microscopy. It may be attributed to easily tilting the polar vector of domain for an electric field and the increase in the number of possible spontaneous polarization direction near the rhombohedral-tetragonal morphotropic phase boundary. The research shows that there are potentional applications for (Na_0.82K_0.18)_0.5Bi_0.5TiO₃ nanofiber in nanoscale lead-free piezoelectric devices.     

Dielectric, ferroelectric and piezoelectric properties of Bi0.5Na0.5TiO3-(Ba0.7Ca0.3)TiO3 ceramics at morphotropic phase boundary composition

(1 − x)Bi_0.5Na_0.5TiO₃-x(Ba_0.7Ca_0.3)TiO₃ (BNT-xBCT, 0 ≤ x ≤ 0.15) solid solutions have been synthesized by a conventional solid state sintering method for obtaining a morphotropic phase boundary (MPB) with good piezoelectric properties. X-ray diffraction patterns reveal that a MPB of rhombohedral and tetragonal phases is formed at compositions 0.09 ≤ x ≤ 0.12. Addition of BCT into BNT greatly lowered coercive field E_c without degrading remanent polarization P_r. The specimen with x = 0.09 has the good piezoelectric properties: d₃₃ = 125 pC/N and k_p = 0.33. A modified Curie-Weiss law was used to fit the dielectric constant of BNT-xBCT ceramics, and a frequency dispersion was observed during the phase transitions from antiferroelectric to paraelectric in specimens with x exceeding 0.06.     

The synthesis of lead-free ferroelectric Bi0.5Na0.5TiO3-Bi0.5K0.5TiO3 thin films by sol-gel method

(1 − x)Bi_0.5Na_0.5TiO₃-xBi_0.5K_0.5TiO₃ [BNT-BKT-100x] thin films have been successfully deposited on Pt/Ti/SiO₂/Si substrates by a sol-gel process together with rapid thermal annealing. A morphotropic phase boundary (MPB) between Bi_0.5Na_0.5TiO₃ and Bi_0.5K_0.5TiO₃ was determined around x ∼ 0.15. Near the MPB, the film exhibits the largest grain size, the highest ε value (360) and the largest P_r value (13.8 μC/cm²). The BNT-BKT thin film system is expected to be a new and promising candidate for lead-free piezoelectric applications.     

Electrical and luminescence properties of Er-doped Bi0.5Na0.5TiO3 ceramics

The influences of Er content on the dielectric and photoluminescence performances of Bi_0.5Na_0.5TiO₃-xEr (x = 0, 0.005, 0.01, 0.015, 0.02, 0.03) ceramics have been investigated. The results show that Bi_0.5Na_0.5TiO₃-xEr ceramics with x = 0.01 Er have maximum values of photoluminescence and piezoelectric properties. A bright green emission at 550 nm and enhanced piezoelectric response are achieved in the ceramic Bi_0.5Na_0.5TiO₃-0.01Er at room temperature. Furthermore, the photoluminescence performance of the ceramics is significantly enhanced by electric poling.     

Topochemical synthesis of plate-like Na0.5Bi0.5TiO3 templates from Bi4Ti3O12

Plate-like templates for the development of grain oriented microstructures are required for lead-free piezoelectric ceramics with directionality of properties. Plate-like Na_0.5Bi_0.5TiO₃ templates with perovskite structure were synthesized by the Topochemical Microcrystal Conversion (TMC) method from bismuth layer-structured ferroelectric compound Bi₄Ti₃O₁₂. The TMC-derived NBT templates, with diameters of 5-15 µm and an average thickness of 0.7 µm, maintained the morphology of Bi₄Ti₃O₁₂ precursors, showing a high degree of preferred pseudocubic < 001> orientation. The Na_0.5Bi_0.5TiO₃ particles prepared could serve as good templates for the preparation of grain oriented lead-free NBT-based piezoelectric ceramics.     

Structure and ferroelectric properties in (K0.5Bi0.5)TiO3-BiScO3-PbTiO3 piezoelectric ceramic system

(K_0.5Bi_0.5)TiO₃-BiScO₃-PbTiO₃ ceramics were synthesized by conventional solid-state method. A morphotropic phase boundary (MPB) was confirmed with the aid of structural analysis. Two dielectric anomalous peaks were observed, the one around dielectric maximum temperature (T_m) due to phase transformation from ferroelectric to paraelectric while the second one could be ascribed to space charges. Furthermore, the existence of space charges also resulted in the independence of T_m with frequency at low lead composition. A new high temperature piezoelectric ceramic, 0.30(K_0.5Bi_0.5)TiO₃-0.30BiScO₃-0.40PbTiO₃ close to MPB exhibited excellent electrical properties with T_m of 384 °C, d₃₃ of 247 pC/N, k_p of 38.9%, P_r of 19.41 μC/cm², and E_c of 2.25 kV/mm, indicative of a candidate for high temperature application.     

Ferroelectric properties of lithia-doped (Bi0.95Na0.75K0.20)0.5Ba0.05TiO3 ceramics

Lead-free piezoelectric (Bi_0.95Na_0.75K_0.20−xLi_x)_0.5Ba_0.05TiO₃ ceramics have been prepared by conventional process for different lithium substitutions. The SEM images show that the ceramics are well sintered at 1428 K. Dielectric and ferroelectric measurements have been performed. With the increasing of lithium substitution, the Curie temperature of the (Bi_0.95Na_0.75K_0.20−xLi_x)_0.5Ba_0.05TiO₃ ceramics shifts from 570 K to 620 K, but the maximum value of the dielectric constant decreases from 6700 to 4700 correspondingly. A relatively larger remanent polarization of 36.8 μC/cm² has been found in the x = 0.05 sample. The coercive field decreases as the lithium substitution amount increases. An optimized d₃₃ = 194 × 10^− 12 C/N and a relative dielectric constant ε_r = 1510 have been obtained in (Bi_0.95Na_0.75K_0.15Li_0.05)_0.5Ba_0.05TiO₃.     

Tunable and microwave dielectric properties of Ba0.5Sr0.5TiO3-BaWO4 composite ceramics doped with Co2O3

Co₂O₃ doped BaWO₄-Ba_0.5Sr_0.5TiO₃ composite ceramics, prepared by solid-state route, were characterized systematically, in terms of their phase compositions, microstructure and microwave dielectric properties. Doping of Co₂O₃ promoted grain growth, reduced Curie temperature and broadened phase-transition temperature range of BaWO₄-Ba_0.5Sr_0.5TiO₃, which were attributed mainly to the substitution of Co³⁺ for Ti⁴⁺ at B site in the perovskite lattice. Dielectric diffusion behaviors of the composite ceramics were discussed. The composite ceramics all had dielectric tunability of higher than 10% at 30 kV/cm and 10 kHz, with promising microwave dielectric properties. Specifically, the sample doped with 0.2 wt.% Co₂O₃ exhibited a tunability of 20%, permittivity of 225 and Q of 292 (at 1.986 GHz), making it a suitable candidate for applications in electrically tunable microwave devices.     

Crystal structure and Eu/Tb doped luminescent properties of a new borate Ba3BiB9O18

Undoped and doped either by Eu³⁺ or Tb³⁺ bismuth borate Ba₃BiB₉O₁₈ was structurally characterized and analyzed by fluorescence spectroscopy. Belonging to synthetic borate member of the family Ba₃XB₉O₁₈, layers of planar triangular B₃O₆ groups connecting with deformed BaO₆ hexagons are interleaved by 9-coordinate Ba atoms, and 6-coordinate Bi atoms. Its crystal structure was determined and refined from powder X-ray diffraction data by the Rietveld method and the results showed that Ba₃BiB₉O₁₈ belongs to space group P6₃/m with unit cell dimensions of a = 7.1999(2) Å, c = 17.3567(6) Å, and z = 2. Curves of differential thermal analysis and thermogravimetric analysis showed that Ba₃BiB₉O₁₈ is a congruent melting compound and chemically stable above 728 °C. Ba₃Bi_1−xEu_xB₉O₁₈ and Ba₃Bi_1−xTb_xB₉O₁₈ form a continuous solid solution from x = 0.01 to x = 0.9. The ultraviolet excited photoluminescence intensity increased with both Eu³⁺ and Tb³⁺ concentration in the matrix of Ba₃BiB₉O₁₈. There may be an interesting correlation between spectroscopic properties and lattice structural features of doped Ba₃BiB₉O₁₈.     

Structure and electrical properties of Bi0.5Na0.5TiO3-Y0.5Na0.5TiO3-BaTiO3 lead-free piezoelectric ceramics

New (1 – x ? y)Bi_0.5Na_0.5TiO₃-xY_0.5Na_0.5TiO₃-yBaTiO₃ lead-free ceramics have been prepared by a conventional ceramic fabrication technique, and their structure and electrical properties have been studied. A morphotropic phase boundary (MPB) of rhombohedral and tetragonal phases is formed at 0.04 < y < 0.10. As compared to pure Bi_0.5Na_0.5TiO₃ ceramic, the partial substitutions of Y³⁺ for Bi³⁺ and Ba²⁺ for (Bi_0.5Na_0.5)²⁺ in the A-sites of Bi_0.5Na_0.5TiO₃ lower effectively the coercive field E _c and increase the remanent polarization P _r of the ceramics. Because of low E _c, large P _r and the MPB, the ceramics with x = 0–0.02 and y = 0.06 exhibit the optimum piezoelectric properties: d ₃₃ = 155–159 pC/N and k _p = 28.8–36.7%. The temperature dependences of dielectric properties of the ceramics show relaxor-like behaviors. The ferroelectric properties at different temperature suggest that the ceramics may contain both the polar and non-polar regions near/above T _d.     

Effects of K4CuNb8O23 on the structure and electrical properties of lead-free 0.94(Na0.5K0.5)NbO3–0.06LiNbO3 ceramics

Dense K₄CuNb₈O₂₃-modified (K_0.5Na_0.5)_0.94Li_0.06NbO₃ ceramics were prepared by normal sintering. The effects of K₄CuNb₈O₂₃ on the phase structure, microstructure and electrical properties of the ceramics were studied. Results showed that K₄CuNb₈O₂₃ induced a perovskite structure transition from coexistence of orthorhombic and tetragonal phases to orthorhombic symmetry. The addition of K₄CuNb₈O₂₃ promoted the sintering of (K_0.5Na_0.5)_0.94Li_0.06NbO₃ ceramics and simultaneously caused the grain growth. Moreover, K₄CuNb₈O₂₃-doping changed the (K_0.5Na_0.5)_0.94Li_0.06NbO₃ to “hard” ceramics and significantly enhanced the mechanical quality factor Q_m. It was found that the (K_0.5Na_0.5)_0.94Li_0.06NbO₃ ceramics doped with 0.60 mol% K₄CuNb₈O₂₃ exhibited a high mechanical quality factor (Q_m  983) as well as relatively large d₃₃ (136 pC/N) and k_p (35.9%), suggesting that this material is a promising candidate for lead-free piezoelectric ceramics for high-frequency applications.     

Synthesis and characterization of (Na0.85K0.15)0.5Bi0.5TiO3 ceramics by different methods

The (Na_0.85K_0.15)_0.5Bi_0.5TiO₃ (BNKT) powders were synthesized by solid-state method, sol-gel method and stearic acid method. Microstructure, piezoelectric and dielectric properties of the ceramics were investigated. Attempts had been made to understand the reaction processes by using thermo gravimetric (TG) and differential scanning calorimetry (DSC). The BNKT powders have a perovskite structure with average crystallite sizes of 168 nm, 85 nm and 79 nm, corresponding to the solid-state method, the sol-gel method and the stearic acid method, respectively. The ceramics derived from the powder synthesized by sol-gel method presents the most homogeneous microstructure and largest grain size (5-7 μm). The effects of average crystallite size on microstructures and electric properties of the BNKT ceramics were investigated. Both the piezoelectric properties and dielectric properties were enhanced with the increase of grain size.     

Synthesis,ferroelectric and piezoelectric properties of some (Na0.5Bi0.5)TiO3 system compositions

Some (Na_0.5Bi_0.5)TiO₃ (NBT) system compositions, including NBT, (Na_0.5Bi_0.5)_0.94Ba_0.06TiO₃ (NBBT) and 0.4 wt.% CoO added NBBT (NBBTC), were prepared by a citrate method. The ferroelectric and piezoelectric properties of the resulting ceramics were investigated. The results confirm that the citrate method is a feasible and advantageous route to produce NBT system ceramics. NBBT ceramic made by the citrate method exhibits a high piezoelectric constant (d₃₃) of 180 pC/N. An essential relation between the piezoelectric properties and the ferroelectric nature of the ceramics was detected. It was found that lowering the coercive field (E_c) and enhancing the remanent polarization (P_r) of NBT system ceramics simultaneously lead to desired piezoelectric properties.     

Effect of CuO on the sintering temperature and piezoelectric properties of lead-free 0.95(Na0.5K0.5)NbO3-0.05CaTiO3 ceramics

The addition of a small amount of CuO to the 0.95(Na_0.5K_0.5)NbO₃-0.05CaTiO₃ (0.95NKN-0.05CT) ceramics sintered at 960 °C for 10 h produced a dense microstructure with large grains due to the liquid phase sintering. Due to the negligible Na₂O evaporation, poling was easy for all specimens sintered at 960 °C. The piezoelectric properties of the specimens were considerably influenced by the relative density, grain size and liquid phase amount. The high piezoelectric properties of d₃₃ = 200 pC/N, k_p = 0.37, and Q_m = 350 were obtained for the 0.95NKN-0.05CT ceramics containing 2.0 mol% CuO sintered at 960 °C for 10 h. Therefore, the 0.95NKN-0.05CT ceramics containing a small amount of CuO are a good candidate material for lead-free piezoelectric ceramics.     

Piezoelectric, ferroelectric and dielectric properties of La2O3-doped (Bi0.5Na0.5)0.94Ba0.06TiO3 lead-free ceramics

La₂O₃ (0–0.8 wt.%)-doped (Bi_0.5Na_0.5)_0.94Ba_0.06TiO₃ (abbreviated as BNBT6) lead-free piezoelectric ceramics were synthesized by conventional solid-state reaction. The influences of La₂O₃ on the microstructure, the dielectric, ferroelectric and piezoelectric properties of the composites were investigated. X-ray diffraction (XRD) patterns indicate that 0.2-0.8 wt.% of La₂O₃ has diffused into the lattice of BNBT6 ceramics. Consequently, a pure perovskite phase is formed. SEM images show that the microstructure of the ceramics is changed with the addition of a small amount of La₂O₃. The temperature dependence of the relative dielectric constant shows that Curie point decreases with the increase of La₂O₃. At room temperature, the ceramics doped with 0.6 wt.% La₂O₃ show superior performance with high piezoelectric constant (d₃₃ = 167 pC/N), high planar electromechanical coupling factor (k_p = 0.30), high mechanical quality factor (Q_m = 118), high relative dielectric constant (ε_r = 1470) and lower dissipation factor (tanδ = 0.056) at a frequency of 10 kHz.     

Morphotropic phase boundary and piezoelectric properties of (Bi1/2Na1/2)1 − x(Bi1/2K1/2)xTiO3-0.03(Na0.5K0.5)NbO3 ferroelectric ceramics

Lead-free piezoelectric ceramics, (Bi_1/2Na_1/2)_1 − x(Bi_1/2K_1/2)_xTiO₃-0.03(Na_0.5K_0.5)NbO₃ (x = 0.10-0.40) were synthesized by conventional solid-state sintering. A morphotropic phase boundary (MPB) between rhombohedral and tetragonal phases was confirmed. Two dielectric anomalies can be observed, showing diffused phase transition behavior. There is no shift of the dielectric maximum temperature with frequency due to the contribution of space charge at high temperatures, similar to pure (Bi_1/2Na_1/2)TiO₃. The materials near MPB show a strong compositional dependence with the optimal properties of a d₃₃ of 167 pC/N, a k_p of 35.5%, a P_r of 27.6 μC/cm² and a E_c of 27.9 kV/cm, suitable for future application.