Effect of MnO addition on structure and electrical properties of (Na0.5Bi0.5)0.94Ba0.06TiO3 ceramics prepared by citrate method

(Na_0.5Bi_0.5)_0.94Ba_0.06TiO₃ ceramics added with 0–0.8 wt.% MnO were prepared by a citrate method, and the influence of the MnO addition on the structure and electrical properties was investigated. The results indicate that the addition of small amounts of MnO did not cause a remarkable change in crystal structure, but resulted in an evident evolution in microstructure. The dielectric constant (_r) and piezoelectric constant (d₃₃) significantly decrease with increasing MnO content, while the electromechanical coupling factor (k_p) presents a slight variation in the range of 0.25–0.28. The dissipation factor (tan δ) and mechanical quality factor (Q_m) attain a minimum value of 1.5% and a maximum value of 304 when adding 0.4 and 0.5 wt.% MnO, respectively. This research demonstrates that doping effect and microstructural evolution contribute cooperatively to the electrical properties of the ceramics.     

Dielectric and piezoelectric properties of Y2O3 doped (Bi0.5Na0.5)0.94Ba0.06TiO3 lead-free piezoelectric ceramics

Y₂O₃ doped lead-free piezoelectric ceramics (Bi_0.5Na_0.5)_0.94Ba_0.06TiO₃ (0-0.7 wt%) were synthesized by the conventional solid state reaction method, and the effect of Y₂O₃ addition on the structure and electrical properties was investigated. X-ray diffraction shows that Y₂O₃ diffuses into the lattice of (Bi_0.5Na_0.5)_0.94Ba_0.06TiO₃ to form a solid solution with a pure perovskite structure. The temperature dependence of dielectric constant of Y₂O₃ doped samples under various frequencies indicates obvious relaxor characteristics different from typical relaxor ferroelectric and the mechanism of the relaxor behavior was discussed. The optimum piezoelectric properties of piezoelectric constant d₃₃ = 137 pC/N and the electromechanical coupling factor k_p = 0.30 are obtained at 0.5% and 0.1% Y₂O₃ addition, respectively.     

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.     

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.     

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.     

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.     

Piezoelectric and ferroelectric properties of K0.5Na0.5NbO3 ceramics synthesized by spray drying method

Potassium-sodium niobate was synthesized at 800 °C for 1 h using dried precursors in a powder form obtained by the spray drying method. Different samples were sintered from 1060 to 1120 °C for 2 h reaching a relative density as high as 96% of the theoretical value. Piezoelectric and ferroelectric properties were studied for these samples and some of the most prominent results are: k_p, d₃₁, 2P_r, and 2E_C of 0.36, 39 pC/N, 29 μC/cm² and 16.5 kV/cm, respectively, for the sample sintered at 1080 °C. The methodology presented in this study can be used to synthesize submicrometer powders.     

Abnormal electrocaloric effect of Na0.5Bi0.5TiO3–BaTiO3 lead-free ferroelectric ceramics above room temperature

We demonstrate the electrocaloric effect (ECE) of Na_0.5Bi_0.5TiO₃–BaTiO₃ (NBT–BT) lead-free ferroelectric ceramics, which were fabricated by the solid-state reaction method. Based on a Maxwell relation, the ECE was characterized via P–T curves under different electric fields. The polarization of NBT increases monotonically within the temperature range of 25–145 °C. It indicates that the NBT has an abnormal ECE with a negative temperature change (ΔT₁₄₀ = −0.33 K at E = 50 kV/cm) opposite to that of the normal ferroelectrics. The 0.92NBT–0.08BT composition near the morphotropic phase boundary has a normal ECE under low electric fields and an abnormal ECE under high electric fields. The abnormal ECE character originates from the relaxor characteristic between ferroelectric and antiferroelectric phases, while the common ECE is always related to the normal ferroelectric–paraelectric phase transition.     

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.     

Influence of A-site nonstoichiometry on sintering, microstructure and electrical properties of (Bi0.5Na0.5)TiO3 ceramics

Lead-free (Bi_0.5Na_0.5)_1+xTiO₃ ceramics (x = −0.02, −0.01, −0.005, 0, 0.005 and 0.01) were prepared by ordinary sintering. The effect of A-site stoichiometry on the densification, microstructure, dielectric properties, high-temperature impedances, and piezoelectric properties was explored. It was found that the high conductivity of (Bi_0.5Na_0.5)TiO₃ (BNT) ceramics should be mainly attributed to the formation of A-site cation vacancies during sintering. Improved physical and electrical properties can be achieved in the sample with A-site cation excess. The control of the stoichiometry proves to be an effective way to improve BNT ceramics for possible application.     

Synthesis of La(Mg0.5Ti0.5)O3 ceramics for microwave applications

La(Mg_0.5Ti_0.5)O₃ ceramics were prepared by a non-conventional chemical route, which was based on the Pechini method. For the synthesis of La(Mg_0.5Ti_0.5)O₃ powders, special attention was paid to calcination and milling conditions. Powder morphology and composition were evaluated. Fine La(Mg_0.5Ti_0.5)O₃ powders were obtained at lower temperatures than by conventional methods. Sintering under different conditions was also tested. Dense La(Mg_0.5Ti_0.5)O₃ ceramics were obtained at lower temperatures showing a single phase composition and a homogeneous microstructure. Preliminary dielectric characterization at microwave frequencies was also performed.     

Effect of BiFeO3 additions on the dielectric and piezoelectric properties of (K0.44Na0.52Li0.04)(Nb0.84Ta0.1Sb0.06)O3 ceramics

(1 − x) (K_0.44Na_0.52Li_0.04)(Nb_0.84Ta_0.1Sb_0.06)O₃ − x BiFeO₃ (x = 0, 0.002, 0.004, 0.006, 0.008, 0.01) lead-free piezoelectric ceramics were prepared by the conventional ceramic processing. The compositional dependence of the phase structure and the electrical properties of the ceramics were studied. A morphotropic phase boundary between the orthorhombic and tetragonal phases was identified in the composition range of 0.004 < x < 0.006. The ceramics near the morphotropic phase boundary exhibit a strong compositional dependence and enhanced piezoelectric properties. The ceramics with 0.6 mol.% BiFeO₃ exhibit good electrical properties (d₃₃ ∼ 246 pC/N, k_p ∼ 43%, T_c ∼ 285 °C, ?_r ∼ 1871, and tan δ ∼ 1.96%). These results show that the (1 − x) (K_0.44Na_0.52Li_0.04)(Nb_0.84Ta_0.1Sb_0.06)O₃ − x BiFeO₃ ceramic is a promising lead-free piezoelectric material for applications in different devices.     

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.     

Effect of mechanical activation on the structure and ferroelectric property of Na0.5K0.5NbO3

Mechanical activation synthesis of Na_0.5K_0.5NbO₃ (NKN) was studied in order to explore the effect of mechanochemical interaction on the crystal structure and microstructure of NKN powder and ceramic. A single phase, nanocrystalline perovskite NKN powder has been derived from a mixture of oxide/carbonates via a mechanical activation route with heating at an elevated temperature. With the increase in milling time, the distortion of orthorhombic structure for NKN was weakened and the cell volume of NKN powder slightly decreased. The relative density and remnant polarization of NKN ceramics were improved, and the grain became uniform and smaller for prolonged milling NKN. The developed method is well suited for the production of NKN nanocrystallite powders and refined grain NKN ceramics.     

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.     

Effects of Mn doping on the structure and electrical properties of high-temperature BiScO3-PbTiO3-Pb(Zn1/3Nb2/3)O3 piezoelectric ceramics

The effects of Mn addition on the structure, ferroelectric, and piezoelectric properties of the 0.35BiScO₃-0.60PbTiO₃-0.05Pb(Zn_1/3Nb_2/3)O₃ ceramics were studied. The results demonstrate that the addition of small amounts of Mn did not cause a remarkable change in crystal structure, but resulted in an evident evolution in microstructure and ferro-piezoelctric properties. The addition of Mn can induce combinatory “hard” and “soft” piezoelectric characteristics due to aliovalent substitutions. The optimal electrical properties are obtained in the 0.25 mol% Mn-doped composition with a high Curie temperature, indicating that Mn doping contributes to the electrical properties of the ceramics. It can be expected that the improved piezoelectric material can be a promising candidate for high-temperature piezoelectric applications.     

Synthesis and electrical properties of sodium bismuth niobate Na0.5Bi2.5Nb2O9

The crystal structure of Na_0.5Bi_2.5Nb₂O₉ was refined from its powder X-ray diffraction (XRD) data. Sodium bismuth niobate at 23 °C is orthorhombic, A2₁am, with a=5.4998(3) Å, b=5.4602(2) Å, c=24.952(1) Å, and Z=4. The piezoelectric properties were investigated using the dense bulk ceramics. The electromechanical coupling coefficients (k_ij) and electrical quality factors (Q_m) are k₃₁=3.2%, k_t=10.0%, and Q_m=3800. Single crystals were also grown from stoichiometric melts using a slow cooling technique. The dielectric and ferroelectric properties of the crystal indicates that a spontaneous polarization clearly occurs in the crystallographic a-b plane.     

Piezoelectric properties of Bi4Ti3O12 thin films annealed in different atmospheres

Bismuth titanate (Bi₄Ti₃O₁₂—BIT) films were evaluated for use as lead-free piezoelectric thin-films in micro-electromechanical systems. The films were grown by the polymeric precursor method on Pt/Ti/SiO₂/Si (1 0 0) (Pt) bottom electrodes at 700 °C for 2 h in static air and oxygen atmospheres. The domain structure was investigated by piezoresponse force microscopy (PFM). Annealing in static air leads to better ferroelectric properties, higher remanent polarization, lower drive voltages and higher piezoelectric coefficient. On the other hand, oxygen atmosphere favors the imprint phenomenon and reduces the piezoelectric coefficient dramatically. Impedance data, represented by means of Nyquist diagrams, show a dramatic increase in the resistivity for the films annealed in static air atmopshere.     

Effect of MnO2 addition on the piezoelectric properties in Pb(Mg1/3Nb2/3)O3 relaxor ferroelectrics

The effects of MnO₂ addition on the piezoelectric properties in Pb(Mg_1/3Nb_2/3)O₃ relaxor ferroelectrics were studied in the ferroelectricity-dominated temperature range from −40 to 30°C. Dielectric, piezoelectric, and electrostrictive properties were examined to clarify the effect of MnO₂ addition. As an added amount of MnO₂ increases, the dielectric constant decreases and the mechanical quality factor increases in Pb(Mg_1/3Nb_2/3)O₃. From the experimental results, it has been found that Mn behaves as a ferroelectric domain pinning element.     

Effect of PbO-SiO2 and PbO-B2O3 flux systems on the crystalline and magnetic properties of Ni0.5Zn0.5Fe2O4 ferrite prepared from the mixed powders

Lead borate and lead silicate were added to lower the sintering temperature of a Ni_0.5Zn_0.5Fe₂O₄ ferrite prepared from the blend of two types of powders and to homogenize the grain size. 5PbO·SiO₂ and 5PbO·B₂O₃ flux systems were added to lower the sintering temperature and diminish the magnetic loss at high frequencies. The ferrites were studied by bulk density, scanning electron microscopy and impedance analysis. It was found that the addition of PbO markedly accelerated the grain growth, while SiO₂ and B₂O₃ were found to be effective to obstruct the movement of grain boundaries and to minimize the grain size. Doping with PbO in the mixed powders appropriately increased the densification and initial permeability. The ferrite doped with 1% of 5PbO·SiO₂ possessed the lowest loss tangent (tgδ) in the range of 5 M-40 MHz and the highest threshold frequency.