Effect of SrZrO3 on phase structure and electrical properties of 0.974(K0.5Na0.5)NbO3–0.026Bi0.5K0.5TiO3 lead-free ceramics

(0.974−x)(K_0.5Na_0.5)NbO₃–0.026Bi_0.5K_0.5TiO₃–xSrZrO₃ lead-free piezoelectric ceramics have been prepared by the conventional solid state sintering method. Systematic investigation on the microstructure, crystalline structures as well as electrical properties of the ceramics was carried out. With the addition of SrZrO₃, the rhombohedral–orthorhombic phase transition temperature of the ceramics increases. Both the rhombohedral–orthorhombic and orthorhombic–tetragonal phase transitions of the ceramics were modified to be around room temperature when x~0.05, and as a result remarkably strong piezoelectricity has been obtained in 0.924(K_0.5Na_0.5)NbO₃–0.026Bi_0.5K_0.5TiO₃–0.05SrZrO₃ ternary system, whose piezoelectric parameters were d₃₃=324 pC/N and k_p=41%.     

Effect of WO3 doping on dielectric and ferroelectric properties of 0.94(Bi0.5Na0.5)TiO3–0.06BaTiO3 ceramics

WO₃(0–6 mol%)-doped 0.94Bi_0.5Na_0.5TiO₃–0.06BaTiO₃ lead-free ceramics were synthesized by conventional solid-state reaction. The effect of WO₃ addition on the structure and electrical properties were investigated. The result revealed that a small amount of WO₃ (≤1 mol%) can diffuse into the lattice and does not significantly affect the phase structure, however, more addition will result in distortion and enlargement of the unit cells. The maximum permittivity temperature (T_m) is suppressed dramatically as the dopant increasing, while the depolarization temperature (T_d) fall to the minimum with 1 mol% WO₃ additive. The remanent polarization (P_r) was enhanced and coercive field (E_c) was reduced by doping with WO₃. The strain shows the largest value for 1 mol% doped sample, which is due to a field-induced antiferroelectric–ferroelectric phase transition.     

Piezoelectric and dielectric properties of (Bi0.5Na0.5)0.94Ba0.06TiO3–Ba(Zr0.04Ti0.96)O3 lead-free piezoelectric ceramics

Lead-free piezoelectric ceramics of (1 − x)(Bi_0.5Na_0.5)_0.94Ba_0.06TiO₃–xBa(Zr_0.04Ti_0.96)O₃ (abbreviated as BNBT–BZT100x, wherein x from 0 to 10 mol%) were fabricated. We have studied effects of amount of BZT content on the electrical properties and microstructures. X-ray diffraction analysis indicates that a solid solution is formed when BZT diffuses into the BNBT lattice, and further the crystal structure of sintered hybrid changes from rhombohedral to tetragonal symmetry along with increasing BZT content. Piezoelectric property measurements reveal that the BNBT–BZT4 ceramics has the highest piezoelectric performance, for example, the piezoelectric constant d₃₃ reaches to 167 pC/N and planar electromechanical coupling factor k_p is up to 0.27. In addition, the effect of Bi₂O₃ on the electrical properties and microstructure of the BNBT–BZT4 ceramics have also been studied, and found that the doping of Bi enhances the piezoelectric properties of ceramics.     

Growth of (K0.5Na0.5)NbO3–SrTiO3 lead-free piezoelectric single crystals by the solid state crystal growth method and their characterization

Lead zirconate titanate (PZT) piezoelectric ceramics are commonly used in various applications, e.g. gas igniters, high-voltage generators and microbalances. However, due to increasing health and environmental concerns over their high lead content, lead-free piezoelectric ceramics are being developed. Lead-free piezoelectric single crystals offer superior performance over their polycrystalline counterparts but are difficult to grow by conventional methods. In this paper, (K_0.5Na_0.5)NbO₃–SrTiO₃ (KNN–ST) single crystals are grown for the first time by the solid state crystal growth (SSCG) method. 〈100〉 KTaO₃ single crystal seeds are buried in the center of pellets of pressed KNN-ST powder. The single crystal grows from the seed crystal during sintering at 1100 °C for 20 h. The grown single crystals contain porosity, which is incorporated from the matrix during growth. The effect of SrTiO₃ addition on single crystal growth behavior, chemical composition and structure is evaluated.     

Sb掺杂对(K0.49Na0.51)0.94Li0.06(Nb0.94Ta0.06)O3无铅压电陶瓷结构与性能的影响

采用固相反应法制备(K0.49Na0.51)0.94Li0.06Nb0.94SbxTa0.06-xO3(KNNLSxT0.06-x,x=0.00～0.06)无铅压电陶瓷,研究了Sb的掺杂量对陶瓷晶体结构与压电性能的影响。X射线衍射结果表明:随着Sb掺杂量x的增加,陶瓷的晶体结构由正交相向四方相转变,并在x=0.04～0.05时出现正交相逐渐转变为四方相的多型相转变(PPT),在x=0.04时具有较佳的性能:压电常数d33=258 pC/N,平面机电耦合系数kp=54%,机械品质因素Qm=61以及较高的居里温度Tc=405℃。     

Large strain of temperature insensitive in (1–x)(0.94Bi0.5Na0.5TiO3–0.06BaTiO3) –xSr0.7La0.2TiO3 lead-free ceramics

Novel (1–x)(0.94Bi_0.5Na_0.5TiO₃–0.06BaTiO₃)–xSr_0.7La_0.2TiO₃ ternary lead-free ceramics (BNBT–xSL, x?=?0.00–0.08) were fabricated by the widely used solid-state sintering technique. The crystal phase, microstructure, dielectric relaxation, piezoelectric, and electromechanical properties of each composition were systematically analyzed. It is found that the addition of SL has little effect on the crystal phase and grain morphology, but it can remarkably improved the relaxation property of the ceramic sample and gave rise to favourable dielectric properties in a wide range of temperatures. In addition, as the SL content increases, the ferroelectric to relaxor temperature (T_F-R) is adjusted to below ambient temperature. More importantly, the decay of ferroelectric phase resulted in a significant increase in strain value: the large strain of 0.5% with normalized strain of 625?pm/V was obtained at 80kv/cm and x?=?0.04. Finally, the composition exhibited high strain of temperature insensitivity range from room temperature to 100?°C, the strain value remained above 0.4% and kept within 5%. The results are due to the coexistence of rhombohedral polar-nanoregions (PNRs) and tetragonal PNRs during the relaxor region. This result is of great importance to the developments of temperature-insensitive strain sensors and actuators.     

Influence of calcination temperature on the piezoelectric properties of Ag2O doped 0.94(K0.5Na0.5)NbO3–0.06LiNbO3 ceramics

The effects of calcination temperature on the bulk density, piezoelectric, and ferroelectric properties were investigated for the Ag₂O doped 0.94(K_0.5Na_0.5)NbO₃–0.06LiNbO₃ ceramics. The calcination temperatures were varied from 750 to 950 °C by 50 °C differences. An tetragonal XRD pattern, consistent with single-phase 0.94(K_0.5Na_0.5)NbO₃–0.06LiNbO₃ was obtained after calcination at 850 °C for 2 h. And the experimental results showed that Ag₂O doped 0.94(K_0.5Na_0.5)NbO₃–0.06LiNbO₃ ceramics calcined at 850 °C had a remnant polarization P_r=24.5 μC/cm², bulk density=4.32 g/cm³, piezoelectric constant d₃₃=282 pC/N and electromechanical coefficient k_p=37.8%.     

Effect of the Nb2O5 content on electrical properties of lead-free BaTiO3–Bi0.5Na0.5TiO3 ceramics

(1−x)BaTiO₃–xBi_0.5Na_0.5TiO₃ (BT–BNT) ceramics were prepared by the solid-state reaction method. With an increase of BNT content, both the Curie temperature and the room temperature resistivity increased. At 1 mol% BNT addition, the sample was not semiconducting, due to Bi₂O₃ volatilization resulting from the decomposition of pre-calcined BNT during sintering. Appropriate extra Nb₂O₅ doping in the raw materials could offset Bi₂O₃ volatilization and neutralize the redundant acceptor Na⁺ ions. When the extra Nb₂O₅ content was 0.6 mg, the sample room-temperature resistivity was 6.3×10³ Ω cm, with the Curie point about 135 °C and a high PTC effect of ∼3 orders of magnitude.     

The effect of pre-milling/pre-synthesis process and excess Ba on the microstructure and dielectric/piezoelectric properties of nano-sized 0.94[(Bi0.5Na0.5)TiO3]–0.06[Ba(1+x)TiO3]

Lead-free piezoelectric ceramic specimens of 0.94[(Bi_0.5Na_0.5)TiO₃]–0.06[Ba_(1+x)TiO₃] (where 0 ≤ x ≤ 0.03) (abbreviated as nano-sized BNBT6(x)) compositions containing excess Ba were synthesized by a modified mixed oxide method. In this modified process (Bi_0.5Na_0.5)TiO₃ and Ba_(1+x)TiO₃ were separately prepared by pre-milling the starting powders in high energy mill (HEM) in order to obtain nano-particle size. BNBT6(x) specimens were also prepared by the conventional process to be compared with the former one. The pre-milling of the raw materials lowered the calcination temperatures of (Bi_0.5Na_0.5)TiO₃ and Ba_(1+x)TiO₃ by 110 and 200 °C, respectively, as compared with the conventional process. High energy milling improved the reaction activity and homogeneity of the materials used throughout the process, enhanced the sintering density and grain uniformity, and decreased the grain size. The effects of excess Ba on the characteristic of nano-sized BNBT6(x) specimens were systematically investigated. The piezoelectric and dielectric properties of BNBT6(x) specimens containing various amounts of excess Ba show maximum values of the planar electromechanical coupling factor (k_p) of 38% and the piezoelectric constant (d₃₃) of 198 pC/N with Ba excess amount of 0.02 mol [BNBT6(0.02)]. The d₃₃ then decreases with increasing excess Ba content to 0.03 mol, whereas the relative dielectric permittivity (K^T₃₃) steadily increases with increasing excess Ba and reaches the maximum value of 785 for this composition. Besides, the depolarization temperature (T_d) slightly decreased within the range of x = 0–0.01 mol and then tends to rapidly decrease with the excess Ba of 0.02 mol. In addition to this, the T_d remains unchanged with the higher excess Ba of 0.03 mol. The modified mixing and milling method were considered to be a new and promising process for lead-free piezoelectric ceramics owing to their excellent piezoelectric/dielectric properties.     

High piezoelectric performance and temperature dependence of ferroelectric and piezoelectric properties of Bi(Mg0.5Zr0.5)O3–PbTiO3 near morphotropic phase boundary

According to consideration on the average radius of B-site cation of BiMeO₃, we reported that the Bi(Mg_0.5Zr_0.5)O₃–xPbTiO₃ compound at the morphotropic phase boundary (MPB) of x=0.58 possesses a piezoelectric coefficient d₃₃ as high as 306 pC/N. The optimal piezoelectric and ferroelectric properties near the MPB might be attributed to its lower lattice distortion, as described by change of FWHM value for {1 1 1}_PC peaks. Furthermore, Bi(Mg_0.5Zr_0.5)O₃–xPbTiO₃ displayed stable ferroelectric and piezoelectric properties over a temperature range from ambient temperature to above 160 °C, as exhibited by temperature dependence polarization and strain versus electric field curves and thermal depoling process.     

(1-x)Li0.05(K0.5Na0.5)0.95NbO3-x(Bi0.5Na0.5)TiO3无铅压电陶瓷的结构与电性能研究

采用固相反应法制备了(1-x)Li0.05(K0.5Na0.5)0.95NbO3-x(Bi0.5Na0.5)TiO3(LKNN-BNT)无铅压电陶瓷,研究了BNT的添加量x(0,0.005,0.01,0.02)对LKNN-BNT陶瓷的结构与电性能影响。X射线衍射(XRD)分析结果表明当x≤0.005时,陶瓷为正交钙钛矿结构,而当x≥0.01时,陶瓷则转变为四方钙钛矿结构,说明该陶瓷的多型相转变(PPT)区域为0.005相似文献   

Magnetoelectric properties of 0.5BiFeO3–0.5Pb(Fe0.5Nb0.5)O3 solid solution

Magnetoelectrics are materials that join magnetic and electric orderings in the same phase. They exhibit magnetoelectric coupling which is important from the fundamental and practical point of view. The subject of the paper is a presentation of magnetic, electric and magnetoelectric properties of 0.5BiFeO₃–0.5Pb(Fe_0.5Nb_0.5)O₃ solid solution. The obtained material belongs to oxide perovskite magnetoelectrics of relatively high magnetic and electric ordering temperatures. Both temperatures are considerably above room what suggests potential application possibilities of the material. The magnetic properties were investigated using Mössbauer spectroscopy and magnetization measurements. The solid solution is an antiferromagnet with incomplete compensated magnetic moments. The electrical properties were determined using impedance spectroscopy analysis. There is an observed change of the electrical properties at the magnetic ordering temperature what indicates magnetoelectric coupling in the system. The electrical conductivity mechanism is also proposed. Magnetoelectric voltage coefficient was determined and possible explanation of its changes was proposed.     

Effect of ZnO–WO3 additives on sintering behavior and microwave dielectric properties of 0.95MgTiO3–0.05CaTiO3 ceramics

The effect of WO₃ addition on the phase formation, the microstructures and the microwave dielectric properties of 1 wt% ZnO doped 0.95MgTiO₃–0.05CaTiO₃ ceramics system were investigated. Formation of second phase MgTi₂O₅ could be effectively restrained through the addition of WO₃, but should be in right amount. WO₃ as additives could not only effectively lower the sintering temperature of the ceramics to 1310 °C, but also promote the densification. A dielectric constant ε_r of 20.02, a Q×f value of 62,000 (at 7 GHz), and a τ_f value of −5.1 ppm/°C were obtained for 1 wt% ZnO doped 0.95MgTiO₃–0.05CaTiO₃ ceramics with 0.5 wt% WO₃ addition sintered at 1310 °C.     

Effects of sintering method and BiFeO3 dopant on the dielectric and ferroelectric properties of BaTiO3–BiYbO3 based solid solution ceramics

(0.95–x) BaTiO₃–0.05 BiYbO₃–x BiFeO₃ (x?=?0, 0.01, 0.02, and 0.04) (abbreviated as (0.95–x) BT–0.05 BY–x BFO) ceramics were fabricated by conventional sintering (CS) and microwave sintering (WS) methods. Effects of sintering method and BFO dopant on the microstructure and electric properties of (0.95–x) BT–0.05 BY–x BFO ceramics were comparatively investigated. X-ray diffraction showed that all CS and WS samples presented a single perovskite phase. It was also found that WS ceramics possessed denser microstructure and finer grains compared to CS samples as indicated by the surface morphology characterization. Dielectric measurements revealed that all samples exhibited the weak relaxation behavior; however, the degree of relaxation behavior of BT–BY based ceramic could be strengthened by addition of BFO and by WS method. Moreover, the temperature and frequency stability could be improved with doped BFO. The density of 0.93BT–0.05BY–0.02BFO ceramic was found to be the largest while that of 0.94BT–0.05BY–0.01BFO ceramic was the smallest, thus, the dielectric constant of 0.93BT–0.05BY–0.02BFO was significantly larger than that of 0.94BT–0.05BY–0.01BFO and 0.94BT–0.05BY–0.04 BFO ceramics. minimum dielectric constant of (0.95–x) BT–0.05 BY–x BFO ceramic was obtained at x?=?0.01. Ferroelectric measurements indicated that all samples showed the slim hysteresis loop. The remnant polarization (P_r) and coercive field (E_C) of (0.95–x) BT–0.05 BY–x BFO ceramics first decreased and then increased with increasing x,the minimum values were obtained at x?=?0.01. Moreover, P_r and E_C of WS ceramics were slightly larger than those of CS ceramics, indicating that higher density and larger grain sizes contributed to enhancing the ferroelectric characteristic. These findings indicate that addition of moderate amount of BFO and use of WS technique can strengthen the degree of relaxation behavior and improve the ferroelectric properties of BT–BY based ceramics.     

Enhanced dielectric and energy-storage properties in ZnO-doped 0.9(0.94Na0.5Bi0.5TiO3−0.06BaTiO3)−0.1NaNbO3 ceramics

[0.9(0.94Na_0.5Bi_0.5TiO₃?0.06BaTiO₃)?0.1NaNbO₃]-xZnO (NBT-BT-NN-xZnO, x=0, 0.5 wt%, 1.0 wt%, 1.5 wt%, and 2.0 wt%) ferroelectric ceramics were fabricated using a conventional solid-state reaction method. The effects of ZnO content on dielectric, energy-storage and discharge properties were systematically investigated. Dielectric constant and difference between maximum and remanent polarization were significantly improved by ZnO doping. Dielectric constant of NBT-BT-NN-1.0-wt% ZnO was 3218 at 1 kHz and room temperature, i.e. one time bigger than that of pure NBT-BT-NN ceramic. As a consequence, a maximum energy-storage density of 1.27 J/cm³ with a corresponding efficiency of 67% was obtained in NBT-BT-NN-1.0-wt% ZnO ceramic. Moreover, its pulsed discharge energy density was 1.17 J/cm³, and 90% of which could be released in less than 300 ns. Therefore, ZnO doped NBT-BT-NN ceramic with a large energy-storage density and short release time could be a potential candidate for applications in high energy-storage capacitors.     

铁钕掺杂K0.5Na0.5NbO3陶瓷的压电介电性能

采用传统陶瓷制备技术制备了新型的K0.5Na0.5NbO3+0.2%molFe2O3+x%molNd2O3压电陶瓷,研究了该体系陶瓷的压电性能及介电性能。研究结果表明,在烧结温度为1120℃、4 h时,该体系陶瓷均具有相对较好的电学性能,并在x为0.2时性能最佳,其压电常数d33为125pC/N,机电耦合系数Kp为37%,机械品质因素Qm为155,介电常数εr为561,介质损耗tanδ为0.08。     

Effect of sintering temperature on the microstructure and mechanical properties of ZrO2-3 mol%Y2O3 sol–gel films

The microstructural evolution and mechanical properties of ZrO₂-3 mol%Y₂O₃ films were investigated as a function of the sintering temperature in the range from 100 °C to 1500 °C, using a battery of characterization techniques including X-ray diffraction (XRD), scanning electron microscopy (SEM), atomic force microscopy (AFM) and nanoindentation. It was found that the crystallization occurs at temperatures close to 300 °C. A gradual increase in the grain and crystallite sizes is observed as the sintering temperature increases up to 1000 °C, and above this sintering temperature the tendency changes abruptly with a rapid increase in these values. Although Young's modulus of the coatings did not change with sintering temperature, a slight decrease was observed in the hardness values above 1000 °C which is attributed to microstructure coarsening. Finally, a slight degradation of the films occurs above 1300 °C, which is due to the occurrence of a process of grain spheroidization.     

Structure and electrical properties of Nd2O3-doped 0.82Bi0.5Na0.5TiO3–0.18Bi0.5K0.5TiO3 ceramics

Nd₂O₃ doped 0.82Bi_0.5Na_0.5TiO₃–0.18Bi_0.5K_0.5TiO₃ (abbreviated to BNKT) binary lead-free piezoelectric ceramics were synthesized by the conventional mixed-oxide method. The results show that the BNKT ceramics with 0–0.15 wt.% Nd₂O₃ doping possesses a single perovskite phase with rhombohedral structure. The grain size of BNKT decreased with the addition of Nd₂O₃ dopant. The temperature dependence of the dielectric constant ?_r revealed that there were two-phase transitions from ferroelectric to anti-ferroelectric and anti-ferroelectric to paraelectric. A diffuse character was proved by linear fitting of the modified Curie–Weiss law. At room temperature, the specimens containing 0.0125 wt.% Nd₂O₃ with homogeneous microstructure presented excellent electrical properties: the piezoelectric constant d₃₃ = 134 pC/N, the electromechanical coupling factor K_p = 0.27, and the dielectric constant ?_r = 925 (1 kHz).     

Microstructure and electrical properties of (Na0.5K0.5)1−2xMgxNbO3–Bi0.5Na0.5TiO3 lead-free piezoelectric ceramics

0.975[(Na_0.5K_0.5)_1−2xMg_xNbO₃]–0.025(Bi_0.5Na_0.5TiO₃) (KNMN–BNT, x=0, 0.01, 0.02, 0.03, 0.04 and 0.05) lead-free piezoelectric ceramics were fabricated by the conventional solid-state sintering method. The dependence of Mg content on the microstructure and electrical properties of the ceramics is investigated. The X-ray diffraction (XRD) analysis revealed that an appropriate amount of Mg diffused into the KNN–BNT lattice to form a stable solid solution, the ceramics possessed a pure perovskite structure, and a morphotropic phase boundary (MPB) between the orthorhombic and tetragonal phases was observed with the composition of 0.02≤x≤0.05. The orthorhombic–tetragonal transition temperature (T_O–T) is less than 95 °C and the Curie temperature (T_c) is almost unchanged (~360 °C) with the increase of MgO content. The ceramics with x=0.02 showed enhanced piezoelectric and ferroelectric properties because of close proximity to the MPB, i.e., d₃₃~210 pC/N, k_p~0.41, 2E_c~22.4 kV/cm and 2P_r~39.2 μC/cm². Moreover, the dielectric properties exhibited optimal effects with x=0.02, that is ε_r~637 and tan δ~0.09. These results indicate that the introduction of MgO is an effective method to improve the density as well as the electrical properties and the temperature stability of the KNN–BNT ceramics. As a result, the KNMN–BNT ceramic is a promising candidate for lead-free piezoelectric materials.