BiFeO3-doped (Na0.5K0.5)NbO3 lead-free piezoelectric ceramics

Abstract

Lead-free piezoelectric ceramics (1?x)(Na_0.5K_0.5)NbO₃-xBiFeO₃ (x=0～0.07) were synthesized by the solid-state reaction. Differential scanning calorimetry (DSC) measurements revealed that an increase in the amount of BiFeO₃ dopant resulted in a decrease in the orthorhombic-tetragonal and tetragonal-cubic phase transition temperature of the material. One percent BiFeO₃ additive suppressed grain growth, which not only benefits the sintering of ceramics but also enhances the piezoelectric and ferroelectric properties, where d₃₃=145pC/N, k_p=0.31, Q_m=80, P_r=11.3 μC cm^?2 and E_c=16.5 kV cm^?1. As x_BF>0.01, both piezoelectric and ferroelectric properties decreased rapidly with an increasing amount of dopant.     

BiFeO3-doped (Na0.5K0.5)NbO3 lead-free piezoelectric ceramics

Lead-free piezoelectric ceramics (1−x)(Na_0.5K_0.5)NbO₃-xBiFeO₃ (x=0∼0.07) were synthesized by the solid-state reaction. Differential scanning calorimetry (DSC) measurements revealed that an increase in the amount of BiFeO₃ dopant resulted in a decrease in the orthorhombic-tetragonal and tetragonal-cubic phase transition temperature of the material. One percent BiFeO₃ additive suppressed grain growth, which not only benefits the sintering of ceramics but also enhances the piezoelectric and ferroelectric properties, where d₃₃=145pC/N, k_p=0.31, Q_m=80, P_r=11.3 μC cm⁻² and E_c=16.5 kV cm⁻¹. As x_BF>0.01, both piezoelectric and ferroelectric properties decreased rapidly with an increasing amount of dopant.     

(Na0.5K0.5)NbO3–LiTaO3 lead-free piezoelectric ceramics

Lead-free piezoelectric ceramics were prepared in the system (1−x)(Na_0.5K_0.5)NbO₃–xLiTaO₃ following the conventional mixed oxide route. The effect of cationic substitution of lithium for sodium and potassium in the A sites and tantalum for niobite in the B sites in (Na_0.5K_0.5)NbO₃ (NKN) perovskite lattice on symmetry and physical properties were investigated. The materials with perovskite structure are in orthorhombic phase when x<5 mol.% and transform to tetragonal phase when x>6 mol.%; when x≥8 mol.%, a K₃Li₂Nb₅O₁₅ phase with tetragonal tungsten bronze structure begins to appear and becomes dominant with increasing content of LiTaO₃. A morphotropic phase boundary (MPB) between orthorhombic and tetragonal phases appears at x=5–6 mol.%. Analogous to Pb(Zr,Ti)O₃, the piezoelectric and electromechanical properties are enhanced for compositions near the morphotropic phase boundary. Piezoelectric constant d₃₃ values reach ∼200 pC/N. Electromechanical coefficients of planar mode reach ∼36%, respectively. Our results show that (Na_0.5K_0.5)NbO₃ with small amount of LiTaO₃ (x=7 mol.%) is a good lead-free piezoelectric ceramic.     

A Rosen-type piezoelectric transformer employing lead-free K0.5Na0.5NbO3 ceramics

Lead-free K_0.5Na_0.5NbO₃–K_5.4Cu_1.3Ta₁₀O₂₉–MnO₂ (KNN–KCT–Mn) ceramics have been prepared by a conventional ceramic sintering technique. The ceramics show excellent piezoelectric properties for application in power devices, and the optimum properties measured are as follows: piezoelectric constant d ₃₃ = 90 pC/N, planar electromechanical coupling factor k _p = 0.40, mechanical quality factor Q _m = 1900, remanent polarization P _r = 11.8 μC/cm², coercive field E _c = 0.85 kV/mm. A Rosen-type piezoelectric transformer with a dimension of 21 mm × 6 mm × 1.2 mm was fabricated using the KNN–KCT–Mn ceramics. Properties of the piezoelectric transformer operating in the first and second modes have been characterized. For the first mode, the transformer has a maximum output power of 0.7 W with a temperature rise of 14 °C. For the second mode, the maximum output power of the transformer is 1.8 W with a temperature rise of 33 °C. KNN–KCT–Mn ceramics have shown to be a potential lead-free candidate to be used in high-voltage–low-current devices.     

Preparation and piezoelectric properties of CuO-doped (Na0.5K0.5)NbO3 ceramics by the citrate precursor method

A low-cost citrate so-gel route was investigated to synthesize nano-sized crystalline powders (<100 nm) of 1 mol% CuO modified (Na_0.5K_0.5)NbO₃ compositions. It was found that amorphous gels can be transformed into crystallite powders with single-phase perovskite structure when calcined at 500?C600 °C for 3 h. The transmission electron microscopy observation showed that the particles are column-like and well dispersed, depending on the calcination condition. The as-pressed samples exhibit improved densification behavior and finer grain morphology after sintering. Electrical properties of the samples sintered at 1,060 °C are as follows: dielectric constant ?? _r  = 605, piezoelectric constant d ₃₃ ~ 117 pC/N, planar electromechanical coupling factor k _p  ~ 0.38 and mechanical quality factor Q _m  ~ 725.     

直接反应烧结法制备(Bi0.5Na0.5)1-xBaxTiO3系无铅压电陶瓷的性能研究

采用直接反应烧结法制备了(Bi0.5Na0.5)1-xBaxTiO3无铅压电陶瓷,研究了陶瓷的压电性能和显微结构.结果表明,直接反应烧结法不影响BNBT陶瓷的钙钛矿相结构,但可使准同型相界处组成的四方相含量增加;直接反应烧结的BNBT陶瓷呈无变形,收缩率稍大于采用传统固相法制成的陶瓷样品,晶粒明显较大,并具有更好的压电介电性能,其中,d33=166pC/N,tanδ=0.03.     

Dielectric and piezoelectric properties in the lead-free system Na0.5K0.5NbO3-BiScO3-LiTaO3

Phase relations, dielectric and piezoelectric properties are reported for the ternary system 98%[(1 - x) (Na(0.5)K(0.5)NbO(3))-x(LiTaO(3))]-2%[BiScO(3)] for compositions x ≤ 10 mol% LiTaO(3). The phase content at room-temperature changed from mixed phase, monoclinic + tetragonal, for unmodified 98%(Na(0.5)K(0.5)NbO(3))-2%(BiScO(3)), to tetragonal phase for compositions >2 mol% LiTaO(3). Curie peaks at 360 to 370°C were observed for all compositions, but peaks became diffuse at x ≥ 3 mol%, and two dielectric peaks, at 370 and 470°C, were observed for 5 mol% LiTaO(3). Phase segregation, and finite size affects associated with the core-shell structure, account for the occurrence of two dielectric peaks in 5 mol% LiTaO(3), and diffuse dielectric behavior. The value of d(33) piezoelectric charge coefficient increased from ~160 pC/N for 0 mol% LiTaO(3) to 205 to 214 pC/N for 1 to 2 mol% LiTaO3 solid solutions, before falling sharply at 3 mol% LiTaO(3). TEM-EDX analysis revealed core-shell grain structures with segregation of Bi, Sc, and Ta in the outer ~100-nm shell of the 5 mol% LT sample.     

Phase diagram and structure-property relationships in the lead-free piezoelectric system: Na0.5K0.5NbO3-LiTaO3

A phase-diagram for the Na(0.5)K(0.5)NbO(3)-LiTaO(3) solid solution series (NKN-LT) is presented for compositions ≤ 10 mol% LT, based on the combined results of temperaturevariable X-ray powder diffraction and dielectric measurements. In addition to the reported orthorhombic and tetragonal polymorphs of NKN-LT, a monoclinic phase is revealed. Changes to electrical properties as a function of LT substitution are correlated to phase content. Increasing the LT content from 5 to 7 mol% LT led to improved temperature stability of piezoelectric properties because of the avoidance of the monoclinic-tetragonal polymorphic phase transition during thermal cycling (at >25°C). For 7 mol% LT samples: d(33) = 200 pC/N; T(c) = 440°C; ε(r) = 550 and tan δ = 0.02 (at 20°C). Modification of this composition by solid solution with BiScO(3) led to a decrease in d(33) values. Transmission electron microscopy of a sample of 0.95[0.93 NKN-0.07LT]-0.05BiScO(3) indicated a core-shell grain structure which led to temperature-stable dielectric properties.     

Phase transition and piezoelectric properties of (1 − x)K0.5Na0.5NbO3–xLiSbO3 ceramics by hydrothermal powders

KNbO₃, NaNbO₃ and LiSbO₃ powders were synthesized by a hydrothermal route have been used to prepare (1 ? x)K_0.5Na_0.5NbO₃–xLiSbO₃ (KNN–LS; x = 0.00–0.08) ceramics. The effects of LiSbO₃ doping on the structures of KNN–LS ceramics have been systematically investigated by X-ray diffraction (XRD) and Rietveld refined XRD patterns. A gradual phase transition from orthogonal to tetragonal with the increase of LiSbO₃ content is demonstrated. Thereinto, the monoclinic phase is identified for the KNN–LS ceramic with the LiSbO₃ content of x = 0.08. Meanwhile, the XRD pattern reveals that the intensity ratio of (200)/(002) crystal face of the ceramic with x = 0.08 was bigger than one, which is different from the tetragonal phase. The tetragonal phase is revealed in the KNN–LS ceramic in the vicinity of x = 0.07, accompanying with relatively higher piezoelectric and ferroelectric properties. Tetragonal phase is beneficial to improve the piezoelectric properties of the KNN–LS ceramics.     

Energy storage performance of silica-coated k0.5Na0.5NbO3-based lead-free ceramics

Potassium sodium niobate-based ceramics have been extensively studied as high-power energy storage capacitor in recent years due to their excellent dielectric properties. We investigated the microstructure, dielectric-temperature spectrum, and energy storage properties of SiO₂-coated 0.9(k_0.5Na_0.5)NbO₃–0.1Bi(Zn_2/3Nb_1/3)O₃ (0.9KNN–0.1BZN) ceramics prepared by solid-state sintering and Stöber method. During the sintering process, SiO₂ reacted with 0.9KNN–0.1BZN to form the second phase K₃Nb₃O₆Si₂O₇. Coating SiO₂ could improve the dielectric-temperature stability of 0.9KNN–0.1BZN ceramics, and had excellent performance adapting to high-temperature conditions. When the SiO₂ content is 1.0 wt%, the maximum energy storage density of 0.9KNN–0.1BZN ceramics is 0.97 J/cm³, and the breakdown field strength is 200 kV/cm. This work expands the application of (k_0.5Na_0.5)NbO₃ ceramics in the field of energy storage capacitors.

     

K_(0.5)Na_(0.5)NbO_3压电纳米纤维柔性发电元件的组装与性能研究

采用静电纺丝技术在Si基衬底上制备无铅压电K_(0.5)Na_(0.5)NbO_3纳米纤维,退火后所得纳米纤维为多晶正交钙钛矿结构,直径约60~80nm。通过柔性聚合物的包覆与剥离实现了纳米纤维向柔性基底的直接转移,采用磁控溅射在纳米纤维两侧沉积Au电极并引线封装后获得了不同尺寸的柔性压电发电元件。由于压电势和电极/纳米纤维界面肖特基势垒的耦合,该元件在受力弯曲时可产生脉冲的输出电压。随着电极间距的增大,输出电压随之增加。当间距达到10mm时,输出电压峰峰值能够达到约12V。     

Microstructure, dielectric and piezoelectric properties of La-modified Bi0.5(Na0.84K0.16)0.5TiO3 lead-free ceramics

Lead-free ceramics (Bi_1?xLa_x)_0.5(Na_0.84K_0.16)_0.5TiO₃ were prepared by a conventional ceramic technique and the effects of La doping and sintering temperature on the microstructure, ferroelectric and piezoelectric properties of the ceramics were studied. All the ceramics possess a pure perovskite structure and La³⁺ diffuses into the Bi_0.5(Na_0.84K_0.16)_0.5TiO₃ lattices to form a solid solution with a rhombohedral symmetry. The addition of La leads to the significant change in the grain morphology and size for the (Bi_1?xLa_x)_0.5(Na_0.84K_0.16)_0.5TiO₃ and a number of rod grains with the length of 10–50 μm and the diameter of 1–2 μm are observed in the ceramic with x = 0.04 sintered at 1,140 °C for 2 h. However, as sintering temperature increases to 1,160 °C, the rod grains disappears and the uniform and rectangular grains are observed in the ceramics with x = 0.04. As x increases from 0 to 0.06, the coercive field E _c of the ceramics decreases from 4.33 to 2.81 kV/mm and the remanent polarization P _r of the ceramics retains the high values of 25.9–27.7 μm/cm². The depolarization temperature T _d decreases from 154 to 50 °C with x increasing from 0 to 0.10. All the ceramics exhibit the diffusive phase transition at high temperature (280–320 °C). The ceramic with x = 0.04 sintered at 1,150 °C for 2 h exhibit the optimum piezoelectric properties, giving d ₃₃ = 165 pC/N and k _p = 32.9 %. The optimum sintering temperature is 1,150 °C at which the improved piezoelectric properties (d ₃₃ = 165 pC/N and k _p = 32.9 %) are obtained. At the high La³⁺ level (x = 0.10 and 0.12), the ceramics exhibit weak ferroelectricity (P _r = 13.0–21.2 μm/cm²) and thus possess poor piezoelectricity (d ₃₃ = 17–27 pC/N).     

铌酸钠钾基压电陶瓷的结构与性能研究

采用传统的固相反应合成法制备了结构较为致密的0.9(K0.5Na0.5)NbO3-0.1LiSbO3(KNN-LS)无铅压电陶瓷,研究了其相结构、压电、介电、损耗以及铁电性质.常温下的压电陶瓷具备四方钙钛矿结构,具有较高的压电系数d33=131pC/N和低的介电损耗tanδ=0.09(10kHz)等优点.另外,常温下的KNN-LS陶瓷存在着较为饱满的电滞回线,其剩余极化率Pr为16.1μC/cm2,矫顽场为EC=14.8kV/cm.性能较KNN压电陶瓷有了较大的提高.     

Microstructure and piezoelectric properties of NaF-doped K0.5Na0.5Nb0.95Ta0.05O3 lead-free ceramics

The effects of NaF on the microstructure and electrical properties of K_0.5Na_0.5Nb_0.95Ta_0.05 lead-free ceramics prepared by conventional sintering method were investigated in this study. The dopant NaF effectively lowers the sintering temperature and promotes the grain growth. Samples with a high relative density up to 96.3 % are achieved by adding 0.6 wt% NaF to improve the sinterability. The electric properties are also enhanced, and the optimum properties are achieved at the doping content of 1.0 wt% (d ₃₃ = 153 pC/N, k _P = 32.2 %, Q _m = 80.5, E _c = 0.89 kV/mm, and P _r = 16.5 μC/cm²). The improvement of ferroelectric and piezoelectric properties is suggested to be largely contributed to the compensation of sodium element from dopant NaF for the volatilization of A-site alkali elements.     

Photoluminescence and electrical properties of Er-doped (K0.5Na0.5)NbO3-based transparent ceramics

Er-doped 0.98(K_0.5Na_0.5)NbO₃-0.02Ba(Bi_0.5Nb_0.5)O₃ transparent fluorescent ceramics were prepared using traditional solid-phase method. The (K_0.5Na_0.5)NbO₃ (KNN) ceramics were modified by introducing the second group elements Ba(Bi_0.5Nb_0.5)O₃ and rare earth ions Er³⁺. The effects of Er³⁺ on the structure, optical and electrical properties of transparent ceramics (K_0.5Na_0.5)NbO₃-Ba(Bi_0.5Nb_0.5)O₃ were investigated. The ceramics form a single perovskite structure and have a pseudo-cubic phase structure. Nanoscale grain size was obtained for ceramics, and the smallest average grain size is 80 nm. The ceramics have high transmittance. The ceramic 0.1 mol% Er-doped 0.98(K_0.5Na_0.5)NbO₃-0.02 Ba(Bi_0.5Nb_0.5)O₃ achieved the highest transmittance for this system with 62% and 52% at near-infrared light (1000 nm) and visible light (700 nm), respectively. The ceramics have up-conversion luminescence properties and also maintain good electrical properties. Under 980 nm excitation, the samples showed two green emission bands (518–536 nm, 536–557 nm) and one red emission band (646–677 nm). In addition, the ceramics have relaxation ferroelectricity, and a high dielectric constant. These functional ceramics with multiple properties will have greater research significance and application value.

     

Properties of B-site non-stoichiometric (K0.5Na0.5)(Nb0.9Ta0.1)1+x O3 lead-free piezoelectric ceramics

The non-stoichiometric (K_0.5Na_0.5)(Nb_0.9Ta_0.1)_1+x O₃ (x = 0, ±0.005, ±0.010) [KN(NT)_1+x ] lead-free piezoelectric ceramics were prepared by normal sintering. The samples were characterized by X-ray diffraction and scanning electron microscopy. All the KN(NT)_1+x ceramics possess orthorhombic perovskite structure. The grain growth of the ceramics is inhibited and the relative density is improved with increasing x. 0.5 mol% (NT)⁵⁺ excess KN(NT)_1+x ceramic which sintered at 1,120 °C has the highest piezoelectric performances among with other samples. Meanwhile, the (NT)⁵⁺ excess ceramics have better time stability than the (NT)⁵⁺ deficient ones. These results show that the KN(NT)_1+x ceramic with x = 0.005 is a promising lead-free piezoelectric material.     

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.     

Low-temperature hydro/solvothermal synthesis of Ta-modified K0.5Na0.5NbO3 powders and piezoelectric properties of corresponding ceramics

K_0.5Na_0.5Nb_1–xTa_xO₃ (KNNTx, x = 0–0.4) powders were synthesized by a novel hydro/solvothermal method at a low reaction temperature (180 °C) and the corresponding ceramics were obtained by normal sintering. Compared with conventional solid-state reaction technique, the optimal sintering temperatures of these ceramics were reduced at least 150 °C. Crystalline structures and surface morphologies were analyzed by X-ray diffraction and scanning electron microscopy. The excellent piezoelectric properties could be obtained by selecting poling temperature near the orthorhombic–tetragonal polymorphic phase transition temperature region. Ta-modified KNN ceramics exhibited better piezoelectric properties than those of pure KNN, and the piezoelectric coefficient d₃₃ showed the maximum value of 156 pC/N for KNNT0.3 ceramics. In addition, the sintering temperature for maximum d₃₃ value differed from that for maximum density. The present hydro/solvothermal method provides a new potential route for preparing KNN-based materials at relatively low temperature.