熔盐法合成Na0.5K0.5NbO3粉体

采用熔盐法在K2CO3和Na2CO3的熔盐（K2CO3／Na2CO3=45／55）中800℃并保温2h的条件下制备出了单相、纯钙态矿型结构的Na0.5K0.5NbO3粉体,运用XRD以及SEM技术对所得粉体进行了相组成及显微结构分析。结果表明：随着盐含量的增加,晶体结构从正交相转变为四方相,晶粒大小先增加而后稍微减小,并且获得较好的介电压电性：ε33^T／ε0（1kHz）=45-264,tgδ=1．5％～2．6％,Tc=402℃,Tτ-o=202℃,d33=88-98pC／N,Qm=465-574,Kp=29．09%～30．47％,在10kHz频率下,介电损耗有一点改变。NKN将有可能成为用于高频下的无铅压电陶瓷之一。     

Piezoelectric Properties of （Na0.5K0.5-xLix）NbO3 Ceramics

Lead-free piezoelectric ceramics （Na0.5K0.5-xLix）NbO3 （x=0.057-0.066） were synthesized by an ordinary sin-tering technique. Substituting Li for K can lead to structural distortion, which improves the Curie temperature （To） greatly. By adding appropriate LiNbO3 content, piezoelectric constant d33 values reach 202-212 pC/N. Electromechanical coefficients of the planar mode reach 44.4%-46.8%. The dielectric loss is below 2.6%, which is much lower than reported （about 50%）. The To of （Na0.5K0.5-xLix）NbO3 （x=0.057-0.066） is in the range of 490-510℃, at least 70℃ higher than that of pure （Na0.5K0.5）NbO3 ceramics. The results show that （Na0.5K0.5-xLix）NbO3 ceramic is a kind of good lead-free high-temperature piezoelectric material.     

表面活性剂辅助溶剂热制备K0.5Na0.5NbO3基陶瓷粉体

采用表面活性剂辅助溶剂热合成K_(0.5)Na_(0.5)NbO_3基陶瓷粉体,系统研究了助表面活性剂、表面活性剂以及助表面活性剂辅助表面活性剂对合成粉体结构和形貌的影响。结果表明,添加不同含量异丙醇(IPA)可得到不同结构和形貌的K_(0.5)Na_(0.5)NbO_3粉体;表面活性剂使得粉体形貌规则,异丙醇含量一定,随着表面活性剂(SBDS、PEG400)浓度的增加,粉体颗粒形貌变得规则且异丙醇具有细化粉体的作用,相比于SBDS、PEG400使得粉体形貌更加规则;表面活性剂(PEG400)浓度一定,需选择合适的异丙醇含量可获得粒径更小的规则形貌粉体,即PEG400=1 g/L,V(IPA)/V(H_2O)=2/3和3/2可得到粒径约300 nm的正方体颗粒。     

Structure and piezoelectric properties of K0.5Na0.5NbO3–Bi0.5Li0.5TiO3 lead-free ceramics

Lead-free (1−x) K_0.5Na_0.5NbO₃–xBi_0.5Li_0.5TiO₃ + 1 mol% MnO₂ piezoelectric ceramics have been prepared by a conventional ceramic technique and their structure and piezoelectric properties have been studied. Our results reveal that Bi_0.5Li_0.5TiO₃ diffuse into K_0.5Na_0.5NbO₃ lattices to form a solid solution with a perovskite structure. The addition of Bi_0.5Li_0.5TiO₃ to the K_0.5Na_0.5NbO₃ solid solution decreases the paraelectric cubic-ferroelectric tetragonal phase transition temperature (T _C) slightly, but shifts the ferroelectric tetragonal-ferroelectric orthorhombic phase transition temperature (T _O−T) significantly to low temperatures. As a result, coexistence of the orthorhombic and tetragonal phases is formed at 0.01 < x < 0.03 near room temperature, leading to a significant improvement in the piezoelectric properties of the ceramics. The ceramic with x = 0.025 exhibits a relatively high T _C (392 °C) and optimum piezoelectric properties: d ₃₃ = 191 pC/N, k _p = 51.5% and k _t = 45.5%. The ceramic also exhibit a good thermal stability of piezoelectric properties.     

LiTaO3掺杂对K0.5Na0.5NbO3基无铅压电陶瓷性能的影响

采用传统陶瓷工艺制备了LiTaO3掺杂的K0.5Na0.5NbO3基无铅压电陶瓷(记为KNN xLT,x=0～8%(摩尔分数)),并研究了陶瓷的晶相、显微结构和压电、铁电等性能.研究结果表明,KNN xLT陶瓷的正交相-四方相准同型相界(MPB)位于4%＜x＜6%处.随着LiTaO3含量的增加,陶瓷的正交→四方结构相变温度(TO-T)向低温方向移动,而四方→立方结构相变温度(Tc)向高温方向移动.陶瓷的压电常数d33和机电耦合系数kp随LiTaO3含量的增加均先增大后减小,而剩余极化强度Pr则随之逐渐减小,矫顽场Ec逐渐增大.当x=6%时,陶瓷具有较好的压电和铁电性能:d33=190pC/N,kp=40.0%,Pr=22.0μC/cm2,Ec=1.78kV/mm,Tc=440℃.该体系陶瓷具有较高的压电常数和比较大的平面机电耦合系数,是一种应用前景良好的压电铁电材料.     

Dielectric nonlinearity and electrical properties of K0.5Na0.5NbO3–SrTiO3 relaxor ferroelectrics

K_0.5Na_0.5NbO₃–xSrTiO₃(x = 0, 0.1 and 0.2) ceramics were prepared using the solid-state method. The phase transition behaviors, electrical properties, and electric field-induced dielectric nonlinearity behaviors were investigated as a function of the SrTiO₃ content. The electrical properties of the investigated compositions exhibited a significant dependence on the content of SrTiO₃. Doped content more than x = 0.1 induced a relaxor transformation, while the dielectric loss decreased quickly. In addition, an “extrinsic” polarization contributed to the dielectric nonlinearity behavior of the composition x = 0.1 with the polar nanoregions and domain-wall motions, by means of the multipolarization-mechanism model fittings of the electric field dependence of the dielectric permittivity. The dielectric tunability and loss angle tangent of the composition x = 0.1 were 32.6 % and 0.028, respectively.     

无铅压电陶瓷K0.5Na0.5NbO3-BiFeO3的烧结工艺与压电性能研究

采用传统常压固相烧结工艺制备了掺杂0.8at%BiFeO₃(BF)的K_0.5Na_0.5NbO₃(KNN) 无铅压电陶瓷,着重研究了烧结温度与保温时间对陶瓷的晶体结构、相转变、致密度与压电、介电性能的影响. 研究结果表明, 所有陶瓷样品都为单一的钙钛矿结构, 烧结温度与保温时间对陶瓷样品的室温晶体结构与相转变温度几乎没有影响, 但对陶瓷的表面形貌、密度和压电性能有较大的影响. 当保温时间为3h,在1100℃至1150℃范围内, 随烧结温度的升高,陶瓷的压电常数d33、平面机电耦合系数Kp及机械品质因数Qm均一直升高, 介电损耗tanδ则显著降低. 当烧结温度为1150℃时, 随保温时间的增加, 陶瓷的压电性能先显著提高后基本保持不变. 1150℃保温2h烧结的陶瓷获得良好的性能：密度ρ=4.50g/cm³（致密度为95.63%）, d₃₃=132pC/N, K_p=45%, Q_m=333.73, tanδ=2.39%.     

Structure and electrical properties of K0.5Na0.5NbO3–SrTiO3 lead-free piezoelectric ceramics with LiSbO3 doping

Lead-free piezoelectric ceramics (1 ? x)K_0.5Na_0.5NbO₃–xSrTiO₃ with 6 mol% LiSbO₃ doping have been prepared by conventional solid state sintering technique at 1,125 °C for 3 h in air. The effects of the SrTiO₃ and LiSbO₃ on the phase structure and electrical properties of the ceramics were systematically investigated. All ceramic samples show a single phase perovskite structure with tetragonal symmetry when LiSbO₃ content was 6 mol% and SrTiO₃ content was 2–10 mol% by X-ray diffraction analysis and highly dense structure by SEM patterns. The ceramic with x = 0.04 exhibits optimum electrical properties at room temperature (d ₃₃ = 267 pC/N, k _p = 46 %, ε _r = 1,168, tanδ = 0.021, P _r = 30.3 μC/cm², E _C = 1.98 kV/mm), which suggests that the ceramic is a promising candidate material for lead-free piezoelectric ceramics.     

(K0.5Na0.5)NbO3-LiNbO3无铅压电陶瓷的烧结特性和压电性能研究

采用传统陶瓷烧结工艺制备了(1-x)(K0.5Na0.5)NbO3-xLiNbO3无铅压电陶瓷,研究了陶瓷的结构、烧结特性及电性能特征.制备的(K0.5Na0.5)NbO3-LiNbO3陶瓷为单一的钙钛矿结构,室温下其相结构随LiNbO3含量增加逐渐由正交相向四方相转变,显微结构也由于LiNbO3含量的不同而表现出很大差异.与(K0.5Na0.5)NbO3陶瓷相比,(K0.5Na0.5)NbO3-LiNbO3陶瓷的烧结温度降低,烧结特性得到改善. (K0.5Na0.5)NbO3-LiNbO3陶瓷表现出优越的压电性能,其中0.94(K0.5Na0.5)NbO3-0.06LiNbO3(x=0.06)陶瓷的压电常数d33达到205pC/N,机电耦合系数kp为40.3%,kt达到49.8%.     

Structures and electrical properties of (Na0.5K0.5)NbO3–Li(Ta0.5Nb0.5)O3 lead-free piezoelectric ceramics

Solid solutions of (Na_0.5K_0.5)NbO₃ (NKN) and Li(Ta_0.5Nb_0.5)O₃ (LTN) were investigated as a potential candidate of lead-free piezoelectric ceramics. It was found that the Curie temperature of solid solutions increases slightly with increasing the LTN content and simultaneously the polymorphic phase transition temperature linearly decrease till below room temperature. An orthorhombic to tetragonal phase transformation at room temperature, or a morphotropic phase boundary, in NKN is induced by ~7 at% LTN addition, where the best dielectric, piezoelectric and electromechanical properties are achieved. The 0.94NKN–0.07LTN ceramics possess a dielectric constant of 765, a loss tangent of 0.04 at 1 kHz, a piezoelectric constant d₃₃ of 253 pC/N and an electromechanical coupling factor k_p of 48%.     

Structure and piezoelectric properties of K0.5Na0.5NbO3–AlFeO3 lead-free ceramics by using AlFeO3 as a sintering aid

The (1 ? x)K_0.5Na_0.5NbO₃–xAlFeO₃ ((1 ? x)KNN–xAF) (x = 0.01–0.08) lead-free piezoelectric ceramics were prepared at low temperature of 1,000 °C by conventional ceramic processing. And AF was used as a sintering aid in order to improve the sintering behavior of KNN. The effect of AF addition on the microstructure, dielectric and piezoelectric properties of the ceramics have been investigated. The results indicate that a small amount of AF can improve the sintering performance and piezoelectric properties of the ceramics effectively. The KNN–AF ceramics for x = 0.03 show the best piezoelectric properties: d ₃₃ = 116 pC/N, k _p  = 32.9 %, Q _m  = 114.8, T _C  = 382 °C, P _r  = 21.8 μC/cm². This also indicates that (1 ? x)KNN–xAF ceramics are a promising lead-free piezoelectric candidate material because of its good properties, low-temperature sintering characteristics and plenty of Al₂O₃ and Fe₂O₃ resources with low cost.     

Reaction-sintering of lead-free piezoceramic compositions: (0.95 − x)Na0.5K0.5NbO3–0.05LiTaO3–xLiSbO3

Incorporation of LiSbO₃ into the lead-free piezoceramic composition 0.95Na_0.5K_0.5NbO₃–0.05LiTaO₃ produced a change from an orthorhombic to tetragonal crystal system in samples produced by reaction-sintering. The inferred limit of solid solution along the compositional join, (0.95 − x)Na_0.5K_0.5NbO₃–0.05LiTaO₃–xLiSbO₃, occurred at x ~ 0.06. Differential scanning calorimetry indicated broad peaks at temperatures associated with ferroelectric–paraelectric transitions. The transition temperatures decreased with increasing values of x, up to x = 0.06. Microstructures showed secondary grain growth; a slight decrease in grain-size with increasing LiSbO₃ modification was identified.     

Effects of NaSbO3 on phase structure and electrical properties of K0.5Na0.5NbO3–LiTaO3–NaSbO3 piezoelectric ceramics

The (0.96–x)K_0.5Na_0.5NbO₃–0.04LiTaO₃–xNaSbO₃ (abbreviated as KNN–LT–xNS, x = 0, 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08) lead-free piezoelectric ceramics were fabricated by conventional ceramic technique. The crystal structure, dielectric, ferroelectric and piezoelectric properties of the ceramics were investigated. The Curie temperature (T _C) and the polymorphic phase transition temperature (T _O?T) of the ceramics decreased gradually with the increase of NaSbO₃. In addition, a coexistence of orthorhombic and tetragonal phases in the ceramics was identified in the composition range of 0.05 ≤ x ≤ 0.08. The ceramic with a composition of x = 0.06, which was close to the orthorhombic side of the polymorphic phase transition (PPT) region, exhibited excellent electrical properties with piezoelectric coefficient d ₃₃ = 233 pC/N, planar electromechanical coupling coefficient k _p = 0.328, remnant polarization P _r = 14.7 μC/cm², coercive field E _c  = 11.7 kV/cm, relative permittivity $ \varepsilon_{33}^{\text{T}} /\varepsilon_{0} $  = 1,033, and loss tangent tan δ = 0.063. The ceramics had relatively low Q _m value in the range of 10–37.     

Phase transition, dielectric and piezoelectric properties of K0.5Na0.5NbO3–CaTi0.9Zr0.1O3 lead-free ceramics

Lead-free (1 − x)K_0.5Na_0.5NbO₃–xCaTi_0.9Zr_0.1O₃ + 0.75 mol%MnO₂ piezoelectric ceramics have been prepared by an ordinary sintering technique and their phase transition, dielectric and piezoelectric properties have been studied. The results of X-ray diffraction show that CaTi_0.9Zr_0.1O₃ diffuse into K_0.5Na_0.5NbO₃ lattices to form a solid solution with a perovskite structure. After the addition of CaTi_0.9Zr_0.1O₃, both the cubic–tetragonal and tetragonal–orthorhombic phase transition temperatures decrease, and a relaxor behavior is induced. Coexistence of the orthorhombic and tetragonal phases is formed in the ceramics with 0.03 < x < 0.07 at room temperature. Owing to the higher number of possible polarization states resulting from the coexistence of the two phases, the piezoelectric properties of the ceramics are enhanced significantly. The ceramic with x = 0.05 exhibits the following optimum properties: d ₃₃ = 203 pC/N, k _p = 45.0%, and T _C = 342 °C.     

(K0.5Na0.5)NbO3–Bi(Mg0.5Ti0.5)O3 solid solution: phase evolution, microstructure and electrical properties

Lead-free piezoelectric ceramics with the composition of (1 ? x)(K_0.5Na_0.5)NbO₃–xBi(Mg_0.5Ti_0.5)O₃ [(1 ? x)KNN–xBMT, 0 ≤ x ≤ 0.04] were synthesized via solid-state reaction method. X-ray diffraction patterns revealed that the orthorhombic—tetragonal phase transition was present for (1 ? x)KNN–xBMT with increasing the content of BMT. The study of dielectric properties illustrated that both peaks of orthorhombic—tetragonal (T _O–T ) and tetragonal—cubic (T _T–C ) phase transitions shifted to lower temperature. Through adding BMT, the electrical properties of KNN ceramics were obviously improved. The optimized piezoelectric and ferroelectric properties with d ₃₃  = 127 pC/N, k _p  = 36.58 %, P _r  = 22.1 μC/cm² were obtained as x = 0.01.     

Microstructure and piezoelectric properties of lead-free 0.95(Na0.5K0.5)NbO3–0.05(Bi0.5K0.5)Zr1−x Ti x O3 ceramics

0.95(Na_0.5K_0.5)NbO₃–0.05(Bi_0.5K_0.5)Zr_1?x Ti _x O₃ (abbreviated as KNN–BKZT _x ) ceramics were prepared by the conventional solid state method, and the effect of the Ti content on the surface morphology, crystalline structure, and electrical properties of KNN–BKZT _x ceramics were mainly investigated. With the increase of Ti content, the temperature of the orthorhombic–tetragonal (O–T) phases transitions shifted to lower temperatures, and the O–T phase boundary of KNN–BKZT _x ceramics was identified in the composition with 0 ≤ x ≤ 0.3 at room temperature. It was considered that the piezoelectric properties of the ceramics were enhanced significantly owing to the more possible polarization states resulting from the coexistence of two phases. The ceramic with x = 0.2 exhibited optimum properties: d ₃₃ = 260 pC/N, k _p = 0.38, and T _C = 323 °C.