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.     

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陶瓷为单一的钙钦矿结构，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％．     

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.     

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。     

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.     

(K_(0.5)Na_(0.5))_(1-x)Li_xNb_(1-y)Sb_yO_3系无铅压电陶瓷的弥散相变研究

采用传统陶瓷工艺制备了(K0.5 Na0.5)1-xLixNb1-ySbyO3(KNLNSx-y,x=0～10%(摩尔分数),y=2%～8%(摩尔分数))系无铅压电陶瓷,研究了Li+和Sb5+的取代对KNLNSx-y系材料的相变弥散性的影响.结果表明,在所研究的组成范围内,KNLN-Sx-y,陶瓷都形成了单一的钙钛矿结构,Li+和Sb5+蚪进入了KNN晶格形成固溶体;随着Li含量的增加,KNLNSx-5陶瓷四方-立方相变的弥散性有所减弱;随着Sb含量的增加,KNLNS2-y,陶瓷四方-立方相变的弥散性有所增强.采用修正的居里-外斯定律能够较好的描述KNLNSx-y陶瓷在高于居里温度情况下的介电常数与温度的关系;利用有序-无序理论对该介电弥散现象进行了解释.     

Fabrication of lead-free piezoelectric (Na(0.5)K(0.5))NbO(3) ceramics by a modified solid-state reaction method

Sodium potassium niobate, (Na(0.5)K(0.5))NbO(3), fine powder has been successfully synthesized at the low temperature of 550 degrees C through a modified solid-state reaction method, in which urea [CO(NH(2))(2)] plays an important role. High-density (Na(0.5)K(0.5))NbO(3) ceramics could be obtained by conventional sintering of the synthesized (Na(0.5)K(0.5))NbO(3) fine powder with the addition of 0.03 mol% Co(3)O(4) as a sintering additive. The crystal structure, microstructure, and dielectric and piezoelectric properties were characterized. The (Na(0.5)K(0.5))NbO(3) ceramic showed a comparatively saturated P-E hysteresis loop. The (Na(0.5)K(0.5))NbO(3) ceramic also displayed piezoelectricity with a piezoelectric constant d(33) of 126 pC/N and a planar electromechanical coupling factor k(p) of 33%.     

Piezoelectric properties in (K0.5Bi0.5)TiO3-(Na0.5Bi0.5)TiO3-BaTiO3 lead-free ceramics.

Lead-free piezoelectric ceramics with compositions around the morphotropic phase boundary (MPB) x(Na0.5Bi0.5)TiO3-y(K0.5Bi0.5)TiO3-zBaTiO3 [x + y + z = 1; y:z = 2:1] were synthesized using conventional, solid-state processing. Dielectric maximum temperatures of 280 degrees C and 262 degrees C were found for tetragonal 0.79(Na0.5Bi0.5)TiO3-0.14(K0.5Bi0.5)TiO3-0.07BaTiO3 (BNBK79) and MPB composition 0.88(Na0.5Bi0.5)TiO3-0.08(K0.5Bi0.5)TiO3-0.04BaTiO3 (BNBK88), with depolarization temperatures of 224 degrees C and 162 degrees C, respectively. Piezoelectric coefficients d33 were found to be 135 pC/N and 170 pC/N for BNBK79 and BNBK88, and the piezoelectric d31 was determined to be -37 pC/N and -51 pC/N, demonstrating strong anisotropy. Coercive field values were found to be 37 kV/cm and 29 kV/cm for BNBK79 and BNBK88, respectively. The remanent polarization of BNBK88 (approximately 40 microC/cm2) was larger than that of BNBK79 (approximately 29 microC/cm2). The piezoelectric, electromechanical, and high-field strain behaviors also were studied as a function of temperature and discussed.     

Elastic, piezoelectric, and dielectric characterization of modified BiScO3-PbTiO3 ceramics

The perovskite solid solution system (1-x)BiScO3-(x)PbTiO3 represents an interesting new family of high-temperature piezoelectric materials. Compositions near the morphotropic phase boundary (x approximately 0.64) have been reported to have high Curie temperatures (Tc > 450 degrees C) and good piezoelectric coefficients (d33 approximately 460 pC/N). In this work, manganese additions were used to improve the high-temperature electrical resistivity and RC time constant of compositions near the morphotropic phase boundary. The addition of manganese was found to shift Tc to slightly lower temperatures (442 degrees C and 456 degrees C for x = 0.64 and x = 0.66, respectively). The piezoelectric activities of the modified materials were found to be reduced slightly due to the hardening effect of manganese; however, the temperature stability and resistivity of the modified materials were significantly enhanced. In this paper we present, for the first time, a complete set of materials constants, including the elastic (sij, cij), piezoelectric (dij, eij, gij, hij), dielectric (epsilonij, betaij), and electromechanical (kij) coefficients and compare them to both unmodified 0.36BiScO3-0.64PbTiO3 and PZT5A ceramics.     

Piezoelectric properties in (K0.5Bi0.5)TiO 3-(Na0.5Bi0.5)TiO3-BaTiO 3 lead-free ceramics

Lead-free piezoelectric ceramics with compositions around the morphotropic phase boundary (MPB) x(Na_0.5Bi_0.5)TiO _3-y(K_0.5Bi_0.5)TiO₃-zBaTiO ₃ [x + y + z = 1; y:z = 2:1] were synthesized using conventional, solid-state processing. Dielectric maximum temperatures of 280degC and 262degC were found for tetragonal 0.79(Na_0.5Bi_0.5)TiO₃-0.14(K_0.5 Bi_0.5)TiO₃-0.07BaTiO$ d3 (BNBK79) and MPB composition 0.88(Na_0.5Bi_0.5)TiO₃-0.08(K _0.5Bi_0.5)TiO₃-0.04BaTiO$ d3 (BNBK88), with depolarization temperatures of 224degC and 162degC, respectively. Piezoelectric coefficients d₃₃ were found to be 135 pC/N and 170 pC/N for BNBK79 and BNBK88, and the piezoelectric d₃₁ was determined to be -37 pC/N and -51 pC/N, demonstrating strong anisotropy. Coercive field values were found to be 37 kV/cm and 29 kV/cm for BNBK79 and BNBK88, respectively. The remanent polarization of BNBK88 (~40 muC/cm²) was larger than that of BNBK79 (~29 muC/cm²). The piezoelectric, electromechanical, and high-field strain behaviors also were studied as a function of temperature and discussed     

Enhancement of Q(m) by co-doping of Li and Cu to potassium sodium niobate lead-free ceramics.

Lead-free piezoelectric ceramics KNN modified by Li-substitution and CuO addition have been synthesized, and the piezoelectric and dielectric properties were measured. A morphotropic phase boundary (MPB) between orthorhombic and tetragonal phases was formed with Li-substitution. The co doping of Li and Cu markedly enhanced the mechanical quality factor (Q(m)) in comparison with the sole doping of Li and Cu. Anomalous anti ferroelectric-like hysteresis curves were observed in 2 mol% CuO-doped ceramics. The anti-ferroelectric-like curves were changed to that of normal ferroelectrics following poling. A model based on the formation of the internal bias field (Ei) due to the movements of space charges was proposed to explain these phenomena. It was considered that the Ei stabilized the spontaneous polarization (Ps) and suppressed the domain wall motion to enhance the Q(m). The highest Qm obtained in this study was 742. The [(Na0(0.5)K0(0.5))(0.96)Li0(0.04) ] NbO(3) + 0.45 mol% CuO ceramics showed a high Q(m) value of 414 with a high piezoelectric constant d(33) of 100 pC/N.     

铌镁酸铋-钛酸铅压电陶瓷准同型相界附近的性能和相变温度研究

利用传统固相烧结法制备了Bi(Mg_2/3Nb_1/3)O₃-PbTiO₃(BMN-PT)压电陶瓷, 分析了不同PbTiO₃含量对BMN-PT压电陶瓷的晶体结构、介电、压电及铁电性能的影响. XRD结果表明: 合成的BMN-PT陶瓷具有纯钙钛矿结构, 并且在PbTiO₃含量为x=0.60时, 其组分的XRD图谱在衍射角2θ=45°出现明显的分峰, 说明该组分相结构中存在三方和四方相的共存. 压电铁电性能显示, BMN-0.60PT有最大的压电常数d₃₃(~170pC/N)和平面机电耦合系数k_p(0.35), 最小的矫顽场E_c(29.4 kV/cm)及最大的剩余极化P_r(31.4 μC/cm²). 确定了BMN-PT压电陶瓷的准同型相界(MPB)为PbTiO₃含量x=0.60的组分. 介电系数温谱表明介电系数峰值温度(Tm)随着PbTiO₃含量的增大而升高, MPB组分的Tm约为276℃.     

Electric field-induced strain behavior in lithium- and copper-added potassium sodium niobate piezoceramics and 1-3 piezocomposites

Potassium sodium niobate (KNN)-based leadfree materials were prepared and their field-induced strain behaviors were investigated. Ceramic lead-free piezoelectric materials were prepared in bulk and fiber forms with 1 mol% CuO-added potassium sodium niobate K0.5Na0.5NbO3 and x = 7 mol% lithium-modified (K(0.5-x/2)Na(0.5-x/2)Li(x))NbO(3) compositions. Fibers were drawn using a novel alginate gelation technique. Piezocomposites were prepared from these fibers with 1-3 connectivity and an epoxy matrix. A fully recoverable electrostrain of up to approximately 0.11% was observed in the CuO-added sample, whereas the Li-modified sample yielded up to 0.10% at 50 kV/cm electric field. A strain value of up to approximately 0.03% at 50 kV/cm electric field was obtained for piezocomposites prepared from lithium-modified fibers. The high-field converse piezoelectric coefficient was calculated from the strain-electric field (x-E) graph for all samples. Strain characteristics of the bulk and piezocomposite samples were analyzed based on the variation of strain with respect to square of the polarization (x-P2) to determine the electrostrictive contribution to the strain.     

Sintering and piezoelectric properties of KNN ceramics doped with KZT

This paper investigates the effect of K(1.94)Zn(1.06)Ta(5.19)O(15) (KZT) addition on the sintering behavior and piezoelectric properties in lead free piezoelectric ceramics of (K(0.5)Na(0.5))NbO(3) (KNN). The apparent density of sintered KNN ceramics was increased with KZT addition, and a relative density of above 96.3% was obtained with the doping of over 0.5 mol% KZT. The maximum dielectric and piezoelectric properties of epsilon(T)(3)/epsilon(0) = 590, d(33) = 126 pC/N, k(p) = 0.42, and P(r) = 18 microC/cm(2) were obtained from 0.5 mol% KZT-doped KNN ceramics. A small amount of KZT (about 0.5 mol%) was effective for improving the sintering behavior and piezoelectric properties, but KZT addition exceeding 1.0 mol% was effective only for densification. A small amount of KZT was effective for densification of KNN ceramics by promoting K(5.75)Nb(10.8)O(30) liquid phase formation. However, even though KNN with 1.0 to approximately -2.0 mol% KZT had a relative density of >98.5%, the piezoelectric properties were inferior to those of 0.5 mol% KZT-doped KNN, presumably due to the smaller grain size and excess liquid phase of the KNN ceramics doped with higher amounts of KZT. It is believed that a small amount of KZT could be one of the suitable sintering aids to obtain highly dense KNN based piezoelectric.     

Field-induced phase transition and relaxor character in submicrometer-structured lead-free (Bi0.5Na0.5)0.94Ba0.06TiO3 piezoceramics at the morphotropic phase boundary

Submicrometer-structured (Bi(0.5)Na(0.5))(0.94)Ba(0.06)TiO(3) ceramics ((G) < 720 nm) from nanopowders were studied. The real part of the optimum room temperature set of piezoelectric coefficients obtained from resonances of the BNBT6 dense ceramic disks and shear plates [d(31) = (-37 + 1.33i) pC·N(-1), d(15) = (158.3 - 8.31i) pC·N(-1), k(t) = 40.4%, k(p) = 26.8%, and k(15) = 40.2%] and d(33) (148 pC·N(-1)) can be compared with the reported properties for coarse-grained ceramics. Shear resonance of thickness-poled plates is observed at T = 140°C. Permittivity versus temperature curves of poled samples show relaxor character up to T(i) = 230°C on heating and T(i) = 210°C on cooling of the depoled samples. The phase transition from the room-temperature ferroelectric (FE) to a low-temperature non-polar at zero field (LTNPZF) phase can be observed as a sharp jump in ε(δ)(33)'(T) curves or, as the degree of poling decreases, as a soft change of slope of the curves at T(FE-LTNPZF) = T(d) = 100°C. This dielectric anomaly is not observed on cooling of depoled samples, because the FE phase is field-induced. The observed macroscopic piezoelectric activity above T(d) is a consequence of the coexistence of nanoregions of the FE phase in the interval between T(FE-LTNPZF) and T(i).     

(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.     

无铅压电陶瓷KNN常压烧结及其电学性能

用常压烧结法制备K_0.5Na_0.5NbO₃陶瓷。研究烧结温度与陶瓷密度和电学性能的关系。研究表明在1065℃~1120℃范围内, 温度对陶瓷的密度有显著影响。当烧结温度为1100℃时, 密度达到4.35 g/cm³ (占理论密度的95%); 1100℃烧结的陶瓷表现出最好的电学性能, 压电常数最大118 pC/N, 相对介电常数最大达538, 介电损耗最小仅4.7%, 剩余极化强度为15.37 μC/cm², 矫顽场为13.16 kV/cm。陶瓷样品在206℃从正交结构转变到四方结构, 居里温度为410℃。     

分凝对Pb(Mg1/3Nb2/3)O3-38%PbTiO3单晶的成分及介电、压电性能的影响

研究了用改进的Bridgman法生长的PMNT62／38单晶在其生长过程中的分凝现象，研究了分凝导致的成分不均匀及其对介电和压电性能的影响。XRFA分析表明，PMNT62／38单晶底部的PbTiO3(PT)含量为x=35.2mol%，而顶部的PT含量为43mol%。底部晶体（001），（110）和（111）三种切型的晶片加电场极化后，其介电和压电性能出现了异常的现象。（110）切型的压电模量最大，为1200pC/N；（111）次之，为789pC/N；（001）最低，为371pC/N。极化后的（110）和（111）晶片在室温、1kHz频率下的相对介电常数（两种切型的εr都在10000左右），约为（001）晶片（εr-5000)的1倍，并且介电常数在低温端有上升的趋势。     

分凝对Pb(Mg1/3Nb2/3)O3-38%PbTiO3单晶的成分及介电、压电性能的影响

研究了用改进的Bridgman法生长的PMNT62/38单晶在其生长过程中的分凝现象,研究了分凝导致的成分不均匀及其对介电和压电性能的影响.XRFA分析表明,PMNT62/38单晶底部的PbTiO3(PT)含量为x=35.2mol％,而顶部的PT含量为43mol％.底部晶体(001),(110)和(111)三种切型的晶片加电场极化后,其介电和压电性能出现了异常的现象.(110)切型的压电模量最大,为1200pC/N;(111)次之,为789pC/N;(001)最低,为371pC/N.极化后的(110)和(111)晶片在室温、1kHz频率下的相对介电常数(两种切型的εr都在10000左右),约为(001)晶片(ε_r-5000)的1倍,并且介电常数在低温端有上升的趋势.     

锰掺杂对(K_(0.5)Na_(0.5))NbO_3-LiNbO_3压电陶瓷结构和性能的影响

采用传统陶瓷制备工艺制备了(K_(0.5)Na_(0.5))NbO_3-LiNbO_3-xMnO_2压电陶瓷,分析了陶瓷样品的微观组织结构.实验结果表明,随MnO_2掺杂量的增多,陶瓷由四方相转变为正交相,晶粒的均匀性下降并生成K_3LiNb_6O_(17)相.研究了MnO_2不同掺杂量对陶瓷压电性能的影响.结果表明,随锰掺杂量的增加,材料逐渐变"硬",机电耦合系数k_p和压电常数d_(33)逐渐减小,同时Q_m逐渐增大;当MnO_2含量为0.8%(质量分数)时,陶瓷的机械品质因数达到最大,此时陶瓷的压电性能为:k_p=0.34,k_t=0.43,d_(33)=110pC/N,Q_m=401.3.