Phase-transition temperatures and piezoelectric properties of (Bi1/2Na1/2)TiO3-(Bi1/2Li1/2)TiO3-(Bi1/2K1/2)TiO3 lead-free ferroelectric ceramics.

The phase-transition temperatures and piezoelectric properties of x(Bi(1/2)Na(1/2))TiO3-y(Bi(1/2)Li(1/2))TiO3-z(Bi(1/2)K(1/2))TiO3 [x + y + z = 1] (abbreviated as BNLKT100(y)-100(z)) ceramics were investigated. These ceramics were prepared using a conventional ceramic fabrication process. The phase-transition temperatures such as depolarization temperatures T(d), rhombohedraltetragonal phase transition temperature T(R-T), and dielectric-maximum temperature T(m) were determined using electrical measurements such as dielectric and piezoelectric properties. The X-ray powder diffraction patterns of BNLKT100(y)-100(z)) show the morphotropic phase boundary (MPB) between rhombohedral and tetragonal at approximately z = 0.20, and the piezoelectric properties show the maximum at the MPB. The electromechanical coupling factor k(33), piezoelectric constant d(33) and T(d) of BNLKT4-20 and BNLKT8-20 were 0.603, 176 pC/N, and 171 degrees C, and 0.590, 190 pC/N, and 115 degrees C, respectively. In addition, the relationship between d33 and Td of tetragonal side and rhombohedral side for BNLKT4-100z and BNLKT8-100z were presented. Considering both high Td and high d(33), the tetragonal side of BNLKT4-100z is thought to be the superior composition. The d(33) and T(d) of BNLKT4-28 were 135 pC/N and 218 degrees C, respectively. Moreover, this study revealed that the variation of T(d) is related to the variation of lattice distortion such as rhombohedrality 90-alpha and tetragonality c/a.     

三元陶瓷Pb(In1/2Nb1/2)O3-Pb(Ni1/3Nb2/3)O3-PbTiO3准同型相界附近组分的介电、铁电和压电性能

铅基复合钙钛矿铁电材料广泛应用于机电传感器、致动器和换能器。二元铁电固溶体Pb(Ni_1/3Nb_2/3)O₃- PbTiO₃(PNN-PT)由于其在准同型相界(MPB)区域具有优异的压电、介电性能而备受关注。然而较大的介电损耗和较低的居里温度限制了其在高温高功率器件方面的应用。本研究通过引入Pb(In_1/2Nb_1/2)O₃ (PIN)作为第三组元改善PNN-PT的电学性能, 提高其居里温度; 通过两步法合成了MPB区域的三元铁电陶瓷Pb(In_1/2Nb_1/2)O₃- Pb(Ni_1/3Nb_2/3)O₃-PbTiO₃ (PIN-PNN-PT), 研究了其结构、介电、铁电和压电性能。制备的所有组分陶瓷具有纯的钙钛矿结构。随着PT含量的增加, 陶瓷结构从三方相转变为四方相。通过XRD分析得到了室温下PIN-PNN-PT体系的MPB相图。体系的居里温度由于PIN的加入得到了很大的提高, 更重要的是PIN的引入降低了PNN-PT体系的介电损耗和电导。MPB处的组分展现出了优异的电学性能, 室温下, 性能最优组分为0.30PIN-0.33PNN-0.37PT: d₃₃=417 pC/N, T_C=200 ℃, ε′= 3206, tanδ=0.033, P_r=33.5 μC/cm², E_C=14.1 kV/cm。引入PNN-PT的PIN第三组元使得体系的居里温度和压电性得到提高的同时降低了的介电损耗和电导率, 因此, PIN-PNN-PT三元铁电陶瓷在高温高功率换能器等方面具备一定的应用潜力。     

Dielectric and piezoelectric properties of PbFe1/2Nb1/2O3-PbTiO3 ceramics from the morphotropic phase boundary compositional range

Dielectric, X-ray, and piezoelectric studies of highly-resistive Li-doped (1-x)PbFe(1/2)Nb(1/2)O(3)-(x)PbTiO(3) (PFN-xPT) ceramics from the 0 ≤ x ≤ 0.2 range fabricated by solid-state synthesis and usual sintering have been carried out. Distinct anomalies of dielectric and piezoelectric parameters, corresponding to the transition between rhombohedral (monoclinic) and tetragonal ferroelectric phases, have been observed in pure PFN and PFN-xPT compositions with PbTiO(3) content up to 8 mol.%. The x,T-phase diagram of the PFN-xPT solid solution system has been constructed using these data.     

Phase-transition temperatures and piezoelectric properties of (Bi/sub 1/2/Li/sub 1/2/)TiO/sub 3/-(Bi/sub 1/2/K/sub 1/2/)TiO/sub 3/ lead-free ferroelectric ceramics

The phase-transition temperatures and piezoelectric properties of x(Bi_1/2Na_1/2)TiO_3-y(Bi_1/2Li_1/2)TiO_3-z(Bi_1/2K_1/2)TiO₃ [x + y + z = 1] (abbreviated as BNLKT100y-100z) ceramics were investigated. These ceramics were prepared using a conventional ceramic fabrication process. The phase-transition temperatures such as depolarization temperatures T_d, rhombohedral-tetragonal phase transition temperature T_R-T, and dielectric-maximum temperature T_m were determined using electrical measurements such as dielectric and piezoelectric properties. The X-ray powder diffraction patterns of BNLKT100y-100z show the morphotropic phase boundary (MPB) between rhombohedral and tetragonal at approximately z = 0.20, and the piezoelectric properties show the maximum at the MPB. The electromechanical coupling factor &33, piezoelectric constant d₃₃ and T_d of BNLKT4-20 and BNLKT8-20 were 0.603, 176 pC/N, and 171degC, and 0.590, 190 pC/N, and 115degC, respectively. In addition, the relationship between d₃₃ and T_d of tetragonal side and rhombohedral side for BNLKT4-100z and BNLKT8-100z were presented. Considering both high T_d and high d₃₃, the tetragonal side of BNLKT4-100z is thought to be the superior composition. The d₃₃ and T_d of BNLKT4-28 were 135 pC/N and 218degC, respectively. Moreover, this study revealed that the variation of Td is related to the variation of lattice distortion such as rhombohedrality 90-alpha and tetragonality c/a.     

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℃.     

Dielectric properties of Pb[(1?x)(Zr1/2Ti1/2)?x(Zn1/3Ta2/3)]O3 ceramics prepared by columbite and wolframite methods

Polycrystalline samples of Pb[(1 − x)(Zr_1/2Ti_1/2) − x(Zn_1/3Ta_2/3)]O ₃ , where x = 0.1–0.5 were prepared by the columbite and wolframite methods. The crystal structure, microstructure, and dielectric properties of the sintered ceramics were investigated as a function of composition via X-ray diffraction (XRD), scanning electron microscopy (SEM), and dielectric spectroscopy. The results indicated that the presence of Pb(Zn_1/3Ta_2/3)O₃ (PZnTa) in the solid solution decreased the structural stability of overall perovskite phase. A transition from tetragonal to pseudo-cubic symmetry was observed as the PZnTa content increased and a co-existence of tetragonal and pseudo-cubic phases was observed at a composition close to x = 0.1. Examination of the dielectric spectra indicated that PZT–PZnTa exhibited an extremely high relative permittivity at the MPB composition. The permittivity showed a ferroelectric to paraelectric phase transition at 330 °C with a maximum value of 19,600 at 100 Hz at the MPB composition.     

Structural and dielectric properties of the phase Pb1−2xKxM3+xNb2O6, M = La or Bi

The Pb_1?2xK_xM³⁺_xNb₂O₆, M = La or Bi, solid solutions have been prepared by solid state reaction and their structural and ferroelectric properties have been established. Complete crystalline solid solubility exists in both systems; in addition, three structurally related phases, namely, the ferroelectric orthorhombic and tetragonal tungsten bronze phases and the paraelectric tetragonal K.₅La.₅Nb₂O₆ type phase, have been identified at room temperature. The composition ranges for three phases are 0.0 ≤ x ≤ 0.47, 0.48 ≤ x ≤ 0.85, 0.86 ≤ x ≤ 1.0, respectively. The ferroelectric phase transition temperature, T_c, decreases with increasing concentration of K⁺ and La³⁺ or Bi³⁺ in the orthorhombic tungsten bronze phase. A few compositions from each system exhibit excellent dielectric and piezoelectric characteristics, indicating that they could be future materials for piezoelectric and high frequency dielectric studies.     

Morphotropic phase boundary (MPB) effect in Pb (Zr,Ti)O3 rhombohedral/tetragonal multilayered films

Alternating rhombohedral/tetragonal Pb(Zr_xTi_1−x)O₃ (P_x) multilayered films were prepared via a chemical solution method. It has been found that the P45/P55 multilayers show significant dielectric enhancement comparing with the uniform P45 and P55 films, and this dielectric enhancement increases as the decrease of the layer periodicity. However, the dielectric constant of the Pb(Zr,Ti)O₃ rhombohedral/tetragonal multilayered films decreases when the layer compositions are away from morphotropic phase boundary (MPB), and no remnant polarization enhancement was observed in all the multilayered films. After comparing the dielectric and ferroelectric properties of the multilayers with the corresponding single-phase films, the dielectric enhancement in P45/P55 multilayers was ascribed to the formation of the MPB region around the interfaces between the P45 and P55 layers.     

新型钙钛矿型铁电陶瓷BSPT研究进展

(1-x)BiScO3-xPbTiO3(BSPT)是一种新型钙钛矿型结构的铁电体.BSPT体系在x=0.64附近有三方相和四方相的准同型相界(MPB).BSPT陶瓷的制备主要采用传统的电子陶瓷制备方法,包括常压法和高压法.BSPT陶瓷具有优良的介电和压电性能,居里温度Tc比Pb(Zr,Ti)O3(PZT)的高.综述了近年来对BSPT陶瓷的研究进展,重点介绍了邻近MPB的0.36BiScO3-0.64PbTiO3铁电陶瓷的性能.同时还介绍了掺杂对BSPT陶瓷的影响.     

弛豫型铁电体PZNT制备与性能研究的进展

本文综述了近年来国际上弛豫型铁电体PZNT的制备与介电、压电及电致伸缩性能研究的进展．PZNT单晶体的制备方法以高温PbO熔剂法为主,其尺寸已达40mm．随PT含量的变化,PZNT的顺电一铁电相交由弥散性、混合型变为一级相变;其铁电-铁电相变可由组份或电场诱导,由介电性能表征．压电性能在MPB处及偏向三方相一侧达到最佳,＜001＞切向的三方相与四方相单晶可分别作为频带宽、分辨率高、且阻抗匹配好的新一代声阵列与单个器件传感器．＜001＞向的PZNT单晶具有巨大的电致伸缩应变,可望成为高性能的固体驱动器．     

Morphotropic phase boundary in Pb(Sc1/2Nb1/2)O3-BiScO3-PbTiO3 high temperature piezoelectrics

The solid solutions in the 0.36BiScO₃-0.64(1 − x)PbTiO₃-0.64xPb(Sc_1/2Nb_1/2)O₃ system were fabricated using wolframite precursor method. A coexistence of rhombohedral and tetragonal phases is formed in the studied compositions range and a wide morphotropic phase boundary region is confirmed by X-ray diffraction results. After the addition of Pb(Sc_1/2Nb_1/2)O₃, a relaxor behavior is induced and the dielectric maximum temperature shifts to higher temperatures with increasing measuring frequencies. The presence of relaxor can be ascribed to the formation of polar nanoregions. The studied composition exhibits the optimal ferroelectric and piezoelectric properties with d₃₃ of 453 pC/N and K_p of 0.58, T_m of 405 °C for x = 0.10 composition, which is suitable for future high-temperature piezoelectric application.     

Synthesis and characterization of pseudo-ternary Pb(Fe<Subscript>1/2</Subscript>Nb<Subscript>1/2</Subscript>)O<Subscript>3</Subscript>-PbZrO<Subscript>3</Subscript>-PbTiO<Subscript>3</Subscript> ferroelectric ceramics via a B-site oxide mixing route

Perovskite phase formation and dielectric/ferroelectric properties of the pseudo-ternary Pb(Fe_1/2Nb_1/2)O₃-PbZrO₃-PbTiO₃ (PFN-PZ-PT) ferroelectric ceramics have been investigated as promising materials for multi-layer ceramic capacitors. Complete solid solution with pure perovskite phase can be formed in this system in the whole composition range studied using conventional solid-state reaction method via a B-site oxide mixing route. Crystal lattice of the ceramics obtained shrinkages with the increase of the concentration of Pb(Fe_1/2Nb_1/2)O₃ (PFN) and expands with the increase of the content of PbZrO₃ (PZ). With the increase of the concentration of PbTiO₃ (PT), crystal structure of PFN-PZ-PT changes from pseudo-cubic ferroelectric phase to tetragonal one while retains the fraction of PFN as constant. A morphotropic phase boundary (MPB) forms at the composition of 42 mol% PT regardless of whatever concentration of PFN, and the content of PFN affects little on the composition of MPB. The preliminary phase diagram of the PFN-PZ-PT system is determined by X-ray diffraction (XRD) measurements combining with dielectric/ferroelectric characterization. Dielectric measurements indicate that the value of dielectric maximum (ɛ_m) and the temperature where ɛ_m appears (T_m) increase with the increase of the concentration of PT. However, PFN exhibits opposite effects, i.e., ɛ_m increases with the increase of the concentration of PFN accompanied by the decrease of T_m.     

Dielectric and piezoelectric properties of (0.97-x) Bi1/2Na1/2TiO3-xBi1/2K1/2TiO3-0.03NaNbO3 ceramics

Ceramics of the series (0.97-x)Bi_1/2Na_1/2TiO₃-xBi_1/2K_1/2TiO₃-0.03NaNbO₃ (x = 0, 0.02, 0.06, 0.10, 0.16, 0.20, 0.30) were prepared by the conventional mixed oxide method. Influence of Bi_1/2K_1/2TiO₃ content on the crystal structure, microstructure, dielectric and piezoelectric properties were studied. All compositions showed single perovskite phase and the morphotropic phase boundary (MPB) between rhombohedral and tetragonal phase existed at the point of x = 0.16. Temperature dependences of permittivity and dissipation factor of unpoled samples revealed that permittivity increased with Bi_1/2K_1/2TiO₃ content and it reached maximum value near the MPB. At the same time, the peak value of dissipation factor increased with the addition of Bi_1/2K_1/2TiO₃. All the samples experienced two phase transitions: from ferroelectric to antiferroelectric at the first transition temperature (T_d) and from antiferroelectric to paraelectric at the temperature (T_m) corresponding to maximum value of permittivity. The phase transition from ferroelectric to antiferroelectric had relaxor characteristic and T_d shifted to lower temperature while increasing Bi_1/2K_1/2TiO₃ content. The best piezoelectric properties were obtained in 0.81Bi_1/2Na_1/2TiO₃-0.16Bi_1/2K_1/2TiO₃-0.03NaNbO₃ ceramic with a piezoelectric constant (d₃₃) of 146pC/N, planar electromechanical coupling factor (k_p) of 30.3% and thickness electromechanical coupling factor (k_t) of 53.2%. Abnormal piezoelectric properties were observed in the sample (x = 0.20), which was attributed to the co-existence of ferroelectric and antiferroelectric phases in it.     

钇掺杂对BSPT高温压电陶瓷铁电性能的影响

利用传统固相法制备了(1-x)Bi(Sc1-yYy)O3-xPbTiO3(BSYPT-x/y)压电陶瓷,采用XRD、SEM、压电工作站等技术表征了体系的晶体结构、微观组织及其铁电性能.发现随着PbTiO3含量的增加,BYSPT-x/y陶瓷相结构由三方结构逐渐转变为四方结构.体系的准同型相界(MPB)位置随BiYO3含量的增加而移向PbTiO3含量更低的一端.在准同型相界附近的BSYPT0.58/0.15陶瓷的电滞回线出现"束腰"现象,这种现象来源于BSYPT0.58/0.15陶瓷内部产生的正极为O2-,负极为Y3+的缺陷偶极子.     

The investigation of (Bi,La)(Ga,Fe)O3-PbTiO3 thin film prepared by PLD technique

In this report, (Bi,La)(Ga,Fe)O₃-PbTiO₃ (BLGF-PT) thin film was prepared on platinum coated Si wafer by pulsed laser deposition (PLD) method. BLGF-PT ceramic with morphotropic phase boundary (MPB) composition was used as the PLD target. The spot of Bi₂Fe₄O₉ impurity phase in X-ray diffraction profile implies a composition deviation in the BLGF-PT thin film from that of target. However, the MPB feature of co-existence of rhombohedral and tetragonal phases remains remarkable in the film. The characterization results of the leakage current and ferroelectric hysteresis loop indicate a desirable insulation in this BLGF-PT thin film. Polarization response by positive-up-negative-down pulse measurement and retention property are further carried out at room temperature to check the intrinsic ferroelectric performance. Moreover, high Curie temperature of 465 °C has been discovered in this BLGF-PT thin film, which may promote the application scope of the thin film.     

弛豫型铁电体PZNT制备与性能研究的进展

本文综述了近年来国际上弛豫型铁电体PZNT的制备与介电、压电及电致伸缩性能研究的进展．PZNT单晶体的制备方法以高温PbO熔剂法为主,其尺寸已达40mm．随PT含量的变化,PZNT的顺电一铁电相交由弥散性、混合型变为一级相变;其铁电-铁电相变可由组份或电场诱导,由介电性能表征．压电性能在MPB处及偏向三方相一侧达到最佳,＜001＞切向的三方相与四方相单晶可分别作为频带宽、分辨率高、且阻抗匹配好的新一代声阵列与单个器件传感器．＜001＞向的PZNT单晶具有巨大的电致伸缩应变,可望成为高性能的固体驱动器．     

Ferroelectric, dielectric and piezoelectric properties of Pb1?xCex(Zr0.60Ti0.40)O3, 0?≤?x?≤?0.08

The ferroelectric, dielectric and piezoelectric properties of compositions Pb_1−x Ce _x (Zr_0.60Ti_0.40)O₃, (x = 0.0, 0.01, 0.02, 0.04, 0.06 and 0.08) are studied. The above compositions are prepared from their constituent oxides, calcined at 900 °C for 4 h and various phases present are characterized by X-ray diffraction (XRD) technique. The above powders are uniaxially pressed into circular compacts, sintered at 1,250 °C for 2 h, electroded, poled at 2 kV/mm D.C. voltage and their electrical properties are measured. The XRD analysis shows the presence of rhombohedral phase up to 2 mol% ceria while tetragonal phase found at higher concentrations. It is observed that the ferroelectric, dielectric and piezoelectric properties increase with the addition of ceria with a maximum at 2 mol% and then decreases. The higher piezo properties associated with low ceria concentration are attributed to rhombohedral phase.     

Effect of Ba(Cu1/3Nb2/3)O3 content on multiferroic properties in BiFeO3 ceramics

The crystal structure, microstructural evolution, and ferroelectric and magnetic properties of BiFeO₃ (BFO) ceramic materials, widely known as room temperature multiferroic materials, were investigated with various contents of Ba(Cu_1/3Nb_2/3)O₃ (BCN). The ceramics were synthesized through the solid state reaction and pressureless sintering in air. By adding tetragonal structured BCN phase to the rhombohedral structured BFO phase, a solid solution was formed. The rhombohedral crystal structure and lattice parameter, densification behavior, and microstructure of BFO were noticeably changed upon the addition of BCB. The electrical properties of BFO were slightly enhanced by the addition of BCN. However, the magnetic properties of BFO which is the most critical issue in BFO multiferroics were drastically changed and the 20 mol% BCN added BFO ceramics showed extremely enhanced magnetization characteristics compared to the other BFO–BCN ceramics. It is expected that BFO–BCN ceramics with this composition could be one of the most promising multiferroic materials for future multiferroic applications.     

Effects of La concentration on the structural and dielectric properties of 0.57BiFeO3-0.43PbTiO3 crystalline solutions

Crystalline solutions of 0.57(Bi(1-x)La(x))FeO(3)-0.43PbTiO(3) (BLF-PT) for x = 0, 0.1, 0.2, and 0.3 were fabricated by the traditional solid state reaction method. X-ray diffraction analysis revealed that the tetragonal torhombohedral phase transformation of BLF-PT occurred with an increase of the La content. The dielectric and ferroelectric properties of BLF-PT were investigated at room temperature for different La contents. BLF-PT revealed strong ferroelectric characteristics for the lower La composition, and transferred to relaxor ferroelectrics for x 0.2. The dielectric constant and remanent polarization were 1461 and 33.5 microC/cm(2), respectively, for BLF-PT of x = 0.2. The dielectric constant and polarization of BLF-PT were enhanced simultaneously with increasing La content. Our results demonstrate that BLF-PT is a competitive piezoelectric ceramic.     

Tem analyses of the local crystal and domain structures in (Na(1-x)K(x))0.5Bi(0.5)TiO3 perovskite ceramics

The local crystal and domain structures of the ((Na(1-x)K(x))(0.5)Bi(0.5)TiO(3) (NBT-KBT) solid solutions were studied because of their influence on the enhanced electromechanical properties of ceramics. Based on X-ray diffraction, the morphotropic phase boundary (MPB) was determined for the composition x = 0.20, in which the rhombohedral and the tetragonal structures were observed to coexist. However, detailed domain-structure analyses using transmission electron microscopy (TEM), performed on the NBT, KBT, and five NBT-KBT solid-solution compositions, revealed some structural changes at/near the MPB. In the samples on the tetragonal side of the MPB, the grains showed a lamellar domain structure with 90° orientations of the individual domains, separated by straight domain boundaries, i.e., (011)/(101) twin planes. The rhombohedral samples on the other side of the MPB showed a typical square-net pattern with needle-like or lamellar ~71°/109° rhombohedral domains with (001) and/or (110) twin planes separating the individual domains. The domain structure at the MPB showed well-defined lamellar domains. Based on the occurrence of the superstructure reflections in the SAED patterns of various crystallographic zones, on the characteristic splitting of the reflections, and on the domain morphology observations, the crystal structure in/near the boundary region was determined to be a tetragonal structure with an in-phase oxygen octahedral tilt system (probably a(0)a(0)c(+)). It is suggested that the tetragonal polar order is partly induced from the rhombohedral structure at the MPB as a result of mechanical loading during TEM sample preparation.