Dielectric and piezoelectric properties of Pb(Sc1/2Nb1/2)O3–Pb(Ni1/3Nb2/3)O3–PbTiO3 ternary ceramic materials

The dielectric and electrical properties of xPb(Sc_1/2Nb_1/2)O₃–yPb(Ni_1/3Nb_2/3)O₃–zPbTiO₃ (PSNNT 100x/100y/100z) ternary ceramic materials near the morphotropic phase boundary (MPB) were investigated. The MPB follows on almost linear region between PSNNT 58/00/42 and PSNNT 00/68/32 of the binary systems. The maximum electromechanical coupling factor kp=70·7% was found at PSNNT 36/26/38, where ε₃₃^T/ε₀=3019 and Tc=210°C were obtained. These values are similar to those of the Pb(Sc_1/2Nb_1/2)O₃–Pb(Mg_1/3Nb_2/3)O₃–PbTiO₃ system and better than those of PZT.     

Large-strain 0.7Pb(ZrxTi1−x)O3–0.1Pb(Zn1/3Nb2/3)O3–0.2Pb(Ni1/3Nb2/3)O3 piezoelectric ceramics for high-temperature application

0.7Pb(Zr_xTi_1−x)O₃–0.1Pb(Zn_1/3Nb_2/3)O₃–0.2Pb(Ni_1/3Nb_2/3)O₃ (0.7PZT–0.1PZN–0.2PNN, x = 0.44–0.47) piezoelectric powders and ceramics have been prepared through conventional solid-state reaction method. Outstanding piezoelectric and dielectric properties occurred at the morphotropic phase boundary (MPB), which was characterized by the X-ray diffraction spectrum. The MPB composition (x = 0.46) performed high d₃₃ value (641 pC/N), indicating that the system suited large-strain application. The field-induced strain reached 0.25% under a considerably low electric field (0.8 kV/mm) according to the bipolar strain *S–E loops. The effect of the grain size on the aging phenomenon and temperature stability has also been investigated. Due to higher Curie temperature and smaller grain size, the 0.7PZT–0.1PZN–0.2PNN ceramics maintained a high d₃₃ level after depoling treatment, revealing a superior strain capacity for high-temperature application.     

Relaxation behavior in 0.24Pb(In1/2Nb1/2)O3–0.49Pb(Mg1/3Nb2/3)O3–0.27PbTiO3 ferroelectric single crystal

Dielectric relaxation properties of the ternary relaxor-based ferroelectric 0.24Pb(In_1/2Nb_1/2)O₃–0.49Pb(Mg_1/3Nb_2/3)O₃–0.27PbTiO₃ single crystal have been investigated as a function of temperature (300–570 K) in the frequency range from 100 Hz to 100 kHz. It was found that the variation of the permittivity maximum temperature T_m with frequency obeys the Vogel–Fulcher relationship. The high-temperature (T>T_m) side of the dielectric permittivity deviated from the Curie–Weiss law, but can be described by the Lorenz-type relationship. The coercive field obtained from the polarization hysteresis loops gradually decreases with increasing temperature, and the remnant polarization persists above T_m due to the existence of polar nanoregions (PNRs).     

Crystal structure and piezoelectric properties of xPb(Mn1/3Nb2/3)O3–(0.2 − x)Pb(Zn1/3Nb2/3)O3–0.8Pb(Zr0.52Ti0.48)O3 ceramics

Pb(Mn_1/3Nb_2/3)O₃–Pb(Zn_1/3Nb_2/3)O₃–Pb(Zr_0.52Ti_0.48)O₃ (designated as PMnN–PZN–PZT) piezoelectric ceramics were prepared and the effects of PMnN content on the crystal structure and electrical properties were investigated. The results show that the pure perovskite phase forms in these ceramics. The crystal structure changes from tetragonal to rhombohedral and the lattice constant decreases with increase of PMnN content. The morphotropic phase boundary (MPB) of xPMnN–(0.2 ? x)PZN–0.8PZT ceramics occurs where the content of PMnN, x, lies between 0.05 and 0.085 mol. The dielectric constant (?), piezoelectric constant (d₃₃) and Curie temperature (T_c) decrease, while the mechanical quality factor (Q_m) increases with the increase of PMnN content. The ceramic with composition 0.075PMnN–0.125PZN–0.8PZT has the optimal piezoelectric properties, ? is 842, d₃₃ is 215 pC/N, T_c is 320 °C, k_p is 0.57 and Q_m amounts to 1020, which makes it a promising material for high power piezoelectric devices.     

Electrophoretic deposition of Pb(Ni1/3Nb2/3)O3–Pb(Zr,Ti)O3 thick film on Pt wire

0.2PbNi_1/3Nb_2/3–0.8Pb(Zr,Ti)O₃ (PNN–PZT) thick films were deposited on Pt wire with the diameter of 50 μm by electrophoretic deposition (EPD) method. The EPD deposition times on the microstructures of PNN–PZT thick films were investigated. By optimizing the EPD process, the Pt wire can be uniformly wrapped with the PNN–PZT powders. During the sintering process, the as-deposited PNN–PZT/Pt wires were buried in the mixed powders of PbCO₃ and ZrO₂, and then sintered in the optimal temperature to get a dense microstructure. The piezoelectric properties of the thick films were characterized by scanning force microscopy (SFM) method. The results show that the PNN–PZT thick films prepared by EPD method have good piezoelectricity.     

Effect of Ba(Zn1/3Nb2/3)O3 modification on structure and ferroelectric properties of 0.6Pb(Mg1/3Nb2/3)O3–0.4Pb(Zr0.52Ti0.48)O3 ceramics

In this study, (1−x)[0.6Pb(Mg_1/3Nb_2/3)O₃–0.4Pb(Zr_0.52Ti_0.48)O₃]–xBa(Zn_1/3Nb_2/3)O₃; (1−x)PMNZT60/40–xBZN having x=0, 2.5, 5, 7.5, and 10 mol% ceramics were prepared by mixed oxide powder method and sintered using a two-step process. Phase transitions were investigated by XRD, microstructure by SEM, crystal morphology by TEM, the dielectric and ferroelectric properties by capacitance measurement setup and modified Sawyer-Tower circuit, respectively. The dielectric constant and dielectric loss tangent were measured as functions of both temperature and frequency. The XRD results show the phase transition from tetragonal phase to pseudo-cubic phase with addition of BZN in PMNZT system. Grain size of about 1.23–2.42 μm and crystallite size in a range of 421–2152 nm were obtained. The pure-phase 0.6PMN–0.4PZT ceramics show the normal ferroelectric behavior. The 0.95(PMNZT60/40)–0.05BZN and 0.925(PMNZT60/40)–0.075BZN showed a broad and diffused dielectric properties and the dispersive phase transition, indicating the relaxor ferroelectric behavior. The transition temperature in the BZN-modified PMNZT system is seen to decrease from 166 °C in pure PMNZT60/40 to 102 °C and 54 °C with increasing BZN content to 5 and 10 mol%, respectively. In addition, the maximum dielectric constant is decreased with increasing BZN content. The P–E hysteresis loop measurements show the change from the normal ferroelectric behavior in PMNZT60/40 ceramic to more relaxor behavior that was induced with BZN addition. These results clearly demonstrated the significance of BZN to the electrical responses of the PMNZT60/40 system.     

Temperature–field phase diagrams in Pb(Zn1/3Nb2/3)O3–4.5%PbTiO3 II

Temperature and field dependences of the dielectric constants under the DC biasing fields along the [011]- and [111]-directions in the cubic coordinate in Pb(Zn_1/3Nb_2/3)O₃–4.5%PbTiO₃ were investigated. The temperature–field phase diagrams were constructed in the field range below 10 kV/cm. It was confirmed that in Pb(Zn_1/3Nb_2/3)O₃–4.5%PbTiO₃ the intermediate tetragonal phase as a ground state of the system exists even without the DC field, and the tetragonal phase disappears in the external field above 4 and 3 kV/cm along the [011]- and [111]-directions, respectively. The field-induced orthorhombic-phase in the field along the [011]-direction was also found.     

A new multiferroic ternary solid solution system: NdFeO3–Pb(Fe1/2Nb1/2)O3–PbTiO3

Ceramic materials were sintered from powders of the NdFeO₃–Pb(Fe_1/2Nb_1/2)O₃–PbTiO₃ (NF–PFN–PT) ternary system synthesized by the conventional solid reaction method and their multiferroic properties investigated. The structure, electric and magnetic properties of the ternary system have been investigated. The introduction of Pb(Fe_1/2Nb_1/2)O₃ into the NdFeO₃–PbTiO₃ binary system can effectively increase its electric properties. The ternary system exhibits enhanced piezoelectric property with optimal piezoelectric constants d₃₃=143 pC/N, reduced coercive fields E_C=5.78 kV/cm and remnant polarization P_r=12.8 μC/cm² for 0.10NF–0.56PFN–0.34PT, near tetragonal phase region. The Curie temperature (T_C) of the NdFeO₃–Pb(Fe_1/2Nb_1/2)O₃–PbTiO₃ ceramics varies in the range from 108.7 °C to 67.9 °C. The magnetic hysteresis loops show that the ternary system is paramagnetic originating from canting of paramagnetic sublattices in NF–PFN–PT, due to the rare earth ions Nd³⁺ influencing on the exchange interaction between Fe³⁺ ions at the octahedral sites.     

Multilayer 0.9Pb(Mg1/3Nb2/3)O3–0.1PbTiO3 elements for electrocaloric cooling

Electrocaloric (EC) cooling elements in the form of multilayers (MLs) were prepared. The elements consist of five layers of the relaxor-ferroelectric 0.9Pb(Mg_1/3Nb_2/3)O₃–0.1PbTiO₃, about 60 μm thick, with internal platinum electrodes and exhibiting a dense, uniform microstructure with a grain size of 1.7 μm. The largest temperature change ΔT_EC of 2.26 K was achieved at an electric field (E) of 100 kV cm⁻¹ and at 105 °C, measured by a high-resolution calorimeter. These results agree well with the indirect measurements. The EC coefficient, ΔT_EC/ΔE, obtained for the MLs, is similar to the value obtained for bulk ceramics of the same composition. The ΔT_EC values above 2 K over a broad temperature range from 75 to 105 °C make the ML elements suitable candidates for EC cooling devices at significantly lower voltages than bulk ceramic plates with comparable dimensions and mass.     

Effects of microstructure on the microwave dielectric properties of Ba(Co1/3Nb2/3)O3 and (1−x)Ba(Co1/3Nb2/3)O3–xBa(Zn1/3Nb2/3)O3 ceramics

Ba(Co_1/3Nb_2/3)O₃(BCN) has a 1:2 ordered hexagonal structure. A large amount of the liquid phase, which contains high concentrations of Ba and Nb ions was found in the BCN ceramics. Q-values of BCN increased with increasing sintering temperature; however, it significantly decreased when the sintering temperature exceeded 1400 °C. The presence of a large amount of liquid phase could be responsible for the decrease of the Q-value. For (1−x)Ba(Co_1/3Nb_2/3)O₃–xBa(Zn_1/3Nb_2/3)O₃ [(1−x)BCN–xBZN] ceramics, the 1:2 ordered hexagonal structure was observed in the specimens with x⩽0.3 and the BaNb₆O₁₆ second phase was found in the specimens with x⩾0.6. Grain growth, which is related to the BaNb₆O₁₆ second phase occurred in the specimens with x⩾0.5. In this work, the excellent microwave dielectric properties of τ_f=0.0 ppm/°C, ε_r=34.5 and Q×f=97,000 GHz were obtained for the 0.7BCN–0.3BZN ceramics sintered at 1400 °C for 20 h.     

Domain structure and evolution in ZnO-modified Pb(Mg1/3Nb2/3)O3–0.32PbTiO3 ceramics

The doping of ZnO is efficient to improve the piezoelectric property and thermal stability of Pb(Mg_1/3Nb_2/3)O₃–PbTiO₃ (PMN–PT) based ceramics. However, the underlying physics, especially the local domain structures of the ZnO modified PMN–PT ceramics, which is strongly associated with the electric properties, is not clear yet. In this paper, we investigated the local domain structures and their evolution as a function of x in PMN–0.32PT:xZnO ceramics. It was found that, the domain evolution is mainly caused by the growth of grain size induced by the sintering aiding effect of ZnO at x < 0.04, and the domain evolution can be attributed to the phase transition induced by the partial replacement of Mg²⁺ by Zn²⁺ in the B-site of PMN–PT lattice at x > 0.06. Furthermore, we also investigated the domain structure evolution as functions of temperature and local external electric field in PMN–0.32PT:0.06ZnO ceramics, which exhibited superior piezoelectric property relative to other compositions. We found that the irregular nanodomains are more stable at high-temperature range, and the regular non-180° domains exhibited more complex rotation behavior under local electric field, which probably leads to the thermal stability and piezoelectric property enhancement in the ZnO-modified PMN–0.32PT ceramics.     

Characterization of 0.93Pb(Zn1/3Nb2/3)O3–0.07BaTiO3 ceramics derived from a novel Zn3Nb2O8 B-site precursor

In this work, perovskite relaxor ferroelectric lead zinc niobate–barium titanate (0.93PZN–0.07BT) ceramics were fabricated by using a combination of Zn₃Nb₂O₈ B-site precursor and reactive sintering process. The effects of sintering condition on phase formation, densification, microstructure and dielectric properties of the final products have been investigated using a combination of X-ray diffraction, Archimedes density measurement, scanning electron microscopy and dielectric measurement techniques. It is seen that pure perovskite phase of PZN-BT solid solutions can be achieved in all samples. Density and average grain size values of sintered samples increased with sintering temperatures and dwell time. With appropriate sintering at 1150 °C for 5 h, 0.93PZN–0.07BT ceramics exhibited a peak dielectric constant of 11,497 and dielectric loss of 0.05 at the Curie temperature of 99 °C measured at 1 kHz.     

Dielectric behaviors of Nb2O5–Co2O3 doped BaTiO3–Bi(Mg1/2Ti1/2)O3 ceramics

Nb₂O₅ and Nb–Co doped 0.85BaTiO₃–0.15Bi(Mg_1/2Ti_1/2)O₃ (0.85BT–0.15BMT) ceramics were investigated. From XRD patterns, undesired phase was observed when the (Nb₂O₅/Nb-Co) doping levels exceed 3 wt.%/2 wt.%, giving rise to the deteriorate dielectric constant. The 0.85BT–0.15BMT ceramics doped with 2 wt.%Nb₂O₅ was found to possess a moderate dielectric constant (? ～ 1000) and low dielectric loss (tan δ = 0.9%) at room temperature and 1 kHz, showing flat dielectric behavior over the temperature range from ?55 to 155 °C. It was found that the formation of core–shell structure in the BT based ceramics is controlled by the doping sequence of Nb- and Bi-oxides.     

Sm掺杂Pb(Mg1/3Nb2/3)O3-PZT压电陶瓷的研究

本文通过一步反应合成法制备了铌镁-锆钛酸铅(Pb(Mg_1/3Nb_2/3)O₃-Pb(Zr,Ti)O₃,PMN-PZT)压电陶瓷,研究了稀土元素钐(Sm)掺杂对PMN-PZT(x%(摩尔分数)Sm-PMN-PZT)结构与电学性能的影响规律,得到了具有高压电性、高机电耦合系数和高居里温度的压电陶瓷。当x=2.0时,压电常数d₃₃=611 pC/N,机电耦合系数k_p=0.68,介电损耗tan δ=1.65%,相对介电常数ε_r=2 650,居里温度T_C=283 ℃。测试压电陶瓷电致应变性能,在3 kV/mm下单极电致应变达到0.20%,显示出其大应变材料的特征。结果表明,Sm掺杂PMN-PZT压电陶瓷具有优异的综合电学性能,有望在换能器、传感器以及致动器等领域广泛应用。     

Modified Pb(Mg1/3Nb2/3)O3-PbZrO3–PbTiO3 ceramics with high piezoelectricity and temperature stability

There is a great demand to develop ferroelectric ceramics with both high piezoelectric coefficient and broad temperature usage range for emerging electromechanical applications. Herein, a series of Sm³⁺-doped 0.25Pb(Mg_1/3Nb_2/3)O₃-(0.75−x)PbZrO₃-xPbTiO₃ ceramics were fabricated by solid-state reaction method. The phase structure, dielectric and piezoelectric properties were investigated, where the optimum piezoelectric coefficient d₃₃ = 745 pC/N and electromechanical coupling factor k₃₃ = 0.79 were obtained at the morphotropic phase boundary composition x = 0.39, with good Curie temperature T_C of 242°C. Of particular importance is that high-temperature stability of the piezoelectric and field-induced strain was obtained over the temperature range up to 230°C for the tetragonal compositions of x = 0.40. The underlying mechanism responsible for the high piezoelectricity and temperature stability is the synergistic contribution of the MPB and local structural heterogeneity, providing a good paradigm for the design of high-performance piezoelectric materials to meet the challenge of piezoelectric applications at elevated temperature.     

添加剂对Ba(Zn1/3Nb2/3)O3-Sr(Zn1/3Nb2/3)O3陶瓷介电性能的影响

研究了MnCO3,BaZrO3对0.35Ba(Zn1/3Nb2/3)O3(BZN)-0.65Sr(Zn1/3Nb2/3)O3(SZN)陶瓷介电性能的影响.研究表明:添加MnCO3,BaZrO3时,对陶瓷的烧结均起促进作用,增大介电常数.加入1%(质量分数)的MnCO3可使陶瓷具有较小的介质损耗,同时MnCO3对陶瓷的介电常数温度系数具有正向调整作用.加入BaZrO3后通过生成液相而减少了第二相Ba5Nb4O15,BaNb2O6的生成.所制备的(0.35BZN0.65SZN)+0.1%MnCO3陶瓷的εr≈43.6,αe≈-8×10-6/K,tanδ＝0.6×10-4,且烧结温度低于1 300℃.     

A new Pb(Lu1/2Nb1/2)O3–PbZrO3–PbTiO3 ternary solid solution with morphotropic region and high Curie temperature

A ceramic ternary system of (1?x?y)Pb(Lu_1/2Nb_1/2)O₃–xPbZrO₃–yPbTiO₃ (PLuN–PZ–PT) has been prepared by two-step synthetic process and characterized by X-ray powder diffraction and electric measurements. A morphotropic phase boundary (MPB) region has been delimited in the ternary system at room temperature. With the PLuN content increasing, the morphotropic phase boundary region becomes broad as well as the dielectric peak. The best comprehensive piezoelectric properties were achieved at MPB composition 0.42PLuN–0.1PZ–0.48PT, with the piezoelectric coefficients d₃₃, the Curie temperature T_c, the planar electromechanical coupling factor K_p, and the remnant polarizations P_r being 367 pC/N, 360 °С, 68% and 35 μС/cm², respectively. The results indicate that the PLuN–PZ–PT ternary ferroelectric material may be a promising candidate for high-power electromechanical transducers that can operate in a large temperature range.     

Piezoelectric properties of highly densified 0.01Pb (Mg1/2W1/2)O3–0.41Pb (Ni1/3Nb2/3)O3–0.35PbTiO3–0.23PbZrO3+0.1 wt% Y2O3+1.5 wt% ZnO thick films on alumina substrate

This paper reports on the formation of highly densified piezoelectric thick films of 0.01Pb(Mg_1/2W_1/2)O₃–0.41Pb(Ni_1/3Nb_2/3)O₃–0.35PbTiO₃–0.23PbZrO₃+0.1 wt% Y₂O₃+1.5 wt% ZnO (PMW–PNN–PT–PZ+YZ) on alumina substrate by the screen-printing method. To increase the packing density of powder in screen-printing paste, attrition milled nano-scale powder was mixed with ball milled micro-scale powder, while the particle size distribution was properly controlled. Furthermore, the cold isostatic pressing process was used to improve the green density of the piezoelectric thick films. As a result of these processes, the PMW–PNN–PT–PZ+YZ thick film, sintered at 890 °C for 2 h, showed enhanced piezoelectric properties such as P_r=42 μC/cm², E_c=25 kV/cm, and d₃₃=100 pC/N, in comparison with other reports. Such prominent piezoelectric properties of PMW–PNN–PT–PZ+YZ thick films using bi-modal particle distribution and the CIP process can be applied to functional thick films in MEMS applications such as micro actuators and sensors.     

部分草酸盐工艺制备Pb(Mg1/3Nb2/3)O3-PbTiO3铁电陶瓷

通过部分草酸盐工艺制备了颗粒尺寸较小、粒度分布较均匀、团聚较少的(1-x)Pb(Mg1/3Nb2/3)O3-xPbTiO3(PMN-PT)前驱体.以活性PMN-PT前驱体为原料,通过固相反应法制备PMN-PT陶瓷.XRD测量表明,通过部分草酸盐工艺制备的PMN-PT陶瓷中含有少量的焦绿石相.随着PbTiO3 (PT)含量的增加,PMN-PT陶瓷的晶体结构从三方铁电相逐渐向四方铁电相转变.烧成的PMN-PT陶瓷具有较高的致密度.组分和烧结温度对PMN-PT陶瓷的电学性能产生影响.随着烧结温度的升高,PMN-PT陶瓷的介电常数最大值εm增大,伴随着εm对应的温度Tc/Tm的不规律变化;剩余极化强度Pr增大,矫顽场Ec减小;压电应变常量d33值增大.随着PT含量的增加,Tc/Tm增大,介电响应特征从弥散型铁电相变向正常铁电相变转变,电滞回线从狭长的回线向接近矩形的形状转变.0.68PMN-0.32PT陶瓷呈现优良的综合电学性能,1200℃烧结的陶瓷1kHz时εm为14070,Tm为148.2℃,d33值为457pC/N,Pr为14.69μC/cm2,Ec为4.72kV/cm.