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。     

Temperature dependence of electrical and electromechanical properties of Pb(Mg1/3Nb2/3)O3–Pb(Ni1/3Nb2/3)O3–Pb(Zr,Ti)O3 thin films

The electrical and electromechanical properties of Pb(Mg_1/3Nb_2/3)O₃–Pb(Ni_1/3Nb_2/3)O₃–Pb(Zr,Ti)O₃ (PMN–PNN–PZT, PMN/PNN/PZT = 20/10/70) on Pt/Ti/SiO₂/Si substrates by chemical solution deposition was investigated. The PMN–PNN–PZT films annealed at 650 °C exhibited slim polarization hysteresis curves and a high dielectric constant of 2100 at room temperature. A broad dielectric maximum at approximately 140–170 °C was observed. The field-induced displacement was measured by scanning probe microscopy, the bipolar displacement was not hysteretic, and the effective piezoelectric coefficient (d₃₃) was 66 × 10⁻¹² m/V. The effective d₃₃ decreased with temperature, but the value at 100 °C remained 45 × 10⁻¹² m/V.     

0.06BiYbO3-0.94Pb(Zr0.48Ti0.52)O3三元系压电陶瓷的氧化物掺杂改性研究

针对新一代声波测井仪器对其核心元件压电陶瓷兼具高居里温度、高压电系数以及高稳定性要求的迫切需求,本文采用传统的固相反应-无压烧结技术制备了一种0.06BiYbO₃-0.94Pb(Zr_0.48Ti_0.52)O₃(BY-PZT)三元系压电陶瓷,并研究了四种氧化物掺杂对其微观结构及电学性能的影响。由XRD和SEM表征可知所有样品均呈纯四方相钙钛矿结构,掺杂Cr₂O₃的样品平均晶粒尺寸最大。介电温谱和谐振频谱研究证实四种氧化物掺杂均能提高其介电性能的温度稳定性。掺杂La₂O₃的样品介电常数温度系数(Tk_ε)最低,掺杂MnO₂的样品机械品质因素(Q_m)最高,而掺杂CeO₂的样品抗热退极化性能最好。高温复阻抗(Cole-Cole图)分析表明,Cr₂O₃掺杂能够显著提高BY-PZT陶瓷的高温电阻率,陶瓷在高温下的电导行为主要由晶界响应控制。综合来看,掺杂La₂O₃的样品兼具高居里温度(T_C=397 ℃)和高压电系数(d₃₃=290 pC/N),并且在300 ℃退火4 h后d₃₃仍能保持在270 pC/N左右,有望在极限工作温度为300 ℃的高温压电器件中获得应用。     

0-3型压电陶瓷/硫铝酸盐水泥复合材料的介电性能和压电性能

用压制成型法，以水泥为基体，铌镁锆钛酸铅(lead magnesium niobate-lead zireonate-lead titanate，PMN)陶瓷颗粒为功能体制备了水泥基压电复合材料。分析讨论了复合材料的压电性能和介电性能。研究了水泥水化龄期对复合材料压电性能的影响，并对其机理进行了初探。结果表明：随着PMN含量的增加，压电复合材料的压电应变常数d33和介电常数均增大；不像压电陶瓷或压电复合材料的压电性能随时问的延长而减弱，水泥基压电复合材料的压电性则是随着水泥水化龄期的延长而增加，当到达一定龄期后，压电性能趋于稳定。     

Properties 0–3 PZT–Portland cement composites

Smart structural composites are multifunctional structural materials which can perform functions such as sensing strain, vibration reduction and are essential because of their relevance to mitigation and structural vibration control. Cement-based piezoelectric composites have been developed as smart structural composites. The goal of this work is to produce cement-based piezoelectric composites using lead zirconate titanate (PZT) and Portland cement (PC) with xPZT–(1 − x)PC (where x = 0.3, 0.6 and 0.9). The composites were pressed together and cured in 100% RH curing chamber for 3 days before measurements. Dielectric constant (_r) at room temperature and piezoelectric coefficient (d₃₃) of the 0–3 piezoelectric PZT–Portland cement composites with different PZT content were investigated. The results show these composites have _r and d₃₃ values of up to 536 and 87 pC/N, respectively, and there is a good potential for the application of these cement-based piezoelectric composites in civil engineering.     

碳纤维增强BT-HA复合材料的制备与性能

目前,人工骨由于力学性能不佳在应用上受到极大的限制,因此,如何在保证人工骨具有压电性能和生物性能的前提下提高其力学性能成为了研究热点。本文以钛酸钡-羟基磷灰石(BT-HA)复合材料为基体,质量分数为5%的碳纤维(C_f)作为增强体,利用传统固相烧结法制备了C_f/BT-HA复合材料,目的是在保证电学性能不变的前提下提高复合材料的力学性能。结果表明,BT-HA复合材料中加入C_f后,电学性能基本保持不变,力学性能得到了很大的提升。样品具有较好的铁电性,压电常数d₃₃为37 pC/N,居里温度为170 ℃,高于人工骨的使用温度。抗弯强度达到121.7 MPa,硬度达到3.56 GPa,均增大到未加C_f样品的3倍,断裂韧性增加了1倍,达到1.21 MPa·m^1/2。C_f/BT-HA复合材料没有细胞毒性且骨诱导性良好,有望应用于骨替代材料领域。     

Synthesis and properties of Bi0.5(Na1−x−yKxAgy)0.5TiO3 lead-free piezoelectric ceramics

Bi_0.5(Na_1−x−yK_xAg_y)_0.5TiO₃ piezoelectric ceramics were prepared by conventional ceramic processes. X-ray diffraction patterns show a pure perovskite structure, indicating that the K⁺ and Ag⁺ ions substitute for the Na⁺ ions in Bi_0.5Na_0.5TiO₃. The temperature dependence of the dielectric constant and dissipation factor shows all ceramics to experience two phase transitions: from ferroelectric to anti-ferroelectric and from anti-ferroelectric to paraelectric. The transition temperature from ferroelectric to anti-ferroelectric and the temperature at which the dielectric constant reaches its maximum value decrease with the increase of K⁺ amount. At room temperature, the ceramics containing 17.5–20 mol% K⁺ and 2 mol% Ag⁺ exhibit high piezoelectric constant (d₃₃ = 180 pC/N) and high electromechanical coupling factor (k_p = 35%).     

镧掺杂PMN-PT陶瓷在准同型相界处的相组成调控

采用两步预烧工艺制备Pb_{0.962 5}La_0.025(Mg_1/3Nb_2/3)_1-zTi_zO₃(z=0.28、0.29、0.30、0.31)陶瓷,其准同型相界(MPB)的化学组成位于PbTiO₃含量为0.29 mol和0.30 mol附近。选取准同型相界两侧的化学组成,制备四方晶相Pb(Mg_1/3Nb_2/3)_0.66Ti_0.34O₃和三方晶相Pb_1-1.5xLa_x(Mg_1/3Nb_2/3)_1-yTi_yO₃(x=0.083 3~0.041 7,y=0.206 7~0.273 3)陶瓷粉体。将两种晶相粉体按照设计比例(三方晶相摩尔分数w=0.3、0.4、0.5、0.6)混合,干压成型,烧结成化学组成相同、晶相占比不同的Pb_{0.962 5}La_0.025(Mg_1/3Nb_2/3)_0.70Ti_0.30O₃陶瓷。研究了晶相组成对陶瓷压电性能、介电性能、铁电性能的影响。结果表明,高温烧结后,陶瓷中的三方晶相和四方晶相占比与配料比基本一致。当w=0.5时,1 250 ℃烧结陶瓷中三方晶相与四方晶相含量占比分别为0.47、0.53,晶粒平均尺寸为(5.24±0.23) μm,相对密度为96.76%。陶瓷的压电应变常数d₃₃、径向机电转换系数k_p、厚度机电转换系数k_t、相对介电常数ε_r、剩余极化强度P_r和场致应变系数S(1 Hz、3.5 kV/mm)分别为1 014 pC/N、0.67、0.64、10 955、24 μC/cm²和0.21%。该方法可人为调控化学组成位于准同型相界的陶瓷的晶相占比。     

Electromechanical coupling coefficient and acoustic impedance of 1-1-3 piezoelectric composites

1-1-3 piezoelectric composites consisting of a PZT-5H ceramic, an epoxy resin matrix and a silicone rubber filler were prepared using a modified 'slice and fill' method. The effect of the ceramic volume percentage on the properties of the composite was analyzed both through experiments and simulations. By adopting the 1-1-3 structure, the electromechanical coupling coefficient of the piezoelectric composites could be increased to 0.69, and the acoustic impedance reduced to 6.81. The experimental results further showed that the variation of the ceramic volume percentage had no effect on the electromechanical coupling coefficient of the composites, but only affected the acoustic impedance. The presented piezoelectric composites can be used to design high-performance transducer.     

Fe2O3原料的预处理对0.7BiFeO3-0.3BaTiO3陶瓷绝缘性与电性能的影响

BiFeO₃基无铅压电陶瓷常因漏电流较大而压电性能欠佳,然而,改善其绝缘性和电性能的方法都较为复杂,限制了其产业化生产与应用。本工作在不针对0.7BiFeO₃-0.3BaTiO₃陶瓷进行组分掺杂以及气氛烧结的条件下,仅通过简单的原料预处理(改变Fe₂O₃原料的干燥时间)即实现了其高绝缘性与高压电性能。研究结果表明,0.7BiFeO₃-0.3BaTiO₃陶瓷的晶粒尺寸和绝缘性随Fe₂O₃原料干燥时间的增加而增大,同时其电性能及温度稳定性也随之增强。当原料干燥时间为192 h时,样品晶粒尺寸最大,绝缘性最好,同时其压电性能(d₃₃=203 pC/N,k_p=0.33)和居里温度(T_c=460 ℃)也达到最佳。这为今后BiFeO₃基陶瓷压电性能的研究提供了一个新思路。     

Influence of isovalent and aliovalent substitutions at Ti site on bismuth sodium titanate-based compositions on piezoelectric properties

The effect of isovalent and aliovalent substitutions in Bi_0.5Na_0.485La_0.005TiO₃ (BNLT) compounds were studied within the additive ranges of 0–2.5 at%. The Zr⁴⁺, Nb⁵⁺ and Fe³⁺ ions were selected as the substituents. The modified BNLT compounds were prepared by conventionally mixed-oxide method. The calcination and sintering were performed at the temperatures of 750–850 °C and 1050–1150 °C, respectively. An increase in the substituents contents affected the physical and piezoelectric properties. The BNLT compositions with the addition of 1 at% Zr⁴⁺, Nb⁵⁺ and Fe³⁺ ions exhibited high relative permittivities (_r) at 730, 735 and 660, respectively. The modified-BNLT with an addition of 1.0 at% Fe provided a piezoelectric coefficient (d₃₃) of 155 pC/N, Curie temperature (T_c) of 320 °C and electromechanical coupling factors in planar (k_p) and thickness (k_t) modes of 15 and 45%, respectively.     

Effects of addition of Pb(Y1/2Nb1/2)O3 (PYN) on microstructure and piezoelectric properties of Pb(Zr0.53Ti0.47)O3

Pure and Pb(Y_1/2Nb_1/2)O₃ (PYN)-doped Pb(Zr_0.53Ti_0.47)O₃ have been characterized. The samples were prepared by conventional mixed-oxide ceramic technology. PYN dopant was added to PZT at content levels ranging from 1 to 2.5 mol%. The microstructures of the samples were examined using SEM and TEM. The average grain size was observed to decrease as the dopant content increased. Herringbone-like and wedge-shaped domain patterns were observed in all the samples. The piezoelectric properties of PZT were greatly improved by the addition of PYN. The highest piezoelectric constant d₃₁ was nearly twice that of pure PZT.     

Design,fabrication and properties of 1–3 piezoelectric ceramic composites with varied piezoelectric phase distribution

Here the 1–3 connectivity cement/polymer based piezoelectric composites with varied piezoelectric phase distribution were designed. The dielectric, piezoelectric and electromechanical properties of the composites were studied. The results indicate that the composite with varied distribution of piezoelectric ceramic has large relative permittivity, piezoelectric strain constant and electromechanical coupling coefficient at the thickness vibration mode. The composites with varied distribution of matrix phase have larger piezoelectric voltage constant, smaller mechanical quality factor and acoustic impedance value than those with varied distribution of piezoelectric ceramic phase. The electromechanical coupling property of the composites at the planar vibration mode shows obvious dependence on matrix phase distribution. The novel piezoelectric composites show potential applications in fabricating ultrasonic transducers with specific surface vibration amplitude.     

Piezoelectric properties of low temperature sintering in Pb(Zr,Ti)O3–Pb(Zn,Ni)1/3Nb2/3O3 ceramics for piezoelectric transformer applications

In this study, in order to develop low-temperature sintering ceramics for a multilayer piezoelectric transformer application, we explored CuO and Bi₂O₃ as sintering aids at low temperature (900 °C) sintering condition for Sb, Li and Mn-substituted 0.8Pb(Zr_0.48Ti_0.52)O₃–0.16Pb(Zn_1/3Nb_2/3)O₃–0.04Pb(Ni_1/3Nb_2/3)O₃ ceramics. These substituted ceramics have excellent piezoelectric and dielectric properties such as d₃₃  347 pC/N, k_p  0.57 and Q_m  1469 when sintered at 1200 °C. The addition of CuO decreased the sintering temperature through the formation of a liquid phase. However, the piezoelectric properties of the CuO-added ceramics sintered below 900 °C were lower than the desired values. The additional Bi₂O₃ resulted in a significant improvement in the piezoelectric properties. The composition Sb, Li and Mn-substituted 0.8Pb(Zr_0.48Ti_0.52)O₃–0.16Pb(Zn_1/3Nb_2/3)O₃–0.04Pb(Ni_1/3Nb_2/3)O₃ + 0.5 wt% CuO + 0.5 wt% Bi₂O₃ showed the value of k_p = 0.56, Q_m = 1042 (planar mode), d₃₃ = 350 pC/N, when it was sintered at 900 °C for 2 h. These values indicated that the newly developed composition might be suitable for multilayer piezoelectric transformer application.     

织构PNN-PZT陶瓷的光固化成型制备及其电学性能研究

为高效制备织构压电陶瓷,以球状Pb(Ni_1/3Nb_2/3)O₃-PbZrO₃-PbTiO₃ (PNN-PZT) 为基体粉体,片状BaTiO₃ （BT）为模板粉体,采用光固化成型技术代替传统流延技术制备织构压电陶瓷。研究了粉体形貌对打印浆料流动性的影响、浆料的光敏参数以及不同BT含量织构陶瓷的晶体结构和电学性能。结果表明,球状粉体浆料具有低黏度的特性,能够有效提高打印浆料的固含量,最大固含量可达86%（质量）。此时陶瓷浆料的临界曝光量与透射深度分别为127.5 mJ/cm²和21.1 μm。打印后的PNN-PZT-BT陶瓷沿[00l]_c方向生长,BT模板粉体含量从1%增长到5%,陶瓷的织构度由42%增到92%。当BT含量为3%时,样品具有最高的压电常数d₃₃=1047 pC/N。与传统的流延法相比,SLA技术的工艺优势在于制备周期短,稳定性高,能够有效降低织构陶瓷的制备难度。     

织构PNN-PZT陶瓷的光固化成型制备及其电学性能研究

为高效制备织构压电陶瓷,以球状Pb(Ni_1/3Nb_2/3)O₃-PbZrO₃-PbTiO₃ (PNN-PZT) 为基体粉体,片状BaTiO₃ （BT）为模板粉体,采用光固化成型技术代替传统流延技术制备织构压电陶瓷。研究了粉体形貌对打印浆料流动性的影响、浆料的光敏参数以及不同BT含量织构陶瓷的晶体结构和电学性能。结果表明,球状粉体浆料具有低黏度的特性,能够有效提高打印浆料的固含量,最大固含量可达86%（质量）。此时陶瓷浆料的临界曝光量与透射深度分别为127.5 mJ/cm²和21.1 μm。打印后的PNN-PZT-BT陶瓷沿[00l]_c方向生长,BT模板粉体含量从1%增长到5%,陶瓷的织构度由42%增到92%。当BT含量为3%时,样品具有最高的压电常数d₃₃=1047 pC/N。与传统的流延法相比,SLA技术的工艺优势在于制备周期短,稳定性高,能够有效降低织构陶瓷的制备难度。     

Properties of CNTs-modified lead-free BCTS ceramic–Portland fly ash cement composites

Fly ash (FA) is widely used as a supplementary cementitious material in the production of Portland cement concrete. The effect of addition of carbon nanotubes (CNTs) and FA on the properties of barium calcium stannate titanate (BCTS) ceramic–Portland FA cement composites was investigated. These composites have potential for use as sensors and transducers in the monitoring of structural health in concrete structures containing FA. CNTs were found to have filled the pores of the composites. All composites showed good compatibility with the concrete mix. The dielectric constant and electrical conductivity of composites were in the range 200–257 and 1.04 × 10^–6 to 1.66 × 10⁻⁶ S/m, respectively. The presence of FA in composites increased the piezoelectric voltage coefficient (g₃₃). Adding CNTs increased the piezoelectric charge coefficient (d₃₃), thickness electromechanical coupling coefficient (K_t), and also g₃₃ but decreased mechanical quality factor (Q_m), which is related to good for the receiving sensor and transducer application. CNTs can improve the properties of these composites and composite with FA content at 10 vol.%, and CNTs at 1 vol.% exhibited the highest compressive strength and piezoelectric values (d₃₃ = 44 pC/N, g₃₃ = 20.21×10^–3 V m/N, and K_t = 18.9%), along with higher g₃₃ values, than pure BCTS ceramic.     

Metal–Ceramic Composite Actuators

A new type of actuator composed of metal (brass) end caps and piezoelectric ceramics has been developed as a displacement transducer. Shallow cavities positioned between the metal caps and the central ceramic disk convert and amplify the radial displacement of the piezoelectric ceramic into a large axial motion of the metal end caps. Large d ₃₃ coefficients exceeding 2500 pC/N are obtained with the composite actuators. The behavior of the electrically induced strain with geometric variables, such as the thickness of the metal end caps, and with pressing force and driving frequency has been evaluated. Sizeable strains are obtained with both PZT (piezoelectric lead zirconate titanate) and PMN (electrostrictive lead magnesium niobate) ceramics.     

Piezoelectric and Dielectric Properties of Acrylonitrile Butadiene Rubber/Lead Magnesio-Niobate Piezoelectric Ceram

A new composite with special piezoelectric property was prepared by using lead magnesio-niobate piezoelectric ceram powders (PMN) as dispersing phase in acrylonitrile butadiene rubber (NBR) matrix. The dielectric and piezoelectric properties of the composite were studied. The result shows that the particle size of 80% of PMN ceram powders was 0.5–2 µm. The piezoelectric constant (d₃₃) of the composite increased with increasing volume fraction of PMN, and the max piezoelectric constant is 33 when the PMN volume fraction is 85%. Appropriate delay of polarizing time with increasing polarizing voltage could be helpful to improve the d₃₃ value. The optional polarizing condition is 25 min, 7–8 kv/mm, and 80°C. The dielectric constant increased with the increasing of the PMN volume fraction. Polarized time, polarized voltage, and polarized temperature have no effect on the dielectric constant.     

Properties of Modified Lead Zirconate Titanate Ceramics Prepared at Low Temperature (800°C) by Hot Isostatic Pressing

High-density lead zirconate titanate (PZT) ceramics were fabricated for the first time at a temperature as low as 800°C via the hot isostatic pressing (HIP) of a PZT powder with a modified composition of 0.92Pb(Zr_0.53Ti_0.47)O₃—0.05BiFeO₃—0.03Ba(Cu_0.5W_0.5)O₃ that contained 0.5 mass% MnO₂. The resultant PZT ceramics exhibited a microstructure that was denser and finer than that of PZT sintered at 935°C, which is the lowest temperature for the densification of the same composition via normal sintering. The relevant dielectric and piezoelectric properties of the HIPed PZT ceramics were as follows: coefficient of electromechanical coupling ( K ₃₁), 31.8%; mechanical quality factor ( Q _m), 1364; piezoelectric constant ( d ₃₁), −73.7 × 10⁻¹² C/N; relative dielectric constant (ɛ₃₃^T/ɛ₀), 633; dielectric loss factor (tan δ), 0.5%; Curie temperature ( T _c), 285°C; and density (ρ), 8.06 g/cm³. In addition to these reasonably good piezoelectric properties, the HIPed PZT exhibited better mechanical properties—particularly, higher fracture strength—than the normally sintered PZT.