制备工艺对(Ba0.85Ca0.15)(Ti0.9Zr0.1)O3无铅压电陶瓷结构与性能的影响

采用液相混合与固相烧结相结合的方法制备了(Ba_0.85Ca_0.15)(Ti_0.9Zr_0.1)O₃ (BCTZ) 无铅压电陶瓷, 系统研究了烧结保温时间对其相结构、介电、压电和铁电性能的影响以及电学性能随温度的变化。研究结果表明: 制备的陶瓷样品具有单一的四方钙钛矿结构。当烧结温度为1540℃时, 随着保温时间的延长, 样品晶粒尺寸变大, 居里温度(T_c)升高, 压电性能提高, 电致伸缩性能下降。当保温时间为24 h时, BCTZ陶瓷综合性能最为优异: T_c ~90℃, tanδ < 0.05, k_p ~ 0.46, d₃₃ ~ 540 pC/N, P_s ~17 μC/cm²。陶瓷电学性能随温度变化测试结果又表明, BCTZ陶瓷的电学性能具有很强的温度依赖性, 随着温度的升高其电学性能逐渐下降。     

低温烧结制备(Ba_(0.9)Ca_(0.1))(Zr_(0.15)Ti_(0.85))O_3无铅压电陶瓷

采用溶胶-凝胶法制备出(Ba0.9Ca0.1)(Zr0.15Ti0.85)O3(简称BCT-BZT)粉体,并采用两段式传统烧结法用较低的烧结温度(1 290℃)制备了该无铅压电陶瓷,运用热重差示扫描测量法分析了反应过程。X射线衍射测试结果表明,BCT-BZT粉体和陶瓷均是典型的钙钛矿结构,根据谢乐公式计算出粉体的晶粒尺寸约为32nm。此外,室温下利用TF Analyzer 2000铁电分析仪测得该陶瓷的介电常数高达6 134,居里温度约为95℃,最大压电系数d33达到263pm/V。利用此方法制备的BCT-BZT无铅压电陶瓷,其烧结温度与固相反应法相比降低了约200℃左右,同时还保持了良好的压电性能,从而降低了烧结成本,有利于实现该陶瓷的大规模工业化生产。     

(0.84-x)Na_(0.5)Bi_(0.5)TiO_3-0.16K_(0.5)Bi_(0.5)TiO_(3-x)SrTiO_3系无铅压电陶瓷结构与电性能

采用固相法制备了Bi补偿的(0.84-x)Na0.5Bi0.5TiO3-0.16K0.5Bi0.5TiO3-x SrTiO3(简称NBTKBT-xST)无铅压电陶瓷,研究不同ST掺量对体系陶瓷的结构与电性能的影响规律。结果表明,在掺杂范围内(0≤x≤0.06),材料均能形成单一的钙钛矿固溶体结构。随着x的增加,陶瓷晶体结构逐渐由三方相向四方相过渡,且该体系的三方-四方准同型相界(MPB)位于0.03≤x≤0.04。在此组成区域内,体系陶瓷的铁电与压电性能较好,其中x=0.04时,材料的电性能较好:压电常数d33=156 pC/N,平面机电耦合系数k p=0.29,相对介电常数εr=1116,介质损耗tanδ=4.1%,剩余极化强度P r=30.5μC/cm2,矫顽场E c=23.9 kV/cm。介电温谱和变温电滞回线表明体系陶瓷在T d以上可能存在极性相与非极性相共存。     

TbDyFe掺杂对(Ba_(0.85)Ca_(0.15))(Ti_(0.9)Zr_(0.08)Sn_(0.02))O_3无铅压电陶瓷组织与电性能的影响

为获得BCZTS无铅压电陶瓷优良的电性能,通过对其掺杂TbDyFe,采用传统固相烧结法制备(Ba0.85Ca0.15)(Ti0.9Zr0.08Sn0.02)O3-x TbDyFe(BCZTS-x TbDyFe)无铅压电陶瓷,分析不同TbDyFe(x=0~0.4wt.%)含量对BCZTS无铅压电陶瓷微结构、压电性能、介电性能和铁电性能的影响,并利用XRD、SEM等方法分析表征样品。结果表明:所有样品均为单一的钙钛矿结构;掺杂TbDyFe后陶瓷的晶粒尺寸变小。由介电温谱可知,掺杂TbDyFe后BCZTS体系出现介电弛豫行为。当掺杂x=0.1wt.%时,无铅压电陶瓷材料的综合性能优异:d33=500 p C/N,kp=40%,εr~5955,tanδ~1.9%,Pr=6.6μC/cm2,Ec=2 k V/cm。     

La2O3、Y2O3掺杂对(Na0.5Bi0.5)0.94Ba0.06TiO3无铅压电陶瓷性能的影响

以(Na0.5Bi0.5)0.94Ba0.06TiO3为基体,研究了单、双组分掺杂La2O3、Y2O3对BNBT6陶瓷的压电和介电性能及微观结构的影响。XRD分析表明:掺杂La2O3、Y2O3均得到钙钛矿结构。SEM分析表明,分别掺杂0.2%La2O3和0.2%Y2O3使得陶瓷晶粒增大,压电常数提高,双组分掺杂La2O3、Y2O3在掺杂量0.12%La2O3+0.08%Y2O3时,压电常数d33增大到最大值144.6×10-12C/N,介质损耗降低到最小值0.039。     

(1-x)(Na0.5K0.5)NbO3-x(Ba0.88Ca0.12Zr0.12Ti0.88O3) 无铅压电陶瓷的制备及性能研究

介绍了一种利用传统固态烧结法制作的无铅压电陶瓷(1-x)(Na_(0.5)K_(0.5))NbO_3-x(Ba_(0.88)Ca_(0.12)Zr_(0.12)Ti_(0.88)O_3)((1-x)KNN-xBCZT)。(1-x)KNN-xBCZT是由KNN和BCZT形成的均匀固溶体。随着BCZT浓度的增加,(1-x)KNN-xBCZT的T_c和四方相-正交相的相变温度呈近似直线方式下降。相变温度的降低,有助于提升固溶体的电性能,当x=0.055时(1-x)KNN-xBCZT陶瓷性能达到最优。MnO_2助烧剂可以进一步降低(1-x)KNN-xBCZT陶瓷的相变温度,使(1-x)KNN-xBCZT陶瓷更为致密。0.055BCZT-0.945KNN-0.01MnO_2陶瓷展现出的性能为d_(33)=212 pC/N,d_(31)=-75 pC/N,k_p=45%,ε=875,tanδ=0.02和T_C=340℃,T_(O-T)=127℃。     

准同型相界(MPB)附近BS-PT高温压电陶瓷研究

（1-x）BiScO3-xPbTiO3陶瓷（简记BS-PT）在x=64．0％附近存在一个从菱方晶系过渡到四方晶系的准同型相界，在此相界附近材料能获得优良的介电和压电性能．本文选取PbTiO3含量在64．0％-65．5％的准同型相界附近的材料组分，利用传统的固相烧结反应法合成了纯钙钛矿相结构的BS—PT陶瓷，通过对材料的相结构形成过程和内部形貌分析以及对介电、压电性能的研究，发现在x=64．5％的组分条件下，BS—PT陶瓷材料获得了准同型相界范围内的最优的压电性能，其室温压电常数d33可达500pC／N，且居里温度（Tc）达到了438℃，剩余极化强度和电致应变分别为44μC／cm^2和3．5‰．研究表明，准同型相界附近的BS-PT陶瓷是一种优良的压电换能器和传感器材料．     

一种改性铌酸盐系无铅压电陶瓷的合成与特性研究

K0.5Na0.5NbO3(KNN)系铌酸盐是一类可能替代铅基压电陶瓷的无铅压电陶瓷.利用Ta和Sb掺杂或者取代KNN中的相关离子,在陶瓷的准同型相界(MPB)处显现出高的压电和介电性能.利用传统技术制作出一种新的致密度较高的无铅压电陶瓷(1-x)(K0.5Na0.5)(Nb0.96Sb0.04)O3-xLiTaO3(简记为KNNS-LT).所有的组分在MPB处都存在纯的钙钛矿结构,主要压电性能在MPB处达极大值,其机电耦合系数kp为40%,压电常数d33为225pC/N,居里温度Tc为355℃.     

0.94[(Na0.96-xKxLi0.04)0.5Bi0.5]TiO3-0.06Ba(Zr0.055Ti0.945)O3无铅压电陶瓷的压电介电特性

对无铅压电陶瓷0.94[(Na0.96-xKxLi0.04)0.5Bi0.5]TiO3-0.06Ba(Zr0.055Ti0.945)O3的性质随K含量的变化进行了系统研究,获得压电应变常数d33高达185pC/N的0.94[(Na0.80K0.16Li0.04)0.5-Bi0.5]TiO3-0.06Ba(Zr0.055Ti0.945)O3压电陶瓷.随着K掺杂量的增加,该陶瓷材料的介电温谱峰值向右明显移动,其介电峰温度明显升高.     

Lead-free (Ba0.85Ca0.15)(Ti0.9Zr0.1)O3-Y2O3 ceramics with large piezoelectric coefficient obtained by low-temperature sintering

Lead-free (Ba_0.85Ca_0.15)(Ti_0.9Zr_0.1)O₃-xwt.%Y₂O₃ (BCZT-xY) piezoelectric ceramics have been synthesized using solid-state reaction technique and the effects of Y₂O₃ addition on the phase structure and piezoelectric properties of the ceramics have been studied. The results reveal that the addition of Y₂O₃ significantly improves the sinterability of BCZT ceramics, resulting in a reduction of sintering temperature from 1,540 to 1,350 °C, and an increase of the Curie temperature T _C from 85 to 95 °C. X-ray diffraction data shows that Y₂O₃ diffuses into the lattice of BCZT-xY ceramics and a pure perovskite phase forms in the ceramics. Scanning electron microscopy images indicate that a small amount of Y₂O₃ addition affects the microstructure, obviously. Main piezoelectric parameters of these ceramics are optimized around x = 0.06 wt % with a large piezoelectric coefficient (d ₃₃  = 560 pC/N), a high planar electromechanical coefficient (k _p  = 53 %) and a low dissipation factor (tan δ = 0.9 %) at 1 kHz. The results indicate that the BCZT-xY ceramics are promising lead-free materials for practical applications.     

Improved energy storage and electrocaloric properties of lead-free Ba0.85Ca0.15Zr0.1Ti0.9O3 ceramic

Lead-free Ba_0.85Ca_0.15Zr_0.1Ti_0.9O₃ (BCZT) ceramic powders were synthesized using the sol–gel method. The ceramics thickness was reduced to achieve high-energy storage and large electrocaloric effect in bulk ceramics. Dielectric, ferroelectric, energy storage, and electrocaloric properties were investigated for BCZT ceramic with 400 µm. Here, pure crystalline structure and homogenous microstructure were identified by XRD analysis and SEM measurements, respectively. The dielectric measurements revealed a maximum dielectric constant associated with ferroelectric–paraelectric phase transition. The maximum of \(\varepsilon^{\prime}_{{\text{r}}}\) was 17841, around 352 K. Furthermore, the BCZT ceramic exhibited improved energy storage and electrocaloric properties. A high recoverable energy density W_rec of 0.24 J/cm³ and a total energy density W_total of 0.27 J/cm³ with an efficiency coefficient of?~?88% at 423 K under an electric field of 55 kV/cm were obtained. Besides, The maximum value of ΔT?=?2.32 K, the electrocaloric responsivity ζ?=?0.42 K mm/kV, the refrigeration capacity RC?=?4.59 J/kg and the coefficient of performance COP?=?12.38 were achieved around 384 K under 55 kV/cm. The total energy density W_total and the temperature change ΔT were also calculated by exploiting the Landau–Ginzburg–Devonshire (LGD) theory. The theoretical results matched the experimental findings. These results suggest that the synthesized BCZT ceramic with reduced thickness could be a promising candidate for energy storage and electrocaloric applications.

     

Orientation-dependent phase transition and dielectric properties of Ba0.85Ca0.15Ti0.9Zr0.1O3 thin films

Polycrystalline Ba_0.85Ca_0.15Ti_0.9Zr_0.1O₃ (BCZT) thin films with (100) preferential and random orientation are prepared on the LaNiO₃ electrodes coated on Si substrates by chemical solution deposition process. The results show that the two types of films stabilize in the pure perovskite structure. The ferro-paraelectric phase transitions of two types of films occur at the temperature ranges of 280.2–297.8 K and 278.4–287.6 K, respectively. The dielectric constant, relaxation time and tunability of the random orientation film are smaller than those of the (100) preferential film but both almost have the similar leakage current characteristics. The mechanism associated with the change of the electrical properties of the thin films is also discussed.     

Dielectric,ferroelectric, and piezoelectric properties of Sb2O3-modified (Ba0.85Ca0.15)(Zr0.1Ti0.9)O3 lead-free ceramics

The microstructures, phase structure, and electrical properties have been investigated for the Sb₂O₃-modified (Ba_0.85Ca_0.15)(Zr_0.1Ti_0.9)O₃ lead-free piezoelectric ceramics. The grain size was strongly affected by Sb₂O₃, and the solid solutions show a single phase perovskite structure. The ceramics with x = 0.1 % exhibit enhanced electrical properties of d ₃₃ ～556 pC/N, k _p ～52 %, ε _r ～3,895, tan δ ～1.3 %, and P _r ～12.6 μC/cm² when sintered at a low temperature of ～1,350 °C. The high temperature stability of ferroelectric properties (P _r ～14.8 μC/cm²) was obtained in the temperature range from ?60 to 0 °C. And with the addition of small amount of Sb₂O₃, Curie temperature (T _c ) maintains virtually unaltered.     

Low temperature sintering and properties of lead-free (Ba0.85Ca0.15)(Zr0.1Ti0.9)O3 ceramics with Ba(Cu0.5W0.5)O3 addition

The low-temperature sintering behavior of (Ba_0.85Ca_0.15)(Zr_0.10Ti_0.90)O₃ (BCZT) piezoelectric ceramics with Ba(Cu_0.5W_0.5)O₃ (BCW) addition has been investigated. The addition of 0.1 wt% BCW promotes the sinterability of BCZT ceramics owing to the generation of a liquid phase, resulting in a reduction of sintering temperature from 1,540 to 1,350 °C. The piezoelectric coefficient (d ₃₃), and the electromechanical coupling factor (kp) of the BCZT ? 0.1 wt%BCW specimen sintered at 1,350 °C were 555 pC/N and 55 %, respectively, while Curie temperature (Tc) increases from 85 to 95 °C.     

无铅Ba(Ce,Ti)O_3陶瓷的电卡效应

本文使用标准固相烧结法制备了Ba(Ti_(1-x)Ce_x)O_3(x=0.10,0.15,0.20)陶瓷,通过XRD分析发现这些陶瓷中除了Ba(Ti_(1-x)Ce_x)O_3主相外,还存在少量的杂相。利用Rietveld拟合的方法,获得了Ba(Ti_(1-x)Ce_x)O_3主相中的Ce/Ti实际比例。介电温谱表明这些陶瓷均存在一个明显的介电峰,且随着x的增加,峰值温度下降,介电峰宽展宽。利用不同温度下的电滞迴线,给出了不同温度和电场强度下的极化值,通过间接法获得了这些陶瓷的电卡效应。结果表明,BaTi_(0.9)Ce_(0.1)O_3的电卡效应最强,其DT值在403K和40kV/cm的电场下达到最大值,为0.48K,电卡强度为0.12×10~(-6)K·m/V。     

Sintering temperature-induced electrical properties of (Ba0.90Ca0.10)(Ti0.85Zr0.15)O3 lead-free ceramics

Effects of the sintering temperature on the microstructure and electrical properties of (Ba_0.90Ca_0.10)(Ti_0.85Zr_0.15)O₃ (BCTZ) lead-free piezoelectric ceramics have been studied, where these ceramics were prepared by the conventional oxide-mixed method at varied sintering temperatures from 1300 °C to 1500 °C. These BCTZ ceramics exhibits a phase transition from a rhombohedral phase to the coexistence of rhombohedral and tetragonal phases with an increase of sintering temperature. With an increase of sintering temperature, their relative density and average grain size gradually increase, and electrical properties are improved greatly. These BCTZ ceramics sintered at ～1440 °C have optimum electrical properties: d₃₃ ～ 442 pC/N and k_p ～ 48.9%, making it a promising material for lead-free piezoelectric ceramics.