CuO掺杂(Ba,Ca)(Ti,Sn)O3陶瓷的结构与压电性能

doi:10.15541/jim20240215

无机材料学报 ›› 2024, Vol. 39 ›› Issue (10): 1100-1106.DOI: 10.15541/jim20240215 CSTR: 32189.14.10.15541/jim20240215

CuO掺杂(Ba,Ca)(Ti,Sn)O₃陶瓷的结构与压电性能

彭萍(), 谭礼涛

福建理工大学材料科学与工程学院, 福州 350108

收稿日期:2024-04-24 修回日期:2024-05-10 出版日期:2024-10-20 网络出版日期:2024-05-16
作者简介:彭萍(1991-), 女, 博士, 副教授. E-mail: xgpengping@163.com
基金资助:
国家自然科学基金青年项目(52102125);福建省自然科学基金青年基金(2021J05223);中国科学院无机功能材料与器件重点实验室开放基金(KLIFMD202101);华东理工大学超细材料制备与应用教育部重点实验室开放基金(JKD01231702);福建理工大学科研启动基金(GY-Z21068)

Structure and Piezoelectric Properties of CuO-doped (Ba,Ca)(Ti,Sn)O₃ Ceramics

PENG Ping(), TAN Litao

School of Materials Science and Engineering, Fujian University of Technology, Fuzhou 350108, China

Received:2024-04-24 Revised:2024-05-10 Published:2024-10-20 Online:2024-05-16
About author:PENG Ping (1991-), female, PhD, associate professor. E-mail: xgpengping@163.com
Supported by:
National Natural Science Foundation of China(52102125);Natural Science Foundation of Fujian Province(2021J05223);Opening Project of Key Laboratory of Inorganic Functional Materials and Devices, Chinese Academy of Sciences(KLIFMD202101);Opening Project of Key Laboratory for Ultrafine Materials, Ministry of Education, East China University of Science and Technology(JKD01231702);Research Fund of Fujian University of Technology(GY-Z21068)

摘要/Abstract

摘要：

(Ba,Ca)(Ti,Sn)O₃(BCTS)压电陶瓷具有优异的压电性能, 在压电传感器、换能器领域表现出巨大的应用潜力。其烧结温度非常高(通常在1450 ℃以上), 导致其在实际应用中受到限制。为了降低烧结温度, 本研究以(Ba_0.95Ca_0.05)(Ti_0.90Sn_0.10)O₃为基体, 选择CuO作为烧结助剂, 通过传统固相烧结法制备BCTS-xCuO压电陶瓷, 系统研究CuO含量对BCTS陶瓷的烧结温度、结构及介电、压电性能的影响规律。研究发现, 加入CuO后, 陶瓷主相为钙钛矿结构, 存在少量杂相, 可能是Ba₂TiO₄和Ba₂Cu₃O_5.9。CuO掺杂能有效将陶瓷的烧结温度从1480 ℃降低至1360 ℃, 提高压电陶瓷的相对致密度, 增大陶瓷的平均晶粒尺寸。当x=0.03时, 陶瓷获得最高相对致密度(98.7%)和最大平均晶粒尺寸(22.5 μm), 同时获得最优异的电学性能: 压电系数d₃₃=573 pC/N, 机电耦合系数k_p=36%, 相对介电常数ε_r=9467, 介电损耗tanδ=0.021。与其他低温烧结的BaTiO₃基陶瓷相比, x=0.03陶瓷组分在低烧结温度下具有更高的d₃₃, 表现出优异的综合性能。本研究结果表明, CuO掺杂可有效降低BCTS陶瓷的烧结温度, 提高压电性能, 为其在压电器件领域的应用提供指导。

关键词: 无铅压电陶瓷, 压电性能, 低温烧结

Abstract:

(Ba,Ca)(Ti,Sn)O₃ (BCTS) piezoelectric ceramics exhibit excellent piezoelectric properties and show great potential in the fields of piezoelectric sensors and transducers. However, their sintering temperature is very high, typically exceeding 1450 ℃, which limits their practical applications. In order to lower the sintering temperature, the oxide CuO was added into (Ba_0.95Ca_0.05)(Ti_0.90Sn_0.10)O₃ceramics as a sintering aid in this work. Herein, BCTS-xCuO piezoelectric ceramics were prepared by the conventional solid-state sintering method, and the influence of CuO content on the sintering temperature, structure as well as dielectric and piezoelectric properties of BCTS ceramics was investigated systematically. After adding CuO, the perovskite crystal structure was mainly formed in BCTS ceramics, with a small amount of secondary phases, which may be Ba₂TiO₄and Ba₂Cu₃O_5.9. Moreover, it was found that CuO doping can effectively reduce the sintering temperature of ceramics from 1480 ℃ to 1360 ℃ and improve the relative density of piezoelectric ceramics. The highest relative density (98.7%) and maximum average grain size (22.5 μm) were obtained at x=0.03. Hence, the optimal electrical properties were obtained at x=0.03 with piezoelectric coefficient d₃₃=573 pC/N, planar electromechanical coupling coefficient k_p=36%, relative permittivity ε_r=9467, and dielectric loss tanδ=0.021. Compared with other reported low-temperature sintered BaTiO₃-based ceramics, the x=0.03 component ceramics in this study obtained higher d₃₃ at a low sintering temperature, showing excellent comprehensive properties. In conclusion, this work demonstrates that CuO doping can successfully reduce the sintering temperature and optimize the piezoelectric properties of BCTS ceramics.

Key words: lead-free piezoelectric ceramic, piezoelectric property, low temperature sintering

中图分类号:

TQ174

彭萍, 谭礼涛. CuO掺杂(Ba,Ca)(Ti,Sn)O₃陶瓷的结构与压电性能[J]. 无机材料学报, 2024, 39(10): 1100-1106.

PENG Ping, TAN Litao. Structure and Piezoelectric Properties of CuO-doped (Ba,Ca)(Ti,Sn)O₃ Ceramics[J]. Journal of Inorganic Materials, 2024, 39(10): 1100-1106.

图/表 9

图1 不同温度烧结BCTS-0.03CuO的SEM照片

Fig. 1 SEM images of BCTS-0.03CuO ceramics sintered at different temperatures (a) 1360 ℃; (b) 1370 ℃; (c) 1380 ℃; (d) 1390 ℃; (e) 1400 ℃

图2 BCTS-xCuO的SEM照片

Fig. 2 SEM images of BCTS-xCuO ceramics (a) x=0, Ts=1480 ℃; (b) x=0.01, Ts=1380 ℃; (c) x=0.03, Ts=1380 ℃; (d) x=0.05, Ts=1360 ℃; (e) x=0.07, Ts=1360 ℃

图3 CuO含量对BCTS陶瓷相对密度(a)和平均晶粒尺寸(b)的影响

Fig. 3 Effects of CuO content on (a) relative density and (b) average grain size of BCTS ceramics

图4 未极化BCTS-xCuO陶瓷在2θ=20°~80°范围内的XRD谱图

Fig. 4 XRD patterns in the range of 2θ=20°-80° for unpoled BCTS-xCuO ceramics

图5 x=0.03组分陶瓷的SEM照片和EDS元素分布面扫图

Fig. 5 SEM image and EDS elemental mappings of x=0.03 ceramics

图6 BCTS-xCuO的变温介电性能

Fig. 6 Temperature-dependent dielectric properties of BCTS-xCuO samples (a) Relative permittivity εr; (b) TC as a function of CuO content; Colorful figures are available on website

图7 室温、10 kHz下BCTS-xCuO的介电性能变化图

Fig. 7 Dielectric properties of BCTS-xCuO ceramics measured at 10 kHz and room temperature (a) εr as a function of CuO content; (b) tanδ as a function of CuO content

图8 BCTS-xCuO的压电性能

Fig. 8 Piezoelectric properties of BCTS-xCuO (a) d33 as a function of CuO content; (b) Impedance and phase angle for the x=0.03 component ceramics; (c) kp as a function of CuO content; (d) Dependence of d33 on sintering temperature for the x=0.03 component ceramics

图9 文献报道BaTiO3基压电陶瓷的压电系数d33与烧结温度Ts对比[22⇓⇓-25,29⇓⇓⇓⇓⇓⇓⇓ -37]

Fig. 9 Comprehensive comparison of d33 and Ts of BaTiO3- based piezoelectric ceramics in literature[22⇓⇓-25,29⇓⇓⇓⇓⇓⇓⇓ -37]

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CuO掺杂(Ba,Ca)(Ti,Sn)O₃陶瓷的结构与压电性能

Structure and Piezoelectric Properties of CuO-doped (Ba,Ca)(Ti,Sn)O₃ Ceramics

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