硅酸盐学报

高温振动传感器用0.365BiScO₃-0.635PbTiO₃压电陶瓷锰掺杂机制再认识

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倪雷坤 ¹ , 许文龙 ¹ , 房远勇 ² , 吴健 ² , 赵俊 ¹ , 郑木鹏 ¹ , 侯育冬 ¹

硅酸盐学报 | 第15届无机非金属材料专题研讨会专题(一)——研究论文 2026,54(4): 1190-1201

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硅酸盐学报 | 第15届无机非金属材料专题研讨会专题(一)——研究论文 2026, 54(4): 1190-1201

高温振动传感器用0.365BiScO₃-0.635PbTiO₃压电陶瓷锰掺杂机制再认识

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倪雷坤¹, 许文龙¹, 房远勇², 吴健², 赵俊¹, 郑木鹏¹, 侯育冬¹

作者信息

^1．北京工业大学材料科学与工程学院，材料循环低碳再生全国重点实验室，新型功能材料教育部重点实验室，北京 100124

^2．北京强度环境研究所，北京 100076

倪雷坤（1999—），男，硕士研究生。

NI Leikun (1999-), male, Master candidate. E-mail: a1812067011@163.com

通讯作者:

侯育冬（1974—），男，博士，教授。

Re-Understanding Manganese Doping Mechanism of 0.365BiScO3-0.635PbTiO3 Piezoelectric Ceramics for High-Temperature Vibration Sensors

Leikun NI¹, Wenlong XU¹, Yuanyong FANG², Jian WU², Jun ZHAO¹, Mupeng ZHENG¹, Yudong HOU¹

Affiliations

^1.State Key Laboratory of Materials Low-Carbon Recycling, Key Laboratory of Advanced Functional Materials, Education Ministry of China, School of Materials Science and Engineering, Beijing University of Technology, Beijing 100124, China

^2.Beijing Institute of Structure and Environment Engineering, Beijing 100076, China

出版时间: 2026-01-30 doi: 10.14062/j.issn.0454-5648.20250834

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摘要

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高温振动传感器是航空航天、核能开发等领域核心装备健康检测不可或缺的关键器件，满足其使用要求的压电陶瓷除需具备高压电性能与高居里温度（T_C）外，还应兼具高绝缘电阻率（ρ）和高时间常数（τ）以增强高温服役稳定性。BiScO₃-PbTiO₃（BS-PT）体系因高居里温度和高压电性能而备受关注，然而，其高温绝缘特性较差，难以用于高温振动传感器。锰掺杂是常用的压电陶瓷改性手段，以往对Mn掺杂BS-PT的研究在Mn离子价态分布和取代位置上尚存争议，且缺乏以高温振动传感器应用为导向的多参数协同研究。本工作采用传统固相法制备系列MnO₂掺杂BS-PT陶瓷，旨在厘清缺陷化学机制并获取满足高温振动传感器用压电陶瓷组分。通过X射线光电子能谱仪、X射线衍射仪和扫描电子显微镜的协同分析，证实Mn元素以Mn²⁺和Mn³⁺价态共存，且主要取代钙钛矿结构B位Sc³⁺。相对于Mn³⁺等价取代，Mn²⁺异价取代形成的缺陷偶极子发挥显著的硬性掺杂作用，有效限制自由氧空位移动，结合与掺杂关联的晶界效应，在Mn掺杂固溶限处的BS-PT组分获得优异的压电性能，T_C为441 ℃，350 ℃压电电压常数g₃₃为0.012 V·m/N，同时高温绝缘特性优异，ρ_350℃保持10⁹ Ω·cm，τ_350℃从0.006 s提升至0.072 s。本工作阐明的缺陷化学机制及优化的综合性能，对高温振动传感器的应用具有重要价值。

关键词

钪酸铋-钛酸铅 / 压电陶瓷 / 锰掺杂 / 固溶限 / 高温电阻率

Abstract

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Introduction

High-temperature vibration sensors are indispensable key components for the health detection of core equipment in fields such as aerospace and nuclear energy. The BiScO₃-PbTiO₃(BS-PT) system has attracted much attention due to its high Curie temperature (T_C≈450 ℃) and excellent piezoelectricity (d₃₃≈450 pC/N). However, the poor insulation properties of this material hinder its application in high-temperature vibration sensors because high electrical resistivity (ρ) and a long time constant (τ) are critical to prevent thermal runaway and ensure signal integrity. Manganese (Mn) doping is a commonly used modification method for piezoelectric ceramics. Previous studies on Mn-doped BS-PT were controversial regarding the valence state distribution and substitution positions of Mn ions, which could not be conducive to the design of high-temperature piezoelectric ceramics with the collaborative optimization of multiple electrical parameters. Therefore, this work was to clarify the defect chemical mechanism associated with manganese doping through refined structural characterization combined with electrical performance analysis, and to obtain the modified BS-PT piezoelectric ceramic components suitable for high-temperature vibration sensors.

Methods

0.365BiScO₃-0.635PbTiO₃-x% MnO₂ (BSPT-x% MnO₂, x=0.00, 0.01, 0.25, 0.50, 0.75, 1.00, 1.25, 1.50, 1.75, 2.00) ceramics were synthesized by a conventional solid-state reaction method. The powders were firstly calcined at 800 ℃ for 2 h and then sintered at 1050 ℃ for 2 h. The phase composition was analyzed by X-ray diffraction (XRD). The rietveld refinements were performed using a software named GSAS. The microstructure and elemental distribution were examined by scanning electron microscopy (SEM) equipped with energy-dispersive X-ray spectroscopy (EDS). The average grain size was estimated by a software named Nano Measurer. The Mn valence states were determined by X-ray photoelectron spectroscopy (XPS). For electrical measurements, poled samples (120 ℃, 5 kV/mm, 30 min) were used. The piezoelectric coefficient (d₃₃) was measured by a model CAS ZJ-6A quasi-static meter. The electromechanical coupling coefficient (k_p) was measured by a model Agilent 4294A impedance analyzer. The temperature-dependent dielectric properties were measured by a model Agilent E4980A LCR analyzer. The high-temperature DC resistivity (ρ) was measured by a model Keithley 6517B high-resistance electrometer. The in-situ d₃₃ was measured by a model Julang TZFD-600 variable temperature quasi-static d₃₃ measurement system.

Results and discussion

The Mn doping mechanism and high-temperature performance of BS-PT ceramics are systematically clarified. The XPS results confirm the coexistence of Mn²⁺ and Mn³⁺. To quantitatively verify the substitution site, the rietveld refinement reveals a non-monotonic evolution of unit cell volume. Based on the EDS evidence of Sc segregation without Ti precipitation, Mn ions preferentially substitute for B-site Sc³⁺. The dominant aliovalent substitution introduces defect dipoles accompanied with strong local random electric fields, significantly enhancing a relaxor behavior, while triggering a "hardening" effect that reduces tanδ and ε_r. The decoupling of piezoelectric and dielectric properties is achieved in specific compositions due to the grain boundary effect compensating for the hardening effect, especially obtaining the optimal piezoelectric voltage constant (g₃₃) at the component with x of 1.00. For high-temperature capabilities, the optimal composition (x=1.00) demonstrates a superior stability, with in-situ d₃₃ variation remaining within 20% up to 400 ℃. The thermally stable defect dipoles effectively trap oxygen vacancies, leading to a high resistivity of 10⁹ Ω·cm and an enhanced time constant of 0.072 s at 350 ℃. Consequently, the ceramic with x of 1.00 exhibits a high g₃₃ of 0.012 V·m/N when evaluated at a unified service temperature of 350 ℃, which is 50% higher than that of the undoped counterpart. These results indicate that the modified ceramic achieves an optimal balance of sensitivity and insulation for high-temperature vibration sensors.

Conclusions

This work clarified the Mn doping mechanism in BS-PT ceramics. The results of correlative XPS, Rietveld refinement, and EDS analysis confirmed that Mn ions could preferentially substitute for B-site Sc³⁺. The dominant aliovalent substitution induced a hardening effect, while the recovery of d₃₃ was dominated by grain size restoration. The optimal composition (x=1.00) exhibited a robust stability with d₃₃variation within 20% at 400 ℃. The thermally stable defect dipoles could obtain a high resistivity (10⁹ Ω·cm) and time constant (0.072 s) at 350 ℃. Meanwhile, a superior piezoelectric voltage coefficient (g₃₃) of 0.012 V·m/N was achieved at 350 ℃, which was 50% higher than that of the undoped counterpart, validating its potential for high-temperature sensors.

Key words

bismuth scandate-lead titanate / piezoelectric ceramics / manganese doping / solid solution limit / high-temperature resistivity

引用本文

倪雷坤, 许文龙, 房远勇, 吴健, 赵俊, 郑木鹏, 侯育冬. 高温振动传感器用0.365BiScO₃-0.635PbTiO₃压电陶瓷锰掺杂机制再认识. 硅酸盐学报, 2026 , 54 (4) : 1190 -1201 . DOI: 10.14062/j.issn.0454-5648.20250834

Leikun NI, Wenlong XU, Yuanyong FANG, Jian WU, Jun ZHAO, Mupeng ZHENG, Yudong HOU. Re-Understanding Manganese Doping Mechanism of 0.365BiScO3-0.635PbTiO3 Piezoelectric Ceramics for High-Temperature Vibration Sensors[J]. Journal of the Chinese Ceramic Society, 2026 , 54 (4) : 1190 -1201 . DOI: 10.14062/j.issn.0454-5648.20250834

基金

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国家自然科学基金(52272103; 52472117)

参考文献

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2026年第54卷第4期

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文章信息

doi: 10.14062/j.issn.0454-5648.20250834

接收时间：2025-11-12
首发时间：2026-05-20
出版时间：2026-01-30

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收稿日期：2025-11-12
修回日期：2025-12-22

基金

国家自然科学基金(52272103; 52472117)

作者信息

^1．北京工业大学材料科学与工程学院，材料循环低碳再生全国重点实验室，新型功能材料教育部重点实验室，北京 100124

^2．北京强度环境研究所，北京 100076

通讯作者:

侯育冬（1974—），男，博士，教授。

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2种不同金属材料的力学参数

科 Family	属数 Number of genus	种数 Number of species	占总种数比例 Percentage of total species (%)	属 Genus	种数 Number of species	占总种数比例 Percentage of total species (%)
鹅膏菌科Amanitaceae	2	11	5.26	鹅膏菌属 Amanita	10	4.78
小菇科 Mycenaceae	2	12	5.74	丝盖伞属 Inocybe	5	2.39
多孔菌科 Polyporaceae	8	14	6.70	蜡蘑属 Laccaria	5	2.39
红菇科 Russulaceae	3	23	11.00	小皮伞属 Marasmius	6	2.87
				小菇属 Mycena	11	5.26
				光柄菇属 Pluteus	5	2.39
				红菇属 Russula	17	8.13
				栓菌属 Trametes	5	2.39

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