超高居里温度钙钛矿层状结构压电陶瓷研究进展

doi:10.15541/jim20170265

摘要/Abstract

摘要：

钙钛矿层状压电陶瓷具有超高居里温度和高温度稳定性, 已成为目前高温压电陶瓷的研究热点。本文针对钙钛矿层状压电陶瓷致密化烧结难以及压电性能低的难题, 主要从晶体结构、制备工艺、掺杂改性和复合固溶体等方面总结了钙钛矿层状高温压电陶瓷的研究进展, 同时归纳和比较了不同制备工艺和掺杂改性的钙钛矿层状高温压电陶瓷的烧结性和压电性能。简要分析了钙钛矿层状结构自发极化的来源, 并对未来研究这类材料的铁电相变机理和提高压电性能作了展望。

关键词: 超高温压电陶瓷, 钙钛矿层状结构, 铁电体, 综述

Abstract:

Perovskite-layer structured (PLS) piezoelectric ceramics have the characteristics of ultra high Curie temperature and good thermal stability, thus PLS ceramics have become one of the hot topics in the field of high temperature piezoelectric ceramics. The present article reviews the research progress on PLS piezoelectric ceramics from the aspects of crystal structure, processing technologies, doping modifications, and forming solid solutions in order to overcome their disadvantages of poor sinterability and low piezoelectricity. Meanwhile, this review summarizes and compares the effects of processing technologies and doping modifications on the sinterability and piezoelectricity of PLS ceramics. Furthermore, the origin of the spontaneous polarization of PLS ferroelectircs is briefly described. The mechanism of ferroelectric phase transition and the approaches to improvement of piezoelectric properties for PLS piezoelectric ceramics are proposed for research work in the near future.

Key words: ultra high temperature piezoceramics, perovskite-layer structure, ferroelectrics, review

中图分类号:

TM282

周志勇, 陈涛, 董显林. 超高居里温度钙钛矿层状结构压电陶瓷研究进展[J]. 无机材料学报, 2018, 33(3): 251-258.

ZHOU Zhi-Yong, CHEN Tao, DONG Xian-Lin. Research Progress of Perovskite Layer Structured Piezoelectric Ceramics with Super High Curie Temperature[J]. Journal of Inorganic Materials, 2018, 33(3): 251-258.

图/表 10

图1 不同晶体结构压电陶瓷的压电系数d33与居里温度Tc之间的关系

Fig. 1 Relationship between d33 and Curie temperature Tc of piezoceramics with different crystal structures(Inset showing schematic diagrams of perovskite, tungsten bronze, bismuth layer and perovskite layer structures)

表1 A2B2O7型化合物和结构

Table 1 A2B2O7-type compounds and their structures

PY*	Formula	Structure	Ferroelectric	Ref.
1955	Cd₂Nb₂O₇	Pyrochlore	Yes	[17]
1955	Ca₂Ta₂O₇	Pyrochlore	No	[17]
1955	Cd₂Ta₂O₇	Pyrochlore	No	[17]
1955	Pb₂Ta₂O₇	Pyrochlore	No	[17]
1970	Ca₂Nb₂O₇	PLS	Yes	[19]
1974	La₂Ti₂O₇	PLS	Yes	[21]
1974	Nd₂Ti₂O₇	PLS	Yes	[22]
1975	Sr₂Nb₂O₇	PLS	Yes	[23]
1975	Sr₂Ta₂O₇	PLS	Yes	[12]
1980	Pr₂Ti₂O₇	PLS	Yes	[24]
1980	Ce₂Ti₂O₇	Pyrochlore	No	[24]
1987	Sm₂Ti₂O₇	Pyrochlore	No	[25]
2015	Ce₂Ti₂O₇	PLS	Yes	[26]

表2 A2B2O7型PLS化合物的晶体特征

Table 2 Crystallographic properties of A2B2O7-type PLS compounds

Compound	Crystal system	Space group	Lattice constants					Cleavage plane	Ref.
Compound	Crystal system	Space group	a/nm	b/nm		c/nm	β	Cleavage plane	Ref.
Sr₂Nb₂O₇	Orthorhombic	Cmc2₁	0.3933		2.6726	0.5683	—	(010)	[27]
Sr₂Ta₂O₇	Orthorhombic	Cmc2₁	0.3950		2.7270	0.5700	—	(010)	[28]
Ca₂Nb₂O₇	Monoclinic	P2₁	1.3400		0.5510	0.7720	98°17°	(100)	[29]
La₂Ti₂O₇	Monoclinic	P2₁	1.3019		0.5547	0.7811	98°43°	(100)	[21]
Nd₂Ti₂O₇	Monoclinic	P2₁	1.3020		0.5480	0.7680	98°28°	(100)	[22]
Pr₂Ti₂O₇	Monoclinic	P2₁	0.7715		0.5488	1.3004	98°33°	(001)	[30]

图2 (a)沿a轴和(b)沿c轴方向Sr2Nb2O7晶体结构示意图

Fig. 2 Crystal structure of Sr2Nb2O7 viewed along a (a) and along c (b)Atoms are labelled in accordance with the nomenclature of Ref [23]

图3 (a) Cmcm相La2Ti2O7中最不稳态模式下最大原子位移示意图和(b)理想钙钛矿结构BaTiO3中典型反铁电畸变模式示意图。箭头表示不同y面上与氧位移相关的电偶极矩[34]

Fig. 3 (a) Sketch of the largest atomic displacements associated with the strongest instability mode obtained for the Cmcm phase of La2Ti2O7; (b) Sketch of a typical anti-ferrodistortive mode occurring in an ideal perovskite structure of BaTiO3. The arrows on the side represent the electric dipoles associated to the displacement of oxygens in different y-planes[34]

图4 计算的单斜P21 La2Ti2O7化合物价电子电荷密度。等高线相差为0.05e Å-3 [35]

Fig. 4 Calculated valence-electron charge density for the monoclinic P21 La2Ti2O7. Contour lines differ by 0.05 e Å-3 [35] (1 Å=0.1 nm)

图5 不同工艺在制备的PLS高温压电陶瓷SEM照片

Fig. 5 SEM images of PLS high temperature piezoceramics fabricated with different techniques(a) Sr2Nb2O7 by solid state reaction method[42]; (b) Sr2Nb2O7 by spark plasma sintering[15]; (c) 0.3wt%ZnO-Sr2Nb2O7 by solid state reaction method[41]; (d) Ce2Ti2O7 at 4 GPa, 1100℃[26]

图6 不同温度下热退极化对Sr2-xBaxNb2O7压电陶瓷压电性能的影响[45]

Fig. 6 Effect of thermal depoling on piezoelectric properties of Sr2-xBaxNb2O7 piezoceramics[45]

图7 不同温度下热退极化对(1-x)Sr2Nb2O7 -x(Na0.5Bi0.5)TiO3压电陶瓷d33的影响[51]

Fig. 7 Temperature dependence of d33 values of (1-x)Sr2Nb2O7-x(Na0.5Bi0.5)TiO3 piezoceramics after thermal annealing[51]

表3 不同方法制备的PLS压电陶瓷的主要性能

Table 3 Characteristics of PLS piezoceramics fabricated via different methods

Materials	Process	T_s/℃	Density/%	T_c/℃	d₃₃/(pC/N)	Ref.
Sr₂(Nb₁_-xTa_x)₂O₇	HF	1400	95	823	1.6	[38]
Sr₂_-xBa_xNb₂O₇	SPS	1200	95	1175	3.6	[45]
La₂_-xCe_xTi₂O₇	SPS	1400	95	1440	3.9	[46]
(Sr₁_-xCe_x)₂Nb₂O₇	SPS	1350	98	1327	1.5	[47]
Sr₂(Nb₁_-xW_x)₂O₇	SPS	1425	98	1308	—	[47]
(Sm_xLa₁_-x)Ti₂O₇	SPS	1400	—	1430	2.8	[48]
(Bi_xLa₁_-x)Ti₂O₇	SPS	1350	95	1395	3.6	[49]
Sr₂Nb₂O₇-xwt%La₂O₃	SSR	1350	—	—	—	[43]
Ca₂_-xBa_xNb₂O₇	SSR	1350	95	1280	—	[44]
Sr₂(Nb₁_-xV_x)₂O₇	SSR	1200	96	—	—	[40]
Sr₂Nb₂O₇-xwt%ZnO	SSR	1400	97	—	—	[41]
Sr₂Nb₂O₇-xwt%CuO	SSR	1180	98	1342	1.1	[42]
(1-x)Sr₂Nb₂O₇-xNa_0.5Bi_0.5TiO₃	SSR	1420	96.8	1330	1.0	[51]

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