Mn改性Na0.5Bi2.5Nb2O9高温压电陶瓷的研究

引用本文

江向平, 温佳鑫, 陈超, 涂娜, 李小红. Mn改性Na_0.5Bi_2.5Nb₂O₉高温压电陶瓷的研究 . 无机材料学报, 2012, 27(8): 827-832
JIANG Xiang-Ping, WEN Jia-Xin, CHEN-Chao, TU-Na, LI Xiao-Hong. Piezoelectric Properties of Mn-modified Na_0.5Bi_2.5Nb₂O₉ for High Temperature Applications . Journal of Inorganic Materials, 2012, 27(8): 827-832 复制到剪切板

Permissions

This is an open-access article distributed under the terms of the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original author and source are credited.

Mn改性Na_0.5Bi_2.5Nb₂O₉高温压电陶瓷的研究

江向平, 温佳鑫, 陈超, 涂娜, 李小红

景德镇陶瓷学院材料工程系, 江西省先进陶瓷材料重点实验室, 景德镇333001

江向平(1964-), 男, 教授. E-mail:jiangxp64@163.com

修回日期:2011-12-10

基金:国家自然科学基金(50862005、51062005、91022027); 江西省高等学校“先进陶瓷材料”科技创新团队; 江西省主要学科学术和技术带头人培养对象计划项目(2010DD00800); 江西省教育厅项目(GJJ11196、GJJ11197、GJJ11204);

摘要

采用固相法获得了Mn改性的Na_0.5Bi_2.5Nb₂O₉(NBN+xmol%MnCO₃, 0≤x≤10.0)铋层状压电陶瓷, 并系统地研究了Mn(掺杂)对NBN基陶瓷显微结构与电性能的影响. 结果表明, 所有获得的样品都是居里点在700℃以上的单一相铁电体. 加入Mn显著地提高了NBN系列陶瓷的机械品质因素Q_m, 明显改善了陶瓷的压电与机电性能. 当MnCO₃掺杂量为8.0mol%时, 陶瓷获得最佳电性能: tanδ=0.749%,d₃₃=20 pC/N,Q_m=3120,k_p=12.37%,k_t=21.09%,P_r=7.01 µC/cm². NBN+xmol% MnCO₃(x=8.0)陶瓷经700℃退极化处理后, 其d₃₃保持为原来的75%(~15 pC/N), 表明该材料在高温领域下具有良好的应用前景.

关键词: 压电陶瓷; 微观结构; 机电性能; 铁电性能; Na_0.5Bi_2.5Nb₂O₉

中图分类号:TQ174 文献标志码:A 文章编号:1000-324X(2012)08-0827-06

Piezoelectric Properties of Mn-modified Na_0.5Bi_2.5Nb₂O₉ for High Temperature Applications

JIANG Xiang-Ping, WEN Jia-Xin, CHEN-Chao, TU-Na, LI Xiao-Hong

Jiangxi Key Laboratory of Advanced Ceramic Materials, Department of Material Science and Engineering, Jingdezhen Ceramic Institute, Jingdezhen 333001, China

Fund:National Natural Science Foundation of China (50862005, 51062005, 91022027); Jiangxi Colleges and Universities “Advanced Ceramics” Scientific and Technological Innovation Team; Foundation of Training Academic and Technical Leaders for Main of Jiangxi (2010DD00800); Foundation of Jiangxi Provincial Department of Education (GJJ11196, GJJ11197, GJJ11204);

Abstract

Bismuth layer-structured ferroelectric ceramics Na_0.5Bi_2.5Nb₂O₉(NBN+xmol% MnCO₃, 0≤x≤10.0) were synthesized by traditional solid state reaction. The effects of Mn addition on the microstructure and electrical properties of ceramics were investigated in detail. The results showed that all the ceramic samples were single-phase ferroelectrics with high Curie points (T_c≥700℃). With the addition of MnCO₃, the mechanical quality factor, piezoelectric activity and electromechanical properties of Na_0.5Bi_2.5Nb₂O₉-based ceramics are enhanced significantly. Besides, the NBN+8.0mol% MnCO₃ ceramic exhibits the optimum electrical properties: tanδ=0.749%,d₃₃=20 pC/N,Q_m=3120,k_p=12.37%,k_t=21.09%,P_r=7.01 µC/cm². After annealing at 700℃, thed₃₃ value of NBN+8.0mol% MnCO₃ ceramic remains 75%(~15 pC/N), which indicates that this ceramic is a promising material for high temperature applications.

Keyword: piezoelectric ceramics; microstructure; electromechanical properties; ferroelectric properties; Na_0.5Bi_2.5Nb₂O₉

Show Figures

自1949年Aurivillius发现铋层状结构化合物以来, 其有趣的结构特性及高居里温度引起了人们的广泛关注. 铋层状(BLSFs)材料具有高居里温度、机电耦合系数, 较好的抗疲劳等特性, 适合做压力传感器、滤波器等^{[ 1, 2, 3, 4, 5, 6]}. Bi₄Ti₃O₁₂、Bi₃NbTiO₉、Na_0.5Bi_4.5Ti₄O₁₅、CaBi₂Nb₂O₉、Na_0.5Bi_2.5Nb₂O₉和CaBi₄Ti₄O₁₅等BLSFs材料已经被广泛研究^{[ 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12]}.

Na_0.5Bi_2.5Nb₂O₉(NBN)是一种典型的高温( T_c~780℃)BLSFs材料^{[ 12]}. 但是, 由于其对称性低、自发极化只能在a-b平面内二维转动, 使它难以获得足够大的剩余极化强度 P_r, 限制了其在器件方面的使用. Mn作为一种常见的添加剂, 具有多种价态(+2,+3,+4), 经常用于钙钛矿与铋层状压电陶瓷的掺杂改性研究^{[ 6, 13, 14, 15, 16, 17, 18, 19]}.

为了改善NBN的电性能, Gai等^{[ 20]}通过(Li,Ce)掺杂使陶瓷的 d₃₃(pc/N)从17提高到27; Jiang等^{[ 21]}通过LiNbO₃改性使陶瓷的 d₃₃(pc/N)从10提高到21. 然而对于Mn掺杂NBN陶瓷却鲜有报道, 本工作通过固相法制备Na_0.5Bi_2.5Nb₂O₉+ xmol%MnCO₃(NBN-Mn)压电陶瓷, 并研究Mn掺杂对NBN陶瓷的物相、显微结构和电性能的影响.

1 实验部分

采用传统固相法制备了Na_0.5Bi_2.5NbO₉+ xmol% MnCO₃(NBN-Mn, x=0、1.0、3.0、5.0、7.0、8.0、9.0、10.0)陶瓷. 以Bi₂O₃(99.0%)、Nb₂O₅(99.5%)、Na₂CO₃ (99.8%)和MnCO₃(98.0%)为反应原料, 按相应的化学计量比称料. 配制的原料经混合、预烧(770℃, 2 h)、粉碎﹑细磨﹑造粒﹑压片(~18 MPa)﹑排胶﹑烧结(1080℃ 4 h). 烧成品烧制银电极, 置于160℃的硅油中, 以8.0~9.5 kV/mm电场极化30 min, 放置24 h 后测其各项电性能.

采用扫描电子探针显微镜(SEM, Model JSM- 6700F, Japan)和XRD(D8 Advance, Bruker axs)分析样品的表面形貌和物相结构. 压电常数 d₃₃利用ZJ-3A 型准静态 d₃₃ 测量仪测出. 用精密阻抗分析仪(Agilent-4294A)在100 kHz下测定其介温曲线. 平面机电耦合系数( k_p)﹑厚度机电耦合系数( k _t)和机械品质因数( Q_m)也是用精密阻抗分析仪(Agilent 4294A)通过谐振和反谐振法测量. 利用Sawyer-T- ower电桥法获得样品的电滞回线.

2 结果与讨论

2.1 微结构分析

图1是NBN-Mn陶瓷样品的XRD图谱, 可以看出, 在所有NBN-Mn陶瓷中最强峰是(115), 与铋层状结构陶瓷最强峰(112 m+1)一致^{[ 22, 23]}. 当 x≤1.0时, 只有NBN相出现; 随着Mn含量增加到3.0, BiMnO₃的(111)和BiNbO₄的(032)衍射峰出现. 从图1(b)可以看出, 在 x≤3.0时, (115)峰朝小角度偏移; 当3.0≤ x≤8.0时, 向大角度方向偏移, 当 x≥9.0时, 其又开始向小角度偏移, 表明其晶面间距先增大后变小又再增大^{[ 24]}.

	Figure Option View Download New Window
	图1 NBN-Mn粉末样品的XRD图谱Fig. 1 XRD patterns of the NBN-Mn samples in the range of 2 θ (a) from 20° to 50° and (b) from 28.5° to 30°

图2是样品的晶胞参数与体积随 x的变化关系, 可以看出, 随着Mn含量增加到3.0, c和 V随之减小. 而当Mn的量继续增加时, c和 V逐渐增大. 而 a与 b的差值在Mn量 x从0到5时越来越大, 继续增加 Mn的掺杂量, 其差值逐渐减小. 由于Mn³⁺(0.0645 nm)与B位的Nb⁵⁺(0.064 nm)相差较小, 而与A 位的Bi³⁺(0.120 nm)和Na⁺(0.118 nm)的半径相差较大, 因此这种晶格的扭曲可能是由Mn取代B位的Nb引起的^{[ 25]}. 适度的扭曲会促进其极化性能, 但是添加过量Mn后, Mn将聚集在晶界, 抑制电畴的反转^{[ 13, 26]}, 并且引入过量Mn伴随着第二相BiMnO₃(111)和BiNbO₄(032)的生成,使其介电损耗增大并导致性能的退化.

	Figure Option View Download New Window
	图2 样品晶胞参数随 x的变化关系Fig. 2 Lattice parameters of the samples as a function of x

图3为NBN-Mn陶瓷热腐蚀表面的SEM照片,由图可见, 所有陶瓷的结构紧密. 随着Mn的引入, 晶粒尺寸显著增大, 说明添加Mn能促进陶瓷晶粒的生长. 类似的现象在Na_0.5Bi_2.5Ta₂O₉、Na_0.5Bi_4.5Ti₄O₁₅、Pb (Zr, Ti) O₃、BiScO₃-PbTiO₃和 (Ca,Sr)Bi₄Ti₄O₁₅陶瓷也出现过^{[ 17, 18, 19, 27]}. 当 x≤1.0时, NBN-Mn陶瓷具有典型的层状结构, 这与(Li, Ce)掺杂NBN和LiNbO₃改性的NBN陶瓷的结构相类似^{[ 20, 21, 24]}. 当 x≥3.0时, 随着引入Mn量的增加, 其晶粒逐渐长大, 晶粒形状由条状逐渐变为盘状, 在La掺杂CaBi₂Nb₂O₉也有类似现象^{[ 28]}.

	Figure Option View Download New Window
	图3 NBN-Mn陶瓷抛光热腐蚀表面的SEM照片Fig. 3 SEM images for polished and thermally etched surfaces of NBN-Mn ceramics(a) x=0; (b) x=1.0; (c) x=3.0; (d) x=8.0

表1列出了NBN系列陶瓷的机电性能. 随着引入NBN的Mn( x≥0)的增加, Q_m先增加后减小, 在 x=8.0时达到最大值3120; 其 d₃₃也表现出相似的变化趋势, 在 x=8.0时 d₃₃达到20 pC/N, 相较于纯的NBN提高了一倍. 此外, 由表1还可看出Mn掺杂对NBN机电性能影响的变化趋势. 样品( x=8.0)的 k_p、 k _t分别为12.37%和21.09%, 其中 k_p远小于 k _t表现出明显的各向异性. 综上所述, 加入Mn明显改善了NBN系列陶瓷的电性能.

表1 Mn掺杂NBN陶瓷电性能随掺杂量 x的变化关系 Table 1 Electrical properties of Mn-doped NBN ceramics as a function of x

图4(a)是Mn掺杂NBN陶瓷的介电常数(ε_r)在100 kHz下测得的随温度的变化关系曲线, 由图4可知所有NBN陶瓷的居里点都在700℃以上. 如表1可知随着掺杂Mn量的增加, 该陶瓷在200~700℃范围内, 介电常数随着Mn的增加而增大.

	Figure Option View Download New Window
	图4 NBN-Mn陶瓷的介电常数( ε_r) (a)和介电损耗(tan δ) (b)与温度的变化关系Fig. 4 Temperature dependence of the dielectric constant ε_r (a) and loss tangent tan δ (b) for the NBN-Mn ceramics

图4(b)是给出了Mn掺杂NBN陶瓷的介电损耗(tan δ)在100 kHz下与温度的关系曲线. 随着Mn的引入, 其损耗稍微增大, 同时NBN陶瓷在200℃时出现了一个反常峰, 且随着Mn的含量增加, 反常峰越来越明显, 这可能是由于过量的Mn与挥发的Bi₂O₃形成了BiMnO₃而产生了相变^{[ 29]}.

图5是在80 kV/cm下, NBN-Mn陶瓷样品的 P-E电滞回线. 随着Mn的引入, 电滞回线逐渐变得饱和. 当 x由1.0增加到8.0时, 其剩余极化值显著提高(尤其是3.0~8.0), 从3.54增加至7.01 μC/cm², 为纯NBN的2倍, 这可能归因于掺杂引起的适度晶格畸变易使样品的 P_r变大^{[ 30]}. 但与 P_r相比较, 其矫顽场 E_c增幅较小, 从27.35增加到35.32. 由此可知, 可以引入Mn改善其铁电性能, 提高极化率, 从而显著地提高NBN-Mn的压电性能.

	Figure Option View Download New Window
	图5 NBN-Mn陶瓷的电滞回线Fig. 5 P- E hysteresis loops of the NBN-Mn ceramics

图6是NBN系列陶瓷的 d₃₃随退火温度变化的曲线图, 如图可知, 随着Mn的引入, 陶瓷 d₃₃先增大后减小, 其高温的稳定性得到很好地改善. 纯NBN陶瓷的 d₃₃在退火温度超过400℃后开始急剧下降, 700℃退火后, d₃₃仅为原来的40%(~4 pC/N). 掺8.0mol%Mn的样品的 d₃₃随退火温度的升高表现较为平稳, 到700℃退火后 d₃₃仍大于室温的75%, 说明其在高温领域有应用前景. 该现象在NBN-LiNbO₃^{[ 21]}中也有类似的报道.

	Figure Option View Download New Window
	图6 NBN-Mn 陶瓷的 d₃₃ 随退火温度变化曲线Fig. 6 Influence of annealing temperature on d₃₃of the NBN-Mn ceramics

图7显示 x=8.0时, 样品 k_p、 k _t、 d₃₃和 Q_m随温度的变化关系曲线. 室温时, k_p为12.37%, 温度升高到600℃时仍接近6%. k _t在室温时为一较高值(21.09%), 继续升高温度至700℃时, 其值仍大于12%. d₃₃随温度升高变化较小, 在温度升高至700℃时仍保持在70%以上. 室温下 Q_m为3120, 比(Li, Ce)掺杂NBN(2600)^{[ 20]}的高, 稍低于NBN单晶(3800)^{[ 12]}. 随着温度升高, Q_m呈直线下降趋势. 由上可知, Na_0.5Bi_2.5Nb₂O₉+ 8.0mol%Mn材料在高温表现出良好的稳定性.

	Figure Option View Download New Window
	图7 NBN-Mn( x=8.0)陶瓷的 k_p、 k_t、 d₃₃和 Q_m随温度的变化Fig. 7 k_p, k_t, d₃₃ and Q_m for the NBN-Mn ceramic x=8.00) as a function of temperature

3 结论

1) 所有样品均具有单一的正交铋层状结构, 其最强峰(115)在 x≤3.0时, 朝小角度偏移; 当3.0≤ x≤8.0时, 向大角度方向偏移, 当 x≥9.0时, 其又开始向小角度偏移.

2) 掺杂Mn能显著地提高其剩余极化强度, 特别是 x从3.0到8.0时, 其 P_r从3.54提高到 7.01 μC/cm²; 同时Mn的引入可以促进陶瓷的极化, 导致其电性能显著升高, 且在最佳性能点 x=8.0时, 其 d₃₃和 Q_m分别为20 pC/N(为纯的NBN陶瓷的一倍)和3120(与纯的NBN陶瓷相比提高了一倍多).

3) 随着引入Mn的量的增加( x≥3.0), 介电温谱在200℃出现了一个BiMnO₃反常峰.

4)引入Mn没有大幅度降低 T _c(且都在700℃以上), 并且随着Mn的引入, 其热稳定性得到显著地提高.

参考文献

View Option

[1]	YAN Hai-Xue, LI Cheng-En, ZHOU Jia-Guang, et al. Structures and properties of bismuth layer-structured piezoelectric ceramics with high T_c. Journal of Inorganic Materials, 2000, 15(2): 209-220. [本文引用:2] [JCR: 0.531] [CJCR: 1.106]
[2]	范素华, 张丰庆, 胡广达, 等. 烧结温度对CaBi₄Ti₄O₁₅陶瓷电性能的影响. 人工晶体学报, 2007, 36(2): 396-399. [本文引用:2]
[3]	Wang C M, Zhang S J, Wang J F, et al. Electromechanical properties of calcium bismuth niobate (CaBi₂Nb₂O₉) ceramics at elevated temperature. Materials Chemistry and Physics, 2009, 118(1): 21-24. [本文引用:2] [JCR: 2.072]
[4]	Wang C M, Wang J F, Zheng L M, et al. Enhancement of the piezoelectric properties of sodium lanthanum bismuth titanate (Na_{0. 5}La_{0. 5}Bi₄Ti₄O₁₅) through modification with cobalt. Materials Science and Engineering B, 2010, 171(1/2/3): 79-85. [本文引用:2] [JCR: 1.846]
[5]	Gai Z G, Wang J F, Sun W B, et al. Ultrahigh temperature Bi₃Ti_{0. 96}Sc_{0. 02}Ta_{0. 02}NbO₉-based piezoelectric ceramics. Journal of Applied Physics, 2008, 104(2): 4106-4109. [本文引用:2] [JCR: 2.21]
[6]	GU Da-Guo, LI Guo-Rong, ZHENG Liao-Ying, et al. Electrical properties of Mn-modified CaBi₄Ti₄O₁₅ piezoelectrics for high temperature application. Journal of Inorganic Materials, 2008, 23(3): 626-630. [本文引用:3] [JCR: 0.531] [CJCR: 1.106]
[7]	ZHANG Li-Na, LI Guo-Rong, ZHAO Su-Chuan, et al. Electrical behavior of Nb-doped Bi₄Ti₃O₁₂ layer-structured ferroelectric ceramics. Journal of Inorganic Materials, 2005, 20(6): 1389-1395. [本文引用:1] [JCR: 0.531] [CJCR: 1.106]
[8]	JIANG Xiang-Ping, YANG Qing, CHEN Chao, et al. Nb-modified Bi₄Ti₃O₁₂ piezoelectric for high temperature applications. Journal of Inorganic Materials, 2010, 25(11): 1169-1174. [本文引用:1] [JCR: 0.531] [CJCR: 1.106]
[9]	Nagata H, Matsuzawa S, Tokutsu T, et al Temperature dependence of piezoelectric properties on Nd and V co-substituted Bi₄Ti₃O₁₂ ceramics for ceramic resonator applications. Ceramics International, 2009, 35(1): 163-167. [本文引用:1] [JCR: 1.789]
[10]	Yokoi A, Masumoto H, Sugishita J. Phase transition-crystal structure relations in ferroelectric Bi_{2. 5}Na_{1. 5}Nb₃O₁₂ compound by molecular dynamics simulation. Materials Chemistry and Physics, 2009, 116(1): 16-20. [本文引用:1] [JCR: 2.072]
[11]	Huang X Y, Chen Z G, Zhen X L, et al. Dielectric and piezoelectric Properties of Ca₁-_x(Li, Ce)_x_/2Bi₄Ti₄O₁₅ ceramics. Journal of Rare Metals. Spl. , 2007, 25(1): 158-162. [本文引用:1]
[12]	Aoyagi Rintaro, Takeda Hiroaki, Okamura Soichiro, et al. Synthesis and electrical properties of sodium bismuth niobate Na_{0. 5}Bi_{2. 5}Nb₂O₉. Materials Research Bulletin, 2003, 38(1): 25-32. [本文引用:3] [JCR: 1.913]
[13]	Hou Y D, Zhu M K, Gao F, et al. Piezoelectric properties of new MnO₂-added 0. 2 PZN–0. 8 PZT ceramic. J. Am. Ceram. Soc. , 2004, 87(5): 847-850. [本文引用:2] [JCR: 2.107]
[14]	Nagata H, Takenaka T J. Additive effects on electrical properties of (Bi_1/2Na_1/2)TiO₃ ferroelectric ceramics. Euro. Ceram. Soc. , 2001, 21(10/11): 1299-1302. [本文引用:1]
[15]	Zhang S J, Eitel R E, Rand all C A, et al. Manganese-modified BiScO₃–PbTiO₃ piezoelectric ceramic for high-temperature shear mode sensor. Appl. Phys. Lett. , 2005, 86(26): 62904. [本文引用:1] [JCR: 3.794]
[16]	Szwagierczak D, Kulawik J J. Influence of MnO₂ and Co₃O₄ dopants on dielectric properties of Pb(Fe_2/3W_1/3)O₃ ceramics. Euro. Ceram. Soc. , 2005, 25(9): 1657-1662. [本文引用:1]
[17]	Matsushita Mitsuhiro, Aoyagi Rintaro, Takeda Hiroaki, et al. Piezoelectric properties of sodium bismuth tantalate Na_{0. 5}Bi_{2. 5}- Ta₂O₉ dense ceramics. Japanese Journal of Applied Physics, 2004, 43(10): 7164-7168. [本文引用:2] [JCR: 1.067]
[18]	Gao Daojiang, Kwok K W, Lin Dunmin. Microstructure, piezoelectric and ferroelectric properties of Mn-added Na_{0. 5}Bi_{4. 5}Ti₄O₁₅ ceramics. Current Applied Physic, 2011, 11(3): 124-127. [本文引用:2] [JCR: 1.814]
[19]	Kano J, Yin Q R, Kojima S, et al. Vibrational and dielectric properties of MnO₂-doped bismuth layered-structure ferroelectrics . Applications of Ferroelectrics, 2007, 16: 478-480. [本文引用:2]
[20]	Gai Zhi-Gang, Wang Jin-Feng, Zhao Ming-Lei, et al. High temperature (NaBi)_{0. 48}□_{0. 04}Bi₂Nb₂O₉-based piezoelectric ceramics. Appl. Phys. Lett. , 2006, 89(20): 012907-1-3. [本文引用:3] [JCR: 3.794]
[21]	Jiang Xiang-Ping, Yang Qing, Chen Chao, et al Microstructure and properties of high-temperature materials (1-x)Na_{0. 5}Bi_{2. 5}Nb₂O₉- xLiNbO₃. J. Am. Ceram. Soc. , 2010, 493: 276-280. [本文引用:3] [JCR: 2.107]
[22]	Wang C M, Wang J F, Zhang S J, et al. Electromechanical properties of A-site (Li Ce) modified sodium bismuth titanate (Na_{0. 5}Bi_{4. 5}Ti₄O₁₅) piezoelectric ceramics at elevated temperature. J. Appl. Phys. , 2009, 105(9): 094110-1-5. [本文引用:1] [JCR: 0.71]
[23]	Wang C. M. , Wang J. F. High performance aurivillius phase sodium- potassium bismuth titanate lead-free piezoelectric ceramics with lithium and cerium modification. Appl. Phys. Lett. , 2006, 89(20): 202905-1-3. [本文引用:1] [JCR: 3.794]
[24]	Gai Zhi-Gang, Feng Yuan-Yuan, Wang Jin-Feng, et al. The effect of (Li, Ce) doping in Aurivillius phase material (Na_{0. 52}K_{0. 42}Li_{0. 06})_{0. 5}Bi_{2. 5}(Nb_{1. 88}Sb_{0. 06}Ta_{0. 06})O₉. Phys. Status Solidi A, 2010, 207(8): 1792-1795. [本文引用:2] [JCR: 1.463]
[25]	Chaker Chiheb, Abdelmoulaa Najmeddine, Gagoub Yaovi, et al. Study of the Na₁-_xBi_xNb₁-_xMn_xO₃ ceramics by X-ray diffraction, dielectric and Raman spectroscopy. Solid State Communications, 2011, 151(10): 763-767. [本文引用:1] [JCR: 1.534]
[26]	杜红亮, 杜红娜, 周万城, 等(DU Hong-Liang, et al). 锰掺杂对PNW-PMS-PZT压电陶瓷结构和性能的影响. 硅酸盐学报(Journal of the Chinese Ceramic Society), 2005, 33(6): 777-779. [本文引用:1] [CJCR: 0.969]
[27]	Li G R, Zheng L Y, Yin Q R. Microstructure, domain morphology and piezoelectric properties of Si-doped Pb(Mn_1/3Sb_2/3)O₃- Pb(Zr, Ti)O₃ systems. J. Appl. Phys. , 2005, 119(1): 46-50. [本文引用:1] [JCR: 0.71]
[28]	Zhang Xiaodong, Yan Haixue, Michael J. Reece. Effect of A site substitution on the properties of CaBi₂Nb₂O₉ ferroelectric ceramics. J. Am. Ceram. Soc. , 2008, 91(9): 2928-2932. [本文引用:1] [JCR: 2.107]
[29]	Santos A M, Parashar S, Raju A R, et al. Evidence for the likely occurrence of magnetoferroelectricity in the simple perovskite, BiMnO₃. Solid State Communications, 2002, 122(1/2): 49-52. [本文引用:1] [JCR: 1.534]
[30]	Chen Q, Xu Z J, Chu R Q, et al. Ferroelectric and dielectric properties of Sr₂-_x(Na, K)_xBi₄Ti₅O₁₈. lead-free piezoelectric ceramics. Physica B: Condensed Matter, 2010, 405(13): 2781-2784. [本文引用:1] [JCR: 1.327]

2000

0.531

1.106

Journal of Inorganic Materials. 2000, 15(2):209-220

Structures and properties of bismuth layer-structured piezoelectric ceramics with high T_c

Shanghai Institute of Ceramics; Chinese Academy of Sciences; Shanghai 200050; China

This paper reviewed the structures and properties of bismuth layer-structured piezoelectric
ceramics. The structures of bismuth layer-structured piezoelectric ceramics are built up by the regular intergrowth of (Bi₂O₂)²⁺
layers and perovskite (A_m-1B_mO_3m+1)^2- slabs where A is a combination of cations adequate for 12-coordinated interstices,
B is a combination of cations well suited to octahedral coordinated, and m is an integer usually lying to the range 1-5. By comparison with
barium titanate (BaTiO_3) or lead zirconate titanate (PZT) ceramics, the bismuth layer-structured piezoelectric ceramics are characterized
by: (1) lower dielectric constant; (2) higher Curie temperature; (3) stronger anisotropy in electromechanical coupling factors; (4) lower
ageing rate; (5) higher resistivity; …etc..

Previous studies showed that Curie temperature depends on atomic displacement of polarization cations, spontaneous polarization, bismuth
content in the cubooctahedral cavities, and the nature of the substituting cations such as inonic radius, electronegativities and electronic
configuration. An essentially weak point of bismuth layer-structured piezoelectric ceramics is low piezoelectric activity which can be
solved by chemical substitution or fabrication methods for orientating the grains in ceramics. It is necessary to study the relationships
between structures and properties of bismuth layer-structured piezoelectric ceramics in order to develop the materials.

综述了铋层状压电陶瓷的结构特点及性能研究．铋层状压电陶瓷的结构由（Ｂｉ_２Ｏ_２）^２＋层和钙钛矿层（Ａ_ｍ－_１Ｂ_ｍＯ_３ｍ＋１）^２－按一定规则共生排列而成．此处Ａ为适合干１２配位的离子；Ｂ为适合于八面体配位的离子，ｍ为一整数，其值一般为１～５．与钛酸钡（ＢａＴｉＯ_３）或锆钛酸铅（ＰＺＴ）陶瓷相比，铋层状压电陶瓷具有以下特点：低介电常数、高Ｔ_ｃ、机电耦合系数各向异性明显、低老化率、高电阻率等．先前研究证明，居里温度不仅与极化原子位移、自发极化强度、Ａ位Ｂｉ含量有关，而且还与取代离子的特性诸如离子半径、电负性、核外电子排布有关．压电活性低是铋层状陶瓷的本质缺点，通常发展该材料的途径为化学取代或晶粒取向技术．研究材料结构与性能之间的关系有助于发展铋层状压电陶瓷材料．

... 铋层状(BLSFs)材料具有高居里温度、机电耦合系数, 较好的抗疲劳等特性, 适合做压力传感器、滤波器等^{[1,2,3,4,5,6]} ...

... 5Nb₂O₉和CaBi₄Ti₄O₁₅等BLSFs材料已经被广泛研究^{[1,2,3,4,5,6,7,8,9,10,11,12]} ...

2007

0.0

... 铋层状(BLSFs)材料具有高居里温度、机电耦合系数, 较好的抗疲劳等特性, 适合做压力传感器、滤波器等^{[1,2,3,4,5,6]} ...

... 5Nb₂O₉和CaBi₄Ti₄O₁₅等BLSFs材料已经被广泛研究^{[1,2,3,4,5,6,7,8,9,10,11,12]} ...

2009

2.072

0.0

... 铋层状(BLSFs)材料具有高居里温度、机电耦合系数, 较好的抗疲劳等特性, 适合做压力传感器、滤波器等^{[1,2,3,4,5,6]} ...

... 5Nb₂O₉和CaBi₄Ti₄O₁₅等BLSFs材料已经被广泛研究^{[1,2,3,4,5,6,7,8,9,10,11,12]} ...

2010

1.846

0.0

... 铋层状(BLSFs)材料具有高居里温度、机电耦合系数, 较好的抗疲劳等特性, 适合做压力传感器、滤波器等^{[1,2,3,4,5,6]} ...

... 5Nb₂O₉和CaBi₄Ti₄O₁₅等BLSFs材料已经被广泛研究^{[1,2,3,4,5,6,7,8,9,10,11,12]} ...

2008

2.21

0.0

... 铋层状(BLSFs)材料具有高居里温度、机电耦合系数, 较好的抗疲劳等特性, 适合做压力传感器、滤波器等^{[1,2,3,4,5,6]} ...

... 5Nb₂O₉和CaBi₄Ti₄O₁₅等BLSFs材料已经被广泛研究^{[1,2,3,4,5,6,7,8,9,10,11,12]} ...

2008

0.531

1.106

Journal of Inorganic Materials. 2008, 23(3):626-630 DOI:10.3724/SP.J.1077.2008.00626

Electrical properties of Mn-modified CaBi₄Ti₄O₁₅ piezoelectrics for high temperature application

State Key Lab of High Performance Ceramics and Superfine Microstructure, Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai 200050, China

Mn-modified CaBi₄Ti₄O₁₅ (CBT+x mol% MnCO₃) layer-structured piezoelectric ceramics were prepared by the solid state reaction technology. All samples have the same Curie temperature of 780℃, but the dielectric loss at high temperature is remarkably lowered by Mn addition. With increasing content of Mn, the remnant polarization is slightly decreased; the dielectric constant at room temperature decreases from 173 to 162; and the mechanical quality factor increases from 2700 to 4400. The piezoelectric constant d₃₃ is enhanced from 7 to 14.5. The resistivity of 1.0mol% Mn modified sample is found to be 10⁸Ω·cm at 500℃, 50 times higher than that of pure CBT. The Arrehenius plot of Mn-modified CBT is fitted by 3 straight lines, while that of pure CBT is fitted by 2 straight lines. The results suggest that the Mn modified CBT is a potential material for high temperature sensing application.

采用固相法制备了Mn改性的CaBi₄Ti₄O₁₅(CBT+x mol% MnCO₃)层状压电陶瓷. 介电温谱显示所有样品居里点在780℃附近, 并且发现该材料在110K处有一介电弛豫峰. Mn的加入显著降低了高温下的介电损耗, 剩余极化轻微降低, 室温介电常数从173减小到162, 同时机械品质因子由2700增加到4400, 显示了硬性掺杂的效果. 在100~600℃范围内, x=1.0的样品比纯组分的电阻率提高了一个数量级以上, 500℃的电阻率提高了约2个数量级(10⁸Ω·cm), 电阻率对温度的Arrhenius拟合由两段过渡到三段, 压电系数d₃₃由7提高到14.5. 实验结果表明, Mn改性的CBT在高温传感器等领域具有应用前景.

... 铋层状(BLSFs)材料具有高居里温度、机电耦合系数, 较好的抗疲劳等特性, 适合做压力传感器、滤波器等^{[1,2,3,4,5,6]} ...

... 5Nb₂O₉和CaBi₄Ti₄O₁₅等BLSFs材料已经被广泛研究^{[1,2,3,4,5,6,7,8,9,10,11,12]} ...

... Mn作为一种常见的添加剂, 具有多种价态(+2,+3,+4), 经常用于钙钛矿与铋层状压电陶瓷的掺杂改性研究^{[6, 13,14,15,16,17,18,19]} ...

2005

0.531

1.106

Journal of Inorganic Materials. 2005, 20(6):1389-1395

Electrical behavior of Nb-doped Bi₄Ti₃O₁₂ layer-structured ferroelectric ceramics

The State Key Lab of High Performance Ceramics and Superfine Microstructure; Shanghai Institute of Ceramics; Chinese Academy of Sciences; Shanghai 200050, China

Nb⁵⁺-doped Bi₄Ti₃O₁₂ layer-structured ferroelectric ceramics were prepared by the solid-state reaction technology. Microstructures of Bi₄Ti₃-_xNb_xO_12+x/2 materials were characterized by XRD and SEM. The results show that Bi₄Ti₃-_xNb_xO_12+x/2 material has a single orthorhombic structure. The grains of polished and thermally etched surfaces reveal a needle-like structure. Electronic conductor mechanism of Bi4Ti_3-xNb_xO_12+x/2 was analyzed by the Arrhe-nius fit of direct current conductivity vs temperature. Dielect constants of Bi₄Ti_3-xNb_xO_12+x/2 ceramics increase by Nb⁵⁺ doping. The Curie temperatures decrease linearly with the increase of Nb⁵⁺ concedntration. DSC results show that Bi₄Ti_3-xNb_xO_12+x/2 materials undergo the firstorder ferroelectric phase transition at the Curie point. Nb⁵⁺ doping Bi₄Ti₃O₁₂ ceramics results in an increase remanent polarizatgion (P_r) according to ferroelectric test results. The reason is that Nb⁵⁺ substituting for Ti⁴⁺ decreases the concentration of oxygen vacancies. The effect of oxygen vacancies on domain pinning is reduced significantly.

采用固相烧结工艺制备了Nb⁵⁺掺杂的Bi₄Ti₃O₁₂层状结构铁电陶瓷.运用XRD 和AFM对Bi₄Ti_3-xNb_xO_12+x/2材料的微观结构进行表征,发现所制备的陶瓷均具有单一的正交相结构,抛光热腐蚀表面晶粒的显微形貌表现为随机排列的棒状结构.通过对材料直流电导率与温度关系的Arrhenius拟合,分析丁Bi₄Ti_3-xNb_xO_12+x/2的导电机理. Nb⁵⁺掺杂提高了材料的介电常数,但居里温度随掺杂含量的增加呈线性下降趋势.DSC结果显示Bi₄Ti_3-xNb_xO_12+x/2材料在居里温度处经历了一级铁电相变.样品的铁电性能测试结果表明, Nb⁵⁺掺杂Bi₄Ti₃O₁₂提高了材料的剩余极化Pr,这主要是由于^_Nb5+取代Ti⁴⁺大大降低了材料中氧空位的浓度,使得氧空位对畴的钉扎作用减弱的缘故.

... 5Nb₂O₉和CaBi₄Ti₄O₁₅等BLSFs材料已经被广泛研究^{[1,2,3,4,5,6,7,8,9,10,11,12]} ...

2010

0.531

1.106

Journal of Inorganic Materials. 2010, 25(11):1169-1174 DOI:10.3724/SP.J.1077.2010.01169

Nb-modified Bi₄Ti₃O₁₂ piezoelectric for high temperature applications

(Department of Material Science and Engineering, Jingdezhen Ceramic Institute, Jingdezhen 333001, China)

Nb-modified Bi₄Ti₃O₁₂ (BIT+xmol%Nb₂O₅) layer-structured piezoelectric ceramics were prepared by the solid state reaction method (at the pressure of about 12MPa). The quantity of grain growth along a-b plane is much more than that along c-axis with the increasing amount of Nb₂O₅. After Nb₂O₅doping, the size of grain becomes small and unanimity. The electrical conductivity and dielectric loss are significantly reduced, while relative density, piezoelectric activity and electromechanical properties of Bi₄Ti₃O₁₂-based ceramics are improved by the modification of Nb₂O₅. The electrical conductivity of BIT+4.00mol% Nb₂O₅(10^-13S/cm) decreases by 2 orders of magnitude compared with the undoped one. Besides, the BIT+4.00mol% Nb2O5 ceramic exhibits optimum electrical properties: relative density r=98.7%, tanδ=0.23%, d₃₃=18pC/N, Q_m=2804, k_p=8.1%, k_t=18.6%, N_p=2227Hz·m and N_t=2025Hz·m, and the d₃₃ remains 17pC/N after annealing at 600℃, which indicates that the ceramic is a potential material for high temperature applications.

采用固相法(成型压力~12MPa)获得了Nb改性的Bi₄Ti₃O₁₂(BIT+xmol%Nb2O5)层状压电陶瓷. 研究发现随着Nb₂O₅含量的增加, a-b面取向的晶粒逐渐增多, 晶粒尺寸愈细化与均匀. Nb₂O₅的引入明显降低了BIT系列陶瓷的导电率和介电损耗, 提高了陶瓷的相对密度﹑压电与机电性能. 适量Nb₂O₅(x=4.00)掺杂时, 陶瓷的电导率(~10?13S/cm)比纯BIT的降低了2个数量级, 且该陶瓷的相对密度r=98.7%, tanδ=0.23%, d₃₃=18pC/N, Q_m=2804, k_p=8.1%, k_t=18.6%, N_p=2227Hz·m, N_t=2025Hz·m. BIT+xmol%Nb₂O₅(x=4.00)陶瓷在600℃经退极化处理后, 其d₃₃基本保持不变(~17pC/N), 表明该材料在高温器件领域具有良好的应用前景.

... 5Nb₂O₉和CaBi₄Ti₄O₁₅等BLSFs材料已经被广泛研究^{[1,2,3,4,5,6,7,8,9,10,11,12]} ...

2009

1.789

0.0

Ceramics International. 2009, 35(1):163-167 DOI:10.1016/j.ceramint.2007.10.022

Temperature dependence of piezoelectric properties on Nd and V co-substituted Bi₄Ti₃O₁₂ ceramics for ceramic resonator applications

Abstract

The temperature dependences of the piezoelectric properties of (Bi_4−yNd_y)_1−(x/12)(Ti_3−xV_x)O₁₂ [BNTV-x, y (x = 0.01, y = 0.00–1.00)] were investigated for environmentally friendly lead-free piezoelectric ceramic resonators with low-temperature coefficients of resonance frequency, TC-f. The |TC-f| in the (33) mode improved with increasing concentration of modified Nd ions, y, and exhibited the smallest |TC-f| value of 77.4 ppm/°C at y = 0.75 (BNTV-0.75). The |TC-f| in the other vibration mode (t), was also investigated for the BNTV-0.75 ceramic, and a smaller value of 42 ppm/°C was obtained. The (t) mode of the BNTV-0.75 ceramic showed excellent piezoelectric properties: Q_m = 4200, Q_e max = 31 and TC-f = −49.8 ppm/°C. These properties are very similar to those of commercialized hard PZT ceramics for resonator applications. The BNTV-0.75 ceramic seems to be a superior candidate material for lead-free piezoelectric applications of ceramic resonators.

... 5Nb₂O₉和CaBi₄Ti₄O₁₅等BLSFs材料已经被广泛研究^{[1,2,3,4,5,6,7,8,9,10,11,12]} ...

2009

2.072

0.0

... 5Nb₂O₉和CaBi₄Ti₄O₁₅等BLSFs材料已经被广泛研究^{[1,2,3,4,5,6,7,8,9,10,11,12]} ...

2007

0.0

... 5Nb₂O₉和CaBi₄Ti₄O₁₅等BLSFs材料已经被广泛研究^{[1,2,3,4,5,6,7,8,9,10,11,12]} ...

2003

1.913

0.0

... 5Nb₂O₉和CaBi₄Ti₄O₁₅等BLSFs材料已经被广泛研究^{[1,2,3,4,5,6,7,8,9,10,11,12]} ...

... 5Nb₂O₉(NBN)是一种典型的高温(T_c~780℃)BLSFs材料^[12] ...

... 室温下Q_m为3120, 比(Li, Ce)掺杂NBN(2600)^[20]的高, 稍低于NBN单晶(3800)^[12] ...

2004

2.107

0.0

... Mn作为一种常见的添加剂, 具有多种价态(+2,+3,+4), 经常用于钙钛矿与铋层状压电陶瓷的掺杂改性研究^{[6, 13,14,15,16,17,18,19]} ...

... 适度的扭曲会促进其极化性能, 但是添加过量Mn后, Mn将聚集在晶界, 抑制电畴的反转^[13,26], 并且引入过量Mn伴随着第二相BiMnO₃(111)和BiNbO₄(032)的生成,使其介电损耗增大并导致性能的退化 ...

2001

0.0

... Mn作为一种常见的添加剂, 具有多种价态(+2,+3,+4), 经常用于钙钛矿与铋层状压电陶瓷的掺杂改性研究^{[6, 13,14,15,16,17,18,19]} ...

2005

3.794

0.0

... Mn作为一种常见的添加剂, 具有多种价态(+2,+3,+4), 经常用于钙钛矿与铋层状压电陶瓷的掺杂改性研究^{[6, 13,14,15,16,17,18,19]} ...

2005

0.0

... Mn作为一种常见的添加剂, 具有多种价态(+2,+3,+4), 经常用于钙钛矿与铋层状压电陶瓷的掺杂改性研究^{[6, 13,14,15,16,17,18,19]} ...

2004

1.067

0.0

... Mn作为一种常见的添加剂, 具有多种价态(+2,+3,+4), 经常用于钙钛矿与铋层状压电陶瓷的掺杂改性研究^{[6, 13,14,15,16,17,18,19]} ...

... 5Ti₄O₁₅、Pb (Zr, Ti) O₃、BiScO₃-PbTiO₃和 (Ca,Sr)Bi₄Ti₄O₁₅陶瓷也出现过^{[17,18,19,27]} ...

2011

1.814

0.0

... Mn作为一种常见的添加剂, 具有多种价态(+2,+3,+4), 经常用于钙钛矿与铋层状压电陶瓷的掺杂改性研究^{[6, 13,14,15,16,17,18,19]} ...

... 5Ti₄O₁₅、Pb (Zr, Ti) O₃、BiScO₃-PbTiO₃和 (Ca,Sr)Bi₄Ti₄O₁₅陶瓷也出现过^{[17,18,19,27]} ...

2007

0.0

... Mn作为一种常见的添加剂, 具有多种价态(+2,+3,+4), 经常用于钙钛矿与铋层状压电陶瓷的掺杂改性研究^{[6, 13,14,15,16,17,18,19]} ...

... 5Ti₄O₁₅、Pb (Zr, Ti) O₃、BiScO₃-PbTiO₃和 (Ca,Sr)Bi₄Ti₄O₁₅陶瓷也出现过^{[17,18,19,27]} ...

2006

3.794

0.0

... 为了改善NBN的电性能, Gai等^[20]通过(Li,Ce)掺杂使陶瓷的d₃₃(pc/N)从17提高到27 ...

... 0时, NBN-Mn陶瓷具有典型的层状结构, 这与(Li, Ce)掺杂NBN和LiNbO₃改性的NBN陶瓷的结构相类似^[20,21,24] ...

... 室温下Q_m为3120, 比(Li, Ce)掺杂NBN(2600)^[20]的高, 稍低于NBN单晶(3800)^[12] ...

2010

2.107

0.0

... Jiang等^[21]通过LiNbO₃改性使陶瓷的d₃₃(pc/N)从10提高到21 ...

... 0时, NBN-Mn陶瓷具有典型的层状结构, 这与(Li, Ce)掺杂NBN和LiNbO₃改性的NBN陶瓷的结构相类似^[20,21,24] ...

... 该现象在NBN-LiNbO₃^[21]中也有类似的报道 ...

2009

0.71

0.0

... 1 微结构分析图1是NBN-Mn陶瓷样品的XRD图谱, 可以看出, 在所有NBN-Mn陶瓷中最强峰是(115), 与铋层状结构陶瓷最强峰(112m+1)一致^[22,23] ...

2006

3.794

0.0

... 1 微结构分析图1是NBN-Mn陶瓷样品的XRD图谱, 可以看出, 在所有NBN-Mn陶瓷中最强峰是(115), 与铋层状结构陶瓷最强峰(112m+1)一致^[22,23] ...

2010

1.463

0.0

... 0时, 其又开始向小角度偏移, 表明其晶面间距先增大后变小又再增大^[24] ...

... 0时, NBN-Mn陶瓷具有典型的层状结构, 这与(Li, Ce)掺杂NBN和LiNbO₃改性的NBN陶瓷的结构相类似^[20,21,24] ...

2011

1.534

0.0

... 118 nm)的半径相差较大, 因此这种晶格的扭曲可能是由Mn取代B位的Nb引起的^[25] ...

2005

0.0

0.969

2005

0.71

0.0

... 5Ti₄O₁₅、Pb (Zr, Ti) O₃、BiScO₃-PbTiO₃和 (Ca,Sr)Bi₄Ti₄O₁₅陶瓷也出现过^{[17,18,19,27]} ...

2008

2.107

0.0

... 0时, 随着引入Mn量的增加, 其晶粒逐渐长大, 晶粒形状由条状逐渐变为盘状, 在La掺杂CaBi₂Nb₂O₉也有类似现象^[28] ...

2002

1.534

0.0

... 随着Mn的引入, 其损耗稍微增大, 同时NBN陶瓷在200℃时出现了一个反常峰, 且随着Mn的含量增加, 反常峰越来越明显, 这可能是由于过量的Mn与挥发的Bi₂O₃形成了BiMnO₃而产生了相变^[29] ...

2010

1.327

0.0

... C/cm², 为纯NBN的2倍, 这可能归因于掺杂引起的适度晶格畸变易使样品的P_r变大^[30] ...