Li/Ce/La共掺杂对CaBi2Nb2O9陶瓷晶体结构及电学性能的影响

doi:10.15541/jim20180225

摘要/Abstract

摘要：

采用固相反应法制备(Li_0.5Ce_0.25La_0.25)_xCa_1-_xBi₂Nb₂O₉铋层状结构压电陶瓷, 分析多元稀土元素掺杂对CaBi₂Nb₂O₉(CBN)陶瓷晶体结构、微观形貌及电学性能的影响。Rietveld结构精修表明, 多元稀土元素进入晶格内部形成固溶体, 掺杂使晶体结构有由斜方晶系向四方晶系转变的趋势, 反位缺陷中A位的Bi ³⁺具备6s2孤对电子, 抑制这种变化趋势。SEM照片显示, 掺杂主要抑制晶粒沿垂直c轴平面生长, 这是由于稀土氧化物具备较高的熔点, 在烧结过程中不易扩散。准同型相界附近, 垂直b轴方向的a滑移面被打破, 极化方向沿a轴和b轴, 导致压电性能增强。其中, (Li_0.5Ce_0.25La_0.25)_0.17Ca_0.83Bi₂Nb₂O₉陶瓷具备最优异的性能: 居里温度为913 ℃, 压电系数高达16.4 pC/N; 经850 ℃退火2 h, 其d₃₃值为14.0 pC/N, 约为原始值的85.4%。

关键词: 稀土掺杂, 铋层状结构, Rietveld精修, 晶体结构, 压电

Abstract:

(Li_0.5Ce_0.25La_0.25)_xCa_1-_xBi₂Nb₂O₉ Aurivillius phase ceramics were prepared via conventional solid-state sintering route. The effects of co-substitution with different types of rare-earth elements on crystal structure, microstructure and electric properties were investigated. Rietveld-refinement analysis showed that the multiple rare earth elements embedded into the lattice point and formed corresponding solid solutions. The crystal structure tended to transform to tetragonal system from pristine orthorhombic system, whereas Bi ³⁺ in A-site with 6s2 lone pair electrons suppressed this change. SEM images exhibited that the grain growth in the direction perpendicular to the c-axis was restrained, which could be attributed to the rare earth oxides’ high melting point and low diffusion during the sintering process. Morphotropic phase boundary of a glide plane between orthorhombic system and pseudo-tetragonal system vanished, which generated spontaneous polarization along a and b axis and resulted in increase of piezoelectric properties. The obtained (Li_0.5Ce_0.25La_0.25)_0.17Ca_0.83Bi₂Nb₂O₉ ceramics performed optimal piezoelectric properties (d₃₃=16.4 pC/N, T_c=913 ℃) and exhibited excellent thermal stability, remaining 85.4% of their initial d₃₃ values after annealing at 850 ℃ for 2 h. All above results demonsrated that the multidoped materials are promising candidates for ultrahigh temperature applications.

Key words: rare earth element doping, bismuth layered structure, Rietveld refinement, crystal structure, piezoelectric property

中图分类号:

TB34

曾祥雄, 杨进超, 左联, 杨奔奔, 秦峻, 彭志航. Li/Ce/La共掺杂对CaBi₂Nb₂O₉陶瓷晶体结构及电学性能的影响[J]. 无机材料学报, 2019, 34(4): 379-386.

Xiang-Xiong ZENG, Jin-Chao YANG, Lian ZUO, Ben-Ben YANG, Jun QIN, Zhi-Hang PENG. Li/Ce/La Multidoping on Crystal Structure and Electric Properties of CaBi₂Nb₂O₉ Piezoceramics[J]. Journal of Inorganic Materials, 2019, 34(4): 379-386.

图/表 14

图1 (a) CBNLCL-100x陶瓷的XRD图谱, (b)~(c)为XRD局部放大图谱

Fig. 1 (a) XRD patterns and (b, c) expanded XRD patterns of CBNLCL-100x ceramics

表1 CBNLCL-100x陶瓷的精修结果及晶胞参数

Table 1 Crystal data and structure refinement results for CBNLCL-100x ceramics

	CBN	CBNLCL-5	CBNLCL-10	CBNLCL-12	CBNLCL-15	CBNLCL-17
Space group	A2₁am	A2₁am	A2₁am	A2₁am	A2₁am	A2₁am
R_p/%	6.31	7.25	4.86	5.16	4.72	5.01
R_wp/%	8.62	9.57	6.35	6.76	6.04	6.66
R_exp/%	4.77	5.26	5.38	5.15	5.37	5.34
Chi2	3.26	3.31	1.39	1.72	1.26	1.56
a/nm	0.54778(3)	0.54802(2)	0.54778(2)	0.54761(2)	0.54725(2)	0.54704(2)
b/nm	0.54355(3)	0.54372(2)	0.54379(2)	0.54378(2)	0.54396(2)	0.54390(2)
c/nm	2.48626(8)	2.48738(7)	2.48689(6)	2.48641(7)	2.48581(8)	2.48495(7)
V/nm³	0.740273(5)	0.741164(4)	0.740778(4)	0.742398(4)	0.739980(5)	0.739362(4)
a/b	1.00778	1.00790	1.00734	1.00706	1.00606	1.00577
Occupancy of Bi³⁺ at A site	0.108	0.116	0.106	0.108	0.092	0.094

表2 CBNLCL-100x陶瓷部分键长(nm)和键角(°)

Table 2 Selected bond lengths (nm) and bond angles (°) for CBNLCL-100x

Bond type	CBN	CBNLCL-5	CBNLCL-10	CBNLCL-12	CBNLCL-15	CBNLCL-17
Nb—O
Nb—O1—Nb/(°)	158.47	151.84	153.94	152.96	158.99	152.68
O1—Nb—O2/(°)	174.11	172.79	172.99	171.85	171.33	171.81
Nb—O1/nm	0.2120	0.2159	0.2148	0.2143	0.2127	0.2151
Nb—O2/nm	0.2047	0.1888	0.1817	0.1836	0.1804	0.1805
Nb—O4 (1)/nm	0.1938	0.1846	0.1854	0.1848	0.1897	0.1872
Nb—O4 (2)/nm	0.2066	0.2180	0.2174	0.2162	0.2146	0.2127
Nb—O5 (1)/nm	0.1837	0.1968	0.1956	0.1945	0.1943	0.1955
Nb—O5 (2)/nm	0.2135	0.1979	0.1971	0.1997	0.1968	0.2002
Ca1/Bi1/Li/Ce/La—O (A—O)
A—O1(1ong bond along a axis)/nm	0.3191	0.3424	0.3233	0.3250	0.3123	0.3167
A—O1(short bond along a axis)/nm	0.2312	0.2058	0.2291	0.2277	0.2382	0.2364
A—O1(short bond along b axis)/nm	0.2365	0.2627	0.2323	0.2337	0.2315	0.2267
A—O1(1ong bond along b axis)/nm	0.3143	0.2980	0.3199	0.3191	0.3176	0.3235
A—O4 (1)/nm	0.2604×2	0.2539×2	0.2532×2	0.2546×2	0.2573×2	0.2526×2
A—O4 (2)/nm	0.2605×2	0.2549×2	0.2567×2	0.2557×2	0.2584×2	0.2585×2
A—O5 (1)/nm	0.2305×2	0.3208×2	0.3226×2	0.3269×2	0.3235×2	0.3257×2
A—O5 (2)/nm	0.2380×2	0.2422×2	0.2466×2	0.2486×2	0.2448×2	0.2477×2
Bi2/Ca2—O
Bi2/Ca2—O2 (1)/nm	0.2660	0.2553	0.2574	0.2516	0.2587	0.2599
Bi2/Ca2—O2 (2)/nm	0.2775	0.3165	0.2832	0.2827	0.2748	0.2789
Bi2/Ca2—O2 (3)/nm	0.2961	0.2733	0.3075	0.3086	0.3170	0.3111
Bi2/Ca2—O2 (4)/nm	0.3039	0.3313	0.3296	0.3356	0.3310	0.3277

图2 CBNLCL-100x陶瓷的(a)晶胞参数以及(b)晶胞体积和a/b值随掺杂浓度变化关系

Fig. 2 Doping content dependencies of (a) lattice parameters and (b) value of a/b and volume of the CBNLCL-100x ceramics

图3 常温下CBNLCL-100x陶瓷的拉曼图谱, 插图为局域放大图谱

Fig. 3 Raman spectra of the CBNLCL-100x samples at room temperature with insets showing regionally enlarged spectra

图4 CBNLCL-100x陶瓷拉曼曲线拟合图谱

Fig. 4 Fitting curves of Raman spectra of CBNLCL-100x ceramicsBlack line is the measured spectra, red line is the fitted spectra and blue lines are the deconvoluted Lorentzian peaks (Please refer it in Web Edition)

图5 (a) CBNLCL-5和(b) CBNLCL-17晶体在a-c平面投影

Fig. 5 The a-c projections of crystal structure of (a) CBNLCL- 5 and (b) CBNLCL-17

图6 (a) CBNLCL-5和(b) CBNLCL-17晶体在b-c平面投影

Fig. 6 The b-c projections of crystal structure of (a) CBNLCL-5 and (b) CBNLCL-17

图7 A-O1键长(a)沿a轴(b)沿b轴随掺杂含量变化关系

Fig. 7 Compositional dependence of the A-O1 length (a) along a and (b) b axis

图8 (a) CBNLCL-5, (b) CBNLCL-10, (c) CBNLCL-12, (d) CBNLCL-15, (e) CBNLCL-17陶瓷的SEM照片

Fig. 8 SEM images of (a) CBNLCL-5, (b) CBNLCL-10, (c) CBNLCL-12, (d) CBNLCL-15, (e) CBNLCL-17 ceramics

图9 CBNLCL-100x陶瓷的(a)晶粒尺寸统计图以及(b)陶瓷相对密度

Fig. 9 (a) Grain sizes and (b) relative density of CBNLCL-100x ceramics

图10 CBNLCL-100x陶瓷的(a)介电常数和(b)介质损耗随温度变化关系

Fig. 10 Temperature dependence of (a) dielectric constant εr and (b) dielectric loss tanδ of CBNLCL-100x ceramics

图11 常温下CBNLCL-100x 陶瓷的压电性能

Fig. 11 Piezoelectric coefficient d33 values at room temperature of CBNLCL-100x ceramics

图12 CBNLCL-100x陶瓷d33和退火温度关系

Fig. 12 Annealing temperature dependence of piezoelectric coefficient (d33) of CBNLCL-100x ceramics

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Li/Ce/La共掺杂对CaBi₂Nb₂O₉陶瓷晶体结构及电学性能的影响

Li/Ce/La Multidoping on Crystal Structure and Electric Properties of CaBi₂Nb₂O₉ Piezoceramics

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