Sc3+和Ru4+联合取代BZN基陶瓷结构与介电性能的研究

doi:10.15541/jim20140173

摘要/Abstract

摘要：

采用传统的固相反应法制备致密的Bi_1.4Sc_0.1ZnNb_1.5-_xRu_xO₇陶瓷样品, 研究Sc³⁺, Ru⁴⁺共同替代对Bi₂O₃-ZnO-Nb₂O₅陶瓷的相结构、晶体化学特性和介电性能的影响。结果表明: 当掺杂量x≤0.055 mol时, 样品保持单一的立方焦绿石结构。当掺杂量x=0.055 mol时, X射线衍射峰强度变弱, 峰形变宽。随着掺杂量的增加(0≤x≤0.04 mol), 陶瓷样品的晶格常数a和A位离子与第7个氧O′平均键长R_(A-O')逐渐减小, 结晶化学参数键价和AV(O')[A₄]增大, AV(O)[A₂B₂]减小, 48f(O)偏移量ξ增加。室温下样品的介电常数随着掺杂量的增加而减小, 介电损耗逐渐增加, 介电松弛特征减弱。低温下样品呈现明显的弛豫现象, 峰值温度T_m随着掺杂量的增加向高温方向移动。利用修正的Curie-Weiss(C-W)公式对样品ε_r-T曲线进行最小二乘法拟合, 得出样品的弛豫度γ由R0样品的1.57减小到R40样品的1.33。

关键词: 立方焦绿石陶瓷, 48f(O)偏移量ξ, 修正Curie-Weiss公式, 介电弛豫

Abstract:

The dense Bi_1.4Sc_0.1ZnNb_1.5-_xRu_xO₇ ceramics were prepared by traditional solid state reaction. The effect of Sc³⁺ and Ru⁴⁺ co-substitution on the phase structure, crystal chemistry and dielectric properties of Bi₂O₃-ZnO- Nb₂O₅ were investigated. The results reveal that all doped samples show a pure α-BZN phase structure. When x=0.055 mol, the intensity of X-ray diffraction becomes weak and diffraction peaks broaden. With the increase of x, the lattice constant a and the average distance R_(A-O')of the ceramics decrease. The bond valance calculation show that the AV(O')[A₄] and oxygen ξ parameter of 48f(O) increase, but the AV(O)[A₂B₂] gradually decreases with the amount of Ru⁴⁺ increasing. Meanwhile, the dielectric constant of samples decreases and the dielectric loss increases. The dielectric relaxation characteristics are weakened at room temperature while the relaxation behavior at low temperature is obvious. With increasing dopant, T_m shifts toward higher temperature. The ε_r-T curves of samples are fitted by the modified Curie-Weiss’s (C-W) formula. The calculations show that the degree of dielectric relaxation (γ) decreases from 1.57 to 1.33 when the Ru⁴⁺ content increases from 0 to 0.04 mol.

Key words: α-BZN, oxygen parameter ξ at 48f site, modified Curie-Weiss’s formula, dielectric relaxation

中图分类号:

TQ174

张倩, 丁士华, 宋天秀, 彭小松, 刘旭, 蒋旭峰. Sc³⁺和Ru⁴⁺联合取代BZN基陶瓷结构与介电性能的研究[J]. 无机材料学报, 2014, 29(11): 1145-1150.

ZHANG Qian, DING Shi-Hua, SONG Tian-Xiu, PENG Xiao-Song, LIU Xu, JIANG Xu-Feng. Structure and Dielectric Properties of Sc³⁺- and Ru⁴⁺-doped BZN Based Ceramics[J]. Journal of Inorganic Materials, 2014, 29(11): 1145-1150.

图/表 9

图 1 不同Ru4+掺杂量的BSZNR陶瓷样品的XRD图谱

Fig. 1 XRD patterns of BSZNR samples being doped with different amounts of Ru4+

表 1 BSZNR陶瓷样品的晶格常数a、平均键长R(A-O')和理想键长R(B-O)

Table 1 Lattice constant a, average distance of A-O' and expected average B-O bond length for BSZNR samples

Sample	a/nm	R_(A-O')/nm	R_(B-O)/nm
R0	1.0588	0.2292	0.19967
R25	1.0561	0.2287	0.19968
R40	1.0543	0.2283	0.19969
R55	1.0609	0.2297	0.19969

表 2 (Bi1.4Sc0.1Zn0.5)(Zn0.5Nb1.5-xRux)O7样品的键价和AV(O')s

Table 2 The AV(O')s for O' dependent upon local [A4] stoichiometry for (Bi1.4Sc0.1Zn0.5)(Zn0.5Nb1.5-xRux)O7 samples

AV(O')[A₄]	[Bi₄]	[Bi₃Zn]	[Bi₂Zn₂]	[Sc₃Zn]
R0	2.3154	1.9405	1.5656	1.1093
R25	2.3517	1.9709	1.5901	1.1267
R40	2.3773	1.9924	1.6074	1.1390

表 3 (Bi1.4Sc0.1Zn0.5)(Zn0.5Nb1.5-xRux)O7样品的键价和AV(O)s

Table 3 The AV(O)s for O dependent upon local [A2B2] stoichiometry for (Bi1.4Sc0.1Zn0.5)(Zn0.5Nb1.5-xRux)O7 samples

AV(O)[A₂B₂]	[Bi₂Ru₂]	[Bi₂RuNb]	[BiZnRu₂]	[BiZnRuNb]
R0	1.2944	1.4435	1.7449	1.6678
R25	1.2942	1.4432	1.7444	1.6673
R40	1.2941	1.4430	1.7444	1.6670

图 2 BSZNR陶瓷样品的SEM照片

Fig. 2 SEM images of BSZNR samples (a) x=0; (b) x=0.025 mol; (c) x=0.040 mol; (d) x=0.055 mol

图 3 BSZNR样品介电常数和损耗随频率的变化曲线

Fig. 3 Frequency dependence of dielectric properties of BSZ-NR samples

图 4 BSZNR陶瓷样品的介电温谱图

Fig. 4 Temperature dependence of dielectric constant of BSZ-NR ceramics

图 5 BSZNR样品的介电温谱图在1MHz下居里外斯拟合曲线

Fig. 5 Fitted curves and experimental data of modified C-W law of BSZNR samples at 1 MHz

表 4 1 MHz 频率下BSZNR样品的介电弛豫峰温度Tm, 最大介电常数εm, 48f(O)的偏移量ξ和C-W弛豫拟合参数

Table 4 Temperature of maximum dielectric constant Tm, maximum dielectric constant εm, oxygen parameter ξ at 48f site and parameter of C-W relaxation

Sample	ε_m	T_m(1MHz)/℃	ξ/nm	C/K	γ
R0	143.6470	-108.1	0.03157	1.0628×10⁷	1.57
R25	125.0102	-92.6	0.03171	2.0416×10⁷	1.40
R40	125.0039	-91.3	0.03180	4.3057×10⁷	1.33

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Sc³⁺和Ru⁴⁺联合取代BZN基陶瓷结构与介电性能的研究

Structure and Dielectric Properties of Sc³⁺- and Ru⁴⁺-doped BZN Based Ceramics

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