Ge掺杂对TiO2-Nb2O5-CaCO3压敏陶瓷结构及性能的影响

doi:10.15541/jim20170237

无机材料学报 ›› 2018, Vol. 33 ›› Issue (4): 447-452.DOI: 10.15541/jim20170237

Ge掺杂对TiO₂-Nb₂O₅-CaCO₃压敏陶瓷结构及性能的影响

康昆勇^1,2,3, 徐开蒙^1,2,3, 刘灿^1,2,3, 杨晓琴^1,2,3, 郑志锋^1,2,3

西南林业大学1. 材料科学与工程学院;
2. 云南省生物质高效利用工程实验室;
3. 云南省高校生物质化学炼制与合成重点实验室, 昆明 650224

收稿日期:2017-05-25 修回日期:2017-08-09 出版日期:2018-04-30 网络出版日期:2018-03-27
作者简介:康昆勇(1973-), 男, 博士. E-mail: kangkunyong@163.com
基金资助:
国家自然科学基金(31670599)

Ge-doping in TiO₂-Nb₂O₅-CaCO₃ Varistor Ceramics: Structure and Property

KANG Kun-Yong^1,2,3, XU Kai-Meng^1,2,3, LIU Can^1,2,3, YANG Xiao-Qing^1,2,3, ZHENG Zhi-Feng^1,2,3

1. Faculty of Materials Science and Engineering, Southwest Forestry University, Kunming 650224, China;
2. Yunnan Provincial Engineering Laboratory for Highly-Efficient Utilization of Biomass, Southwest Forestry University, Kunming 650224, China;
3. Yunnan Provincial University Key Laboratory for Biomass Chemical Refinery & Synthesis, Southwest Forestry University, Kunming 650224, China;

Received:2017-05-25 Revised:2017-08-09 Published:2018-04-30 Online:2018-03-27
About author:KANG Kun-Yong. E-mail: kangkunyong@163.com
Supported by:
National Natural Science Foundation of China (31670599)

摘要/Abstract

摘要：

TiO₂压敏电阻是一种典型的非线性电流-电压电子器件, 本文研究了Ge掺杂对TiO₂-Nb₂O₅-CaCO₃压敏陶瓷的非线性系数α和压敏电压E_B的影响。采用传统的球磨-成型-烧结方法成功制备Ge掺杂TiO₂-Nb₂O₅-CaCO₃压敏陶瓷, 用压敏直流参数仪测试样品的非线性系数α、压敏电压E_B和漏电流J_L等电学性质, 并根据相关公式计算样品平均势垒高度。XRD、XPS、SEM和STEM分析表明, Ge掺杂显著改变TiO₂-Nb₂O₅-CaCO₃压敏陶瓷微结构, 提高非线性系数α和减小压敏电压E_B。当施主Nb₂O₅和受主CaCO₃掺杂浓度分别为0.5mol%时, 掺杂1.0mol% Ge的压敏陶瓷获得了最高的非线性系数和较低的压敏电压(α=10.6, E_B=8.7 V/mm), 明显优于不掺杂Ge的TiO₂-Nb₂O₅-CaCO₃压敏陶瓷。此外, Ge熔点较低, 作为烧结助剂可以降低陶瓷的烧结温度, TiO₂-Nb₂O₅-CaCO₃-Ge压敏陶瓷最佳烧结温度是1300℃。

关键词: TiO₂压敏陶瓷, 非线性系数, 压敏电压, Ge

Abstract:

TiO₂ varistors are typical electronic devices with nonlinear current-voltage property fabricated from TiO₂ ceramics. This study investigated the influence of Ge doping on the nonlinear coefficient α and the breakdown electric field E_B of TiO₂-Nb₂O₅-CaCO₃ varistor ceramics. TiO₂-Nb₂O₅-CaCO₃ varistor ceramics doped with Ge were successfully prepared by using traditional method of ball milling-molding-sintering. The electrical performance, including nonlinear coefficient α, breakdown electric field E_B, and leakage current J_L, was tested with a varistor-direct current-parameter instrument. Average barrier height Φ_B of each sample was calculated by relevant formula. Analysis of X-ray diffraction, X-ray photoelectron spectroscopy, scanning electron microscopy, and scanning transmission electronic microscopy demonstrated that Ge doping notably changed the microstructure of TiO₂-Nb₂O₅-CaCO₃ ceramics, thereby increasing α and decreasing E_B. When Nb₂O₅ and CaCO₃ doping content were 0.5mol%, the TiO₂-Nb₂O₅-CaCO₃ varistor ceramics doping with 1.0 mol% Ge exhibited high α (10.6), low E_B (8.7 V/mm), and highest Φ_B (1.73 eV), superior to previous published findings. Furthermore, Ge with low melting point as sintering aid could reduce the sintering temperature of the varistor ceramics, with optimal sintering temperature at 1300℃.

Key words: TiO₂varistor, nonlinear coefficient, breakdown voltage, Ge

中图分类号:

TP204

康昆勇, 徐开蒙, 刘灿, 杨晓琴, 郑志锋. Ge掺杂对TiO₂-Nb₂O₅-CaCO₃压敏陶瓷结构及性能的影响[J]. 无机材料学报, 2018, 33(4): 447-452.

KANG Kun-Yong, XU Kai-Meng, LIU Can, YANG Xiao-Qing, ZHENG Zhi-Feng. Ge-doping in TiO₂-Nb₂O₅-CaCO₃ Varistor Ceramics: Structure and Property[J]. Journal of Inorganic Materials, 2018, 33(4): 447-452.

图/表 10

表1 样品掺杂含量

Table 1 Doping contents of samples

Sample	Doping content/mol%
Sample	TiO₂	Nb₂O₅	CaCO₃	Ge
#1	99.0	0.5	0.5	0
#2	98.8	0.5	0.5	0.2
#3	98.6	0.5	0.5	0.4
#4	98.4	0.5	0.5	0.6
#5	98.2	0.5	0.5	0.8
#6	98.0	0.5	0.5	1.0
#7	97.8	0.5	0.5	1.2
#8	97.6	0.5	0.5	1.4

表2 烧结温度对样品电学性质的影响(EB/(V·mm-1))

Table 2 Influence of sintering temperature on the electrical properties of samples (EB/(V·mm-1))

Sample	1200℃		1250℃		1300℃		1350℃		1400℃
Sample	α	E_B	α	E_B	α	E_B	α	E_B	α	E_B
#1	—	—	—	—	4.8	28.7	5.8	24.5	6.6	23.7
#2	—	—	4.1	25.2	5.2	23.6	5.1	23.2	4.9	24.5
#3	3.7	28.9	4.7	24.0	6.3	20.5	6.2	21.5	6.1	21.3
#4	4.5	27.4	6.2	21.4	8.4	16.8	8.2	16.4	8.0	16.8
#5	5.4	26.8	6.9	20.1	9.1	12.4	8.9	12.1	8.5	12.7
#6	7.1	26.2	8.5	19.5	10.6	8.7	9.7	8.4	9.3	9.2
#7	6.7	25.4	8.1	18.3	9.2	8.3	8.6	7.6	7.8	8.0
#8	6.2	23.5	7.6	15.6	8.5	7.2	8.0	7.2	7.1	7.5

表3 烧结温度为1300℃, 不同Ge含量TiO2-Nb2O5-CaCO3陶瓷的电学性质

Table 3 Electrical properties of TiO2-Nb2O5-CaCO3 ceramics with different doping contents of Ge sintered at 1300℃

Sample	D_g/μm	ρ_r	α	E_B/(V·mm^-1)	J_L/(μA·cm^-2)	Φ_B/eV
#1	1.05	93.5	4.8	28.7	12.7	0.63
#2	1.46	94.3	5.2	23.6	11.8	0.87
#3	1.92	95.1	6.3	20.5	11.2	1.05
#4	2.48	95.8	8.4	16.8	10.5	1.36
#5	2.83	96.8	9.1	12.4	9.8	1.56
#6	3.15	97.2	10.6	8.7	9.2	1.73
#7	3.75	97.8	9.2	8.3	8.9	1.51
#8	4.12	98.5	8.5	7.2	8.5	1.42

图1 不同Ge含量TiO2-Nb2O5-CaCO3陶瓷的J-E性质

Fig. 1 J-E characteristics of TiO2-Nb2O5-CaCO3 ceramics with different Ge contents

图2 TiO2-Nb2O5-CaCO3陶瓷(a)非线性系数α和压敏电压EB, (b)晶界势垒高度ΦB和漏电流JL与Ge含量的函数关系

Fig. 2 (a) Nonlinear coefficient α and breakdown voltage EB, and (b) grain boundary barrier height ΦB and leakage current density JL as a function of Ge contents

图3 不同Ge含量TiO2-Nb2O5-CaCO3陶瓷的XRD图谱

Fig. 3 XRD patterns of TiO2-Nb2O5-CaCO3 ceramics with different Ge contents (#1,#2, #3, #6, #7, #8) (a) and the enlarged partial spectra (b) of (a)

图4 样品#6的XPS图谱

Fig. 4 XPS spectra of sample #6(a) Full spectrum; (b) Narrow spectrum of Ge in the sample #6

图5 不掺杂Ge(#1)和不同Ge含量(#2, #3, #6, #8)的TiO2-Nb2O5-CaCO3陶瓷SEM照片

Fig. 5 SEM images of TiO2-Nb2O5-CaCO3 ceramics without Ge (#1) and doped with different Ge contents (#2, #3, #6, #8)

图6 TiO2-Nb2O5-CaCO3陶瓷晶粒和晶界元素含量

Fig. 6 Element contents in grain and grain boundary of TiO2-Nb2O5-CaCO3 ceramics(a) Without Ge (#1); (b) Doped with 1.0mol% Ge (#6)

表4 样品#1和样品#6中各元素含量

Table 4 Element contents of sample #1 and sample #6

Position	Element/at%
	O K		Ti K		Nb K		Ca K		Ge K
	#1	#6	#1	#6	#1	#6	#1	#6	#1	#6
1	74.35	73.40	23.25	23.41	0.12	0.09	2.28	2.89	-	0.21
2	73.43	70.48	24.61	25.46	0.20	0.15	1.76	3.75	-	0.16
3	73.64	69.41	25. 48	28.50	0.67	0.69	0.21	0.08	-	1.32
4	77.55	76.12	21.63	21.73	0.55	0.48	0.27	0. 16	-	1.51

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Ge掺杂对TiO₂-Nb₂O₅-CaCO₃压敏陶瓷结构及性能的影响

Ge-doping in TiO₂-Nb₂O₅-CaCO₃ Varistor Ceramics: Structure and Property

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