BaTiO3陶瓷的低温冷烧结制备及性能研究

doi:10.15541/jim20220115

无机材料学报 ›› 2022, Vol. 37 ›› Issue (8): 903-910.DOI: 10.15541/jim20220115

BaTiO₃陶瓷的低温冷烧结制备及性能研究

韦婷婷(), 徐华蕊(), 朱归胜, 龙神峰, 张秀云, 赵昀云, 江旭鹏, 宋金杰, 郭宁杰, 龚祎鹏

桂林电子科技大学, 材料科学与工程学院,电子信息材料与器件教育部工程研究中心, 广西信息材料重点实验室,桂林 541004

收稿日期:2022-03-04 修回日期:2022-04-12 出版日期:2022-08-20 网络出版日期:2022-04-26
通讯作者: 徐华蕊, 教授. E-mail: huaruixu@guet.edu.cn
作者简介:韦婷婷(1995-), 女, 硕士研究生. E-mail: 631359334@QQ.com
基金资助:
国家自然科学基金重点项目(U21A2065);广西科技计划项目(桂科AA21077018);广西科技计划项目(桂科AB20297053);“科技助力经济2020”重点专项(SQ2020YFF0425649);广西信息材料重点实验室基金(201002-Z)

Preparation and Properties of BaTiO₃ Ceramics by Low Temperature Cold Sintering

WEI Tingting(), XU Huarui(), ZHU Guisheng, LONG Shenfeng, ZHANG Xiuyun, ZHAO Yunyun, JIANG Xupeng, SONG Jinjie, GUO Ningjie, GONG Yipeng

Engineering Research Center of Electronic and Information Materials and Devices, Ministry of Education; Guangxi Key Laboratory of Information Materials; College of Materials Science and Engineering, Guilin University of Electronic Science and Technology, Guilin 541004, China

Received:2022-03-04 Revised:2022-04-12 Published:2022-08-20 Online:2022-04-26
Contact: XU Huarui, professor. E-mail: huaruixu@guet.edu.cn
About author:WEI Tingting(1995-), female, Master candidate. E-mail: 631359334@QQ.com
Supported by:
National Natural Science Foundation of China(U21A2065);Guangxi Science and Technology Project(AA21077018);Guangxi Science and Technology Project(AB20297053);“Science and Technology Help the Economy 2020” Key Project(SQ2020YFF0425649);Guangxi Key Laboratory of Information Materials Fund(201002-Z)

摘要/Abstract

摘要：

近年来, 冷烧结低温制备陶瓷引起了很大关注, 并在BaTiO₃陶瓷的制备上取得了一定进展。为了提高冷烧结BaTiO₃陶瓷性能, 本研究采用水热法制备了分散性好、粒径为100 nm的四方相(晶格参数c/a为1.0085) BaTiO₃粉末。采用0.1 mol/L的乙酸在100 ℃/1 h的条件下对粉末进行水热活化处理。以质量分数10% Ba(OH)₂·8H₂O为熔剂, 在350 MPa、400 ℃/1 h的条件下对粉体进行冷烧结, 最后经600 ℃/0.5 h退火获得了相对密度为96.62%、晶粒尺寸为180 nm, 常温介电(ε_r)为2836, 介电损耗(tanδ)低至0.03的BaTiO₃陶瓷。乙酸处理后高活性粉末表面形成的非晶钛层有效促进了陶瓷的致密化, 抑制了杂相的生成和晶粒长大, 提高了介电性能, 大幅改善了冷烧结BaTiO₃陶瓷出现的介电弥散现象, 从而实现了BaTiO₃陶瓷的低温冷烧结制备。

关键词: 纳米BaTiO₃, 介电陶瓷, 冷烧结, 低温制备, 介电性能

Abstract:

Preparation of ceramics by cold sintering process has attracted great attention, and some progress has been made in the preparation of BaTiO₃ ceramics. In order to improve the performance of cold sintered BaTiO₃ ceramics, BaTiO₃ powder with good dispersion, particle size of 100 nm and tetragonality (crystal parameter c/a of 1.0085) was prepared by hydrothermal method, and then the powder was hydrothermally activated at 100 ℃ for 1 h with 0.1 mol/L acetic acid. Dense BaTiO₃ ceramics were prepared by the Cold Sintering Process at 400 ℃, under a uniaxial pressure of 350 MPa for 1 h using 10% Ba(OH)₂·8H₂O (in mass) as flux. The as-prepared ceramic pellets were further annealed at 600 ℃ for 0.5 h. In the end, BaTiO₃ceramic sample obtained excellent characteristics with relative density of 96.62%, grain size of 180 nm, dielectric constant (ε_r) of 2836, and dielectric loss (tanδ) of 0.03. An amorphous titanium layer is formed on the surface of the highly active powder after acetic acid treatment, which effectively promotes the densification of ceramics, inhibits the formation of impurity phases and grain growth, improves the dielectric properties, greatly improves the dielectric dispersion phenomenon of cold sintered BaTiO₃ ceramics, and realizes the low temperature cold sintering of BaTiO₃ ceramics.

Key words: nano-BaTiO₃, dielectric ceramics, cold sintering, low temperature preparation, dielectric properties

中图分类号:

TQ174

韦婷婷, 徐华蕊, 朱归胜, 龙神峰, 张秀云, 赵昀云, 江旭鹏, 宋金杰, 郭宁杰, 龚祎鹏. BaTiO₃陶瓷的低温冷烧结制备及性能研究[J]. 无机材料学报, 2022, 37(8): 903-910.

WEI Tingting, XU Huarui, ZHU Guisheng, LONG Shenfeng, ZHANG Xiuyun, ZHAO Yunyun, JIANG Xupeng, SONG Jinjie, GUO Ningjie, GONG Yipeng. Preparation and Properties of BaTiO₃ Ceramics by Low Temperature Cold Sintering[J]. Journal of Inorganic Materials, 2022, 37(8): 903-910.

图/表 12

图1 A1、A2粉末的XRD图谱

Fig. 1 XRD patterns of A1 and A2 powders (b) Local magnification XRD patterns in the range of 2θ=43°-47°

图2 (a)A1和(b)A2粉末的PSD曲线

Fig. 2 PSD curves of powders (a)A1 and (b)A2

表1 粉体粒径分布数据

Table 1 Size distribution of powders

Powder	D₁₀/nm	D₅₀/nm	D₉₀/nm
A₁	74	103	124
A₂	76	107	129

图3 (a~c)A1和(d~f)A2粉末的SEM和TEM照片

Fig. 3 SEM and TEM images of powders (a-c)A1 and (d-f)A2

图4 粉末(a)A1和(b)A2的Ba3d轨道光电子能谱图

Fig. 4 Ba3d orbital photoelectron spectra of powders (a) A1 and (b) A2

表2 粉末A1、A2表面各元素的相对原子比

Table 2 Relative atomic ratio of A1 and A2 powder surfaces

Powder	Ba	Ti	O	C	Ba/Ti
A₁	10.88	10.81	39.81	38.45	1.0075
A₂	7.52	13.47	39.14	39.87	0.5583

图5 BaTiO3陶瓷的XRD图谱

Fig. 5 XRD patterns of BaTiO3 ceramics (b, c) Local magnification XRD patterns in the range of 2θ=43°-47° and 21.5°-25°, respectively

图6 BaTiO3陶瓷的SEM断面照片

Fig. 6 Section SEM images of BaTiO3 ceramics (a) A2-CSP; (b) A1-CSP-CS; (c) A2-CSP-CS

图7 陶瓷的介电温谱图

Fig. 7 Dielectric temperature spectra of ceramics (a) A2-CSP; (b) A1-CSP-CS; (c) A2-CSP-CS

表3 陶瓷的相对密度与介电性能

Table 3 Relative density and dielectric properties of ceramics

Process	Relative density	ε_r(1 kHz)	ε_r@T_c(1 kHz)	T_c(1 kHz)	tanδ
A₂-CPS	92.73%	930	1413	128 ℃	0.08
A₁-CPS-CS	95.78%	2768	5813	124 ℃	0.06
A₂-CPS-CS	96.62%	2836	7274	123 ℃	0.03

图8 BaTiO3冷烧结致密化过程示意图

Fig. 8 Densification process of cold sintering of BaTiO3

表4 文献报道的BaTiO3陶瓷冷烧结性能对比

Table 4 Summary of cold sintering of BaTiO3 ceramics

Process	Flux (in mass)	Temperature/Pressure	Time/h	Density/%	ε_r(1 kHz)	tanδ (1 kHz)	Heat treatment	Ref.
CSP-CS	Ba(OH)₂/TiO₂ soultion	180 ℃/430 MPa	1-3 h	95	1760	0.04	700-900 ℃/3 h	[11]
CSP	NaOH-KOH	300 ℃/520 MPa	12 h	98	1800	0.04	-	[15]
Surface coating/CSP-CS	H₂O, Ba(OH)₂ solution	220 ℃/500 MPa	1 h	97	1550	0.02	700-900 ℃/3 h	[10]
1 mol/L acetic acid/powder-CSP	20% Ba(OH)₂∙8H₂O	225 ℃/350 MPa	1 h	95	1440	0.09	-	[16]
1 mol/L acetic acid/powder-CSP	11% Sr(OH)₂∙8H₂O	275 ℃/350 MPa	1 h	92	1500	0.08	-	[21]
0.1 mol/L acetic acid/powder-CSP	10% Ba(OH)₂∙8H₂O	400 ℃/350 MPa	1 h	96	2830	0.03	600 ℃/0.5 h	Thiswork

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BaTiO₃陶瓷的低温冷烧结制备及性能研究

Preparation and Properties of BaTiO₃ Ceramics by Low Temperature Cold Sintering

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