基于BaO-CaO-Al2O3-B2O3-SiO2体系探究BaCO3的残余量及其对玻璃热性能的影响

doi:10.15541/jim20170411

无机材料学报 ›› 2018, Vol. 33 ›› Issue (8): 861-865.DOI: 10.15541/jim20170411

基于BaO-CaO-Al₂O₃-B₂O₃-SiO₂体系探究BaCO₃的残余量及其对玻璃热性能的影响

刘亮光, 罗凌虹, 吴也凡, 程亮, 徐序, 王乐莹

景德镇陶瓷大学材料科学与工程学院, 江西省燃料电池材料与器件重点实验室, 景德镇 333403

收稿日期:2017-08-22 修回日期:2018-02-07 出版日期:2018-08-28 网络出版日期:2018-07-17
作者简介:刘亮光(1991-), 男, 硕士研究生. E-mail: 478718955@qq.com
基金资助:
国家自然科学基金(51662015, 51462011);江西省教育厅科技落地计划(KJLD13072)

Residual Amount of BaCO₃ on Glass Thermal Property Based on BaO-CaO-Al₂O₃-B₂O₃-SiO₂System

LIU Liang-Guang, LUO Ling-Hong, WU Ye-Fan, CHEN Liang, XU Xu, WANG Le-Ying

Jiangxi Province Key Laboratory of Fuel Cell Materials and Devices, School of Materials Science and Engineering, Jingdezhen Ceramic Institute, Jingdezhen 333403, China

Received:2017-08-22 Revised:2018-02-07 Published:2018-08-28 Online:2018-07-17
About author:LIU Liang-Guang. E-mail: 478718955@qq.com
Supported by:
National Natural Science Foundation of China (51662015, 51462011);Science and Technology Landing Program of Jiangxi Provincial Education Department (KJLD13072)

摘要/Abstract

摘要：

采用中温固体氧化物燃料电池(IT-SOFC, Intermediate Temperature-Solid Oxide of Fuel Cell)封接玻璃BaO-CaO-Al₂O₃-B₂O₃-SiO₂体系探究三种熔制工艺(1300℃保温1 h; 1400℃保温1 h; 1400℃保温3 h)对玻璃原料BaCO₃的残余量及玻璃热性能的影响。利用差热-热重分析(DTA-TG)对配方粉体和不同熔制工艺获得玻璃的热性能进行表征, 根据DTA-TG数据进行了计算并验证BaCO₃的残余量。通过傅里叶红外光谱、XRD和热膨胀系数测定仪对样品进行了表征。结果表明: 采取1300℃保温1 h制备的玻璃中仍有59wt% BaCO₃未分解, 并且析出的单斜BaAl₂Si₂O₈晶体降低了玻璃的膨胀系数; 1400℃保温3 h制备的玻璃由于Al₂O₃含量增加, 玻璃软化点(T_s)明显升高(>800℃), 1400℃保温1 h制备的玻璃在室温到玻璃温度转变点范围内的膨胀系数为10.3×10^-6 K^-1。因此对于本实验玻璃配方, 1400℃保温1 h是最为合适的熔制工艺, 可以用于SOFC电堆的封接。

关键词: 碳酸钡, 烧制工艺, 差热-热重分析, 热性能

Abstract:

A BaO-CaO-Al₂O₃-B₂O₃-SiO₂system for the sealing glass in intermediate temperature solid oxide fuel cell (IT-SOFC) was prepared. The effects of three fusion processes (heating at 1300℃ for 1 h, heating at 1400℃ for 1 h, and heating at 1400℃ for 3 h) were explored with focus on the residual amount of BaCO₃and the thermal properties of the glasses by thermal-thermogravimetric analysis (DTA-TG). Samples were characterized by Fourier transform infrared spectroscopy (FT-IR), X-ray diffractometer (XRD) and thermal expansion coefficient meter. The results showed that 59wt% BaCO₃ retained undecomposed in the glass prepared via heat treatment at 1300℃ for 1 h and its expansion coefficient decreased due to devitrification of monoclinic BaAl₂Si₂O₈. Softening temperature (>800℃) of the glass produced via heating at 1400℃ for 3 h increased obviously owing to the increment of Al₂O₃amount. The expansion coefficient of the glass produced via heat treatment at 1400℃ for 1 h was 10.3×10^-6K^-1 from room temperature to the glass transition temperature, indiating the process of heat treatment at 1400℃ for 1 h the optimal condition in three candidates for the specific formula, which was found to be eligible for SOFC sealing.

Key words: barium carbonate, fusion, DTA-TG, thermal properties

中图分类号:

TQ174

刘亮光, 罗凌虹, 吴也凡, 程亮, 徐序, 王乐莹. 基于BaO-CaO-Al₂O₃-B₂O₃-SiO₂体系探究BaCO₃的残余量及其对玻璃热性能的影响[J]. 无机材料学报, 2018, 33(8): 861-865.

LIU Liang-Guang, LUO Ling-Hong, WU Ye-Fan, CHEN Liang, XU Xu, WANG Le-Ying. Residual Amount of BaCO₃ on Glass Thermal Property Based on BaO-CaO-Al₂O₃-B₂O₃-SiO₂System[J]. Journal of Inorganic Materials, 2018, 33(8): 861-865.

图/表 9

图1 玻璃制备工艺

Fig. 1 Schematic diagram of glass preparation process

图2 原配方粉体的差热-热重分析图

Fig. 2 DTA-TG curves of the original formula powders

图3 A玻璃粉体的差热-热重分析图

Fig. 3 DTA-TG curves of A glass powders

表1 原配方粉料中可分解组份量及其理论分解量

Table 1 Theoretical and realistic decomposition content of the initial powder prepared with formula

Initial ingredient (content/mg)	Product	Product quantity/mg	Theoretical total loss, M1/mg	Real total loss, M2/mg
BaCO₃(13.179)	CO₂	2.9384	5.9396	4.4120
CaCO₃(2.9286)	CO₂	1.2886
Na₂CO₃(0.2746)	CO₂	0.1140
H₃BO₃(3.6608)	H₂O	1.5986
H₃BO₃(3.6608)	B₂O₃	2.0610

图4 BaCO3与A玻璃粉的红外光谱图

Fig. 4 FT-IR spectra of BaCO3 and A glass powders

图5 A、B与C玻璃粉的热重分析

Fig. 5 TG curves of A, B and C samples

图6 不同工艺条件下玻璃的热膨胀曲线

Fig. 6 Thermal expansion curves of the samples obtained under different process conditions

表2 不同工艺条件下各玻璃的热性能参数

Table 2 Thermal parameters of glass under different processes

Process	Transition temperature, T_g/℃	Softening temperature, T_s/℃	Expansion coefficient, TEC/ (×10^-6, K^-1)
A	558	640	5.4
B	562	633	10.3
C	564	>800	10.9

图7 A、B、C玻璃在850℃热处理10 min后的XRD图谱

Fig. 7 XRD patterns of A, B and C glass treated at 850℃ for 10 min

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基于BaO-CaO-Al₂O₃-B₂O₃-SiO₂体系探究BaCO₃的残余量及其对玻璃热性能的影响

Residual Amount of BaCO₃ on Glass Thermal Property Based on BaO-CaO-Al₂O₃-B₂O₃-SiO₂System

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