热处理对Mg-Al-Si-Ti-B系微晶玻璃析晶及介电性能的影响

doi:10.15541/jim20180102

无机材料学报 ›› 2018, Vol. 33 ›› Issue (12): 1309-1315.DOI: 10.15541/jim20180102

热处理对Mg-Al-Si-Ti-B系微晶玻璃析晶及介电性能的影响

屈婧婧^1,2, 魏星², 刘飞¹, 袁昌来³, 陈国华³, 黄先培³

1. 桂林电子科技大学机电工程学院, 桂林 541004;
2. 桂林航天工业学院科技处, 桂林 541004;
3. 桂林电子科技大学广西信息材料重点实验室, 桂林 541004

收稿日期:2018-03-06 修回日期:2018-06-08 出版日期:2018-12-20 网络出版日期:2018-11-27
作者简介:屈婧婧(1988-), 女, 博士研究生, 讲师. E-mail: qujingjing@guat.edu.cn
基金资助:
广西自然科学基金(2017GXNSFBA198093);国家自然科学基金(11464006)

Heat-treatment on Crystallization and Dielecty Property of Mg-Al-Si-Ti-B Glass-ceramics

QU Jing-Jing^1,2, WEI Xing², LIU Fei¹, YUAN Chang-Lai³, CHEN Guo-Hua³, HUANG Xian-Pei³

1. School of Mechanical and Electrical Engineering, Guilin University of Electronic Technology, Guilin 541004, China;
2. Department of Science and technology, Guilin University of Aerospace Technology, Guilin 541004, China;
3. Guangxi Key Laboratory of Information Materials, Guilin University of Electronic Technology, Guilin 541004, China

Received:2018-03-06 Revised:2018-06-08 Published:2018-12-20 Online:2018-11-27
About author:QU Jing-Jing. E-mail: qujingjing@guat.edu.cn
Supported by:
Natural Science Foundation of Guangxi (2017GXNSFBA198093);National Natural Science Foundation of China (11464006)

摘要/Abstract

摘要：

采用差热分析仪(DSC), X射线衍射仪(XRD)及扫描电子显微镜(SEM)等测试手段, 研究了不同烧结制度下19MgO-23Al₂O₃-53SiO₂-4TiO₂-2.5B₂O₃(wt%, M-A-S-T-B)系微晶玻璃样品的析晶过程、相成分与含量及微观形貌, 并分析了核化与晶化时间对材料微波介电性能的影响关系。结果表明, 根据玻璃受控析晶机制, 当热处理制度为850℃/2 h+950℃/2 h时, 斜顽辉石(MgSiO₃)相得以较好的析出, 且伴随有α-堇青石(Mg₂Al₄Si₅O₁₈)、镁铝硅酸盐(xMgO-yAl₂O₃-zSiO₂)和方石英(α-SiO₂)相的析出。随着核化时间的延长, M-A-S-T-B体系各晶相种类及析出量变化不明显; 而随着晶化时间的延长(20 h), 材料的晶化程度提高, 品质因数(Q×f)得以提升, 颗粒状晶粒析出趋于显著; 但当晶化时间进一步延长至30 h时, 样品致密度降低, 介电损耗略有增大。在热处理制度为850℃/2 h+950℃/20 h下, 样品获得的微波介电性能较优: ε_r=3.85、τ_f≈-5.37×10^-6/℃和Q×f ≈12740 GHz(f₀=13.973 GHz)。

关键词: 热处理, 微晶玻璃, MgSiO₃, 微波介电性能

Abstract:

Effects of different heat-treatment process on the crystallization, phase composition and content, and microstructure of 19MgO-23Al₂O₃-53SiO₂-4TiO₂-2.5B₂O₃ (wt%, M-A-S-T-B) were studied by means of differential scanning calorimeter (DSC), X-ray diffraction (XRD) and scanning electron microscope (SEM) techniques. The influence of different nucleation and crystallization time on the microwave dielectric properties were discussed as well. The results showed that, based on the controlled crystallization mechanism of glass, MgSiO₃ phase was precipitated adequately for M-A-S-T-B samples heat-treated at 850℃/2 h + 950℃/2 h, and also, the α-cordierite, xMgO-yAl₂O₃-zSiO₂ and α-SiO₂ phases could be precipitated from matrix phase. Additionally, with the increase of nucleation time, types of crystalline and phase content were found no discernible changes in the M-A-S-T-B glass-ceramics. While crystallization time increased to 20 h, the crystallized volume fraction of the glass increased, leading to the improvement of the quality factor (Q×f) and the obvious precipitation of granular grains. However, the dielectric loss slightly increased and the relative density of specimens decreased with further increase of crystallization time (30 h). Wherein, the M-A-S-T-B glass-ceramic sample heat-treated at 850℃/2 h + 950℃/20 h exhibited the excellent microwave dielectric properties of ε_r ~ 3.85, Q×f ~ 12740 GHz (at 13.973 GHz) and τ_f ~-5.37×10^-6/℃.

Key words: heat-treatment, glass-ceramics, MgSiO₃, microwave dielectric properties

中图分类号:

TM277

屈婧婧, 魏星, 刘飞, 袁昌来, 陈国华, 黄先培. 热处理对Mg-Al-Si-Ti-B系微晶玻璃析晶及介电性能的影响[J]. 无机材料学报, 2018, 33(12): 1309-1315.

QU Jing-Jing, WEI Xing, LIU Fei, YUAN Chang-Lai, CHEN Guo-Hua, HUANG Xian-Pei. Heat-treatment on Crystallization and Dielecty Property of Mg-Al-Si-Ti-B Glass-ceramics[J]. Journal of Inorganic Materials, 2018, 33(12): 1309-1315.

图/表 7

图1 M-A-S-T-B基础玻璃的DSC曲线

Fig. 1 DSC curve of M-A-S-T-B base glass sample Inset shows the heat treatment process of the glass

表1 M-A-S-T-B玻璃的热处理制度

Table 1 Heat treatment process of M-A-S-T-B glass

Specimens	T_g/sintering time	T_p/sintering time
1	850℃/1 h	950℃/2 h
2	850℃/2 h	950℃/2 h
3	850℃/4 h	950℃/2 h
4	850℃/8 h	950℃/2 h
5	850℃/20 h	950℃/2 h
6	850℃/2 h	950℃/1 h
7	850℃/2 h	950℃/4 h
8	850℃/2 h	950℃/8 h
9	850℃/2 h	950℃/12 h
10	850℃/2 h	950℃/20 h
11	850℃/2 h	950℃/30 h

图2 同一核化与晶化温度保温不同时间下M-A-S-T-B微晶玻璃的XRD图谱

Fig. 2 XRD patterns of the M-A-S-T-B glass-ceramics heat- treated at the same nucleation and crystallization temperatures for different time(a) 850℃/1-20 h + 950℃/2 h; (b) 850℃/2 h + 950℃/1-30 h; (c) the enlarged pattern at 2θ = 23.5-27º

图3 相同核化与晶化温度保温不同时间M-A-S-T-B微晶玻璃的SEM照片

Fig. 3 SEM images of the M-A-S-T-B glass-ceramics heat-treated at the same nucleation and crystallization temperatures for different time

图4 (a)M-A-S-T-B玻璃样品经850℃/20 h + 950℃/ 2 h热处理后的SEM照片, (b)图(a)中标定晶相‘A’的EDS图谱

Fig. 4 (a) SEM images of the M-A-S-T-B glass-ceramics heat-treated at 850℃/20 h + 930℃/2 h, and (b) EDS pattern of region ‘A’ marked in (a)

图5 同一核化与晶化温度保温不同时间M-A-S-T-B微晶玻璃的体积密度与孔隙率的变化曲线

Fig. 5 Curves of density(r) and porosity of the M-A-S-T-B glass-ceramics heat-treated at the same nucleation and crystallization temperatures for different time

图6 同一核化与晶化温度下M-A-S-T-B微晶玻璃的εr与Q×f随保温时间变化的关系曲线

Fig. 6 Curves of εr and Q×f values of the M-A-S-T-B glass-ceramics heat-treated at the same nucleation and crystallization temperatures for different time

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热处理对Mg-Al-Si-Ti-B系微晶玻璃析晶及介电性能的影响

Heat-treatment on Crystallization and Dielecty Property of Mg-Al-Si-Ti-B Glass-ceramics

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