SiO2疏松体真空烧结致密化与透明化机理研究

doi:10.15541/jim20180603

摘要/Abstract

摘要：

采用化学气相沉积方法制备出低密度、无定形的SiO₂疏松体, 通过TG-DSC、SEM、TEM、XRD、压汞法、氮气吸附法和高温熔炼观测系统等方法研究了低密度SiO₂疏松体烧结过程宏观尺度和微观结构的演化规律。结果表明: 当烧结温度为1000 ℃, 疏松体开始收缩; 烧结温度升至1200 ℃, 宏观尺度收缩完成, 收缩比为30%。当烧结温度高于1200 ℃, SiO₂小微粒开始熔化; 随着温度升至1250 ℃, 固相疏松体与液相玻璃体之间有明显的过渡界限, 气孔由连通状逐渐演变为孤立、球形闭气孔; 随着温度继续升高, 闭气孔通过粘性流动传质作用进一步收缩; 当温度达到1500 ℃时气孔完全消除, 得到透明石英玻璃体。此外, 在整个烧结过程中, 疏松体物相组成始终保持无定形态。

关键词: SiO₂疏松体, 真空烧结, 孔结构, 致密化, 透明化

Abstract:

Low density and amorphous SiO₂ soot body was prepared by chemical vapor deposition. Its macro deformation and micro-structure evolution rule in the sintering process were characterized by TG-DSC, SEM, TEM, XRD, mercury intrusion method, nitrogen adsorption method, and high temperature melting observation system, etc. The results indicated that SiO₂ soot body began to shrink at the sintering temperature of 1000 ℃. The macro scale soot body stopped shrinking when the sintering temperature rose to 1200 ℃, with 30% ratios shrinkage. When the sintering temperature was higher than 1200 ℃, the small particles of SiO₂ started to melt. There is a clear transition boundary between solid-phase soot body and liquid-phase glass body when the sintering temperature is higher than 1250 ℃. Meanwhile, it is interesting that the pores shape of soot body evolved gradually from connective to isolated, spherical and hole-closed. When the sintering temperature reached 1500 ℃, but the transparent silica glass is obtained without pores. More importantly, the state of SiO₂ soot body remains amorphous throughout the sintering process.

Key words: SiO₂ soot body, vacuum sintering, pore structure, densification, transparency

中图分类号:

TQ174

聂兰舰, 顾真安, 王玉芬, 向在奎, 张辰阳, 饶传东. SiO₂疏松体真空烧结致密化与透明化机理研究[J]. 无机材料学报, 2019, 34(10): 1060-1066.

NIE Lan-Jian, GU Zhen-An, WANG Yu-Fen, XIANG Zai-Kui, ZHANG Chen-Yang, RAO Chuan-Dong. SiO₂ Soot Body at Vacuum Sintering Process: Densification and Transparency Mechanism[J]. Journal of Inorganic Materials, 2019, 34(10): 1060-1066.

图/表 13

图1 SiO2疏松体的TG-DSC曲线

Fig. 1 TG-DSC curves of SiO2 soot body

图2 SiO2疏松体及经1500 ℃真空烧结体实物照片

Fig. 2 Photographs of intact SiO2 soot body and sintered body under 1500 ℃ and vacuum condition

图3 SiO2疏松体的原位动态烧结样品照片

Fig. 3 In-situ dynamic sintering photographs of SiO2 soot body

图4 不同烧结温度下SiO2疏松体的SEM照片

Fig. 4 SEM images of SiO2 soot bodies sintered at different temperatures

图5 未烧结SiO2疏松体的TEM照片

Fig. 5 TEM images of unsintered SiO2 soot bodies

图6 烧结过程中SiO2微粒间烧结颈的形成示意图[16]

Fig. 6 Schematic of neck formation and growth of SiO2 soot body during the sintering process[16]

图7 粘性玻璃中闭气孔坐标模型[17]

Fig. 7 Corrdinates for a closed pore initiated in viscous glass[17]

图8 透明石英玻璃的粘度-温度曲线[18]

Fig. 8 Temperature dependence of viscosity of clear silica glass[18]

图9 SiO2疏松体的变温XRD图谱

Fig. 9 XRD patterns of SiO2 soot bodies sintered at different temperatures

图10 不同烧结温度下SiO2疏松体的累积进汞体积曲线

Fig. 10 Cumulative intrusion volume curves of SiO2 soot bodies sintered at different temperatures

图11 不同烧结温度下SiO2疏松体孔径分布曲线

Fig. 11 Pore size distribution curves of SiO2 soot bodies sintered at different temperatures

表1 压汞法测试得到的SiO2疏松体孔结构数据

Table 1 Data analysis of pore structure of SiO2 soot bodies by mercury porosimetry

Sample	Pore volume/ (mL?g^-1)	Surface area/ (m²?g^-1)	Porosity/%	Average pore size/nm	Median pore diameter (Volume)/nm	Median pore diameter (Area)/nm
A (1250 ℃)	0.03	3.36	3.50	30.76	288.10	10.39
B (1000 ℃)	3.80	78.79	56.70	192.90	468.80	118.50
C (Unsintered)	5.33	60.55	67.52	351.90	10059.40	114.20

图12 SiO2疏松体透明化样品的光谱透过率曲线

Fig. 12 Spectral transmittance curves of transparent sample of SiO2 soot body

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SiO₂疏松体真空烧结致密化与透明化机理研究

SiO₂ Soot Body at Vacuum Sintering Process: Densification and Transparency Mechanism

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