稀土掺杂对ZnO-B2O3-SiO2玻璃热稳定性及结构的影响

doi:10.15541/jim20160509

摘要/Abstract

摘要：

为了探索镧系与非镧系元素对ZnO-B₂O₃-SiO₂系统玻璃热稳定性及结构的影响, 本研究采用差示扫描量热仪(DSC)和傅立叶变化红外光谱仪(FTIR)开展了La₂O₃和Y₂O₃掺杂对该系统玻璃析晶行为、热稳定性和结构变化的系统研究。结果表明: 当La₂O₃掺杂量大于8mol%、Y₂O₃掺杂量大于6mol%时, 60ZnO-30B₂O₃-10SiO₂系统玻璃开始出现析晶现象; 当La₂O₃掺杂量为4mol%、Y₂O₃掺杂量为2mol%时, 该玻璃的热稳定性能最好。结构研究表明, 少量添加稀土氧化物会使该系统玻璃的网络链接程度提高, 而当掺杂量超过一定量时会使该系统玻璃的网络链接程度降低。

关键词: ZnO-B₂O₃-SiO₂玻璃, La₂O₃, Y₂O₃, 热稳定性, 玻璃结构

Abstract:

To investigate the effect of the lanthanides and non-lanthanides elements on the thermal stability and structure of ZnO-B₂O₃-SiO₂ glass, the crystallization behavior, thermal stability and structural changes of ZnO-B₂O₃-SiO₂ glass doped with La₂O₃and Y₂O₃ were characterized by the differential scanning calorimetry (DSC) and Fourier Transform Infrared spectroscope (FTIR). The results showed that when the La₂O₃ and Y₂O₃additions are more than 8mol% and 6mol%, respectively, the 60ZnO-30B₂O₃-10SiO₂ glass system begins to crystallize. When La₂O₃and Y₂O₃ additions are 4mol% and 2mol%, respectively, this glass is of the best thermal stability. According to the structure research, the network linking performance of this kind of glass can be improved by a small amount addition of rare earth oxide. In contrast, the network linking performance of this kind of glass can be decreased by rare earth oxide’s addition exceeding a certain threshold value.

Key words: ZnO-B₂O₃-SiO₂ glass, La₂O₃, Y₂O₃, thermal stability, structure

中图分类号:

TQ174

王觅堂, 方龙, 李梅, 柳召刚, 胡艳宏, 张晓伟. 稀土掺杂对ZnO-B₂O₃-SiO₂玻璃热稳定性及结构的影响[J]. 无机材料学报, 2017, 32(6): 643-648.

WANG Mi-Tang, FANG Long, LI Mei, LIU Zhao-Gang, HU Yan-Hong, ZHANG Xiao-Wei. Effect of Rare Earth Dopant on Thermal Stability and Structure of ZnO-B₂O₃-SiO₂ Glass[J]. Journal of Inorganic Materials, 2017, 32(6): 643-648.

图/表 10

图1 掺杂不同量稀土氧化物的玻璃样品的实物照片

Fig. 1 Pictures of different content of rare earth oxide doped glass samples

图2 掺杂稀土氧化物玻璃的DSC曲线

Fig. 2 DSC curve of glasses doped with REO

表1 掺杂稀土氧化物玻璃的特征温度

Table 1 Characteristic temperature of glasses doped with REO

Glass	T_g /℃	T_c /℃	T_p /℃	S
B0	570	699	727	6.3
L1	568	701	734	7.7
L2	565	692	728	8.1
L3	565	689	724	7.7
L4	565	695	728	7.6
Y1	573	708	739	7.3
Y2	575	715	744	7.1
Y3	576	724	750	6.7

图3 稀土氧化物对玻璃热稳定性的影响

Fig. 3 Thermal stability of glass vs. content of REO

图4 掺杂稀土氧化物玻璃的红外光谱图

Fig. 4 FT-IR spectra of glasses dopedwith REO

图5 B0样品的高斯拟合图

Fig. 5 Deconvoluted FT-IR spectra of B0

图6 稀土掺杂对[ZnO4]的Zn-O伸缩振动峰P1的影响

Fig. 6 Effect of REO on the peak position of Zn-O P1 in [ZnO4] tetrahedron

表2 拟合结果所对应的FT-IR谱带的峰值和面积(C表示振动峰的中心, A表示相对的面积)

Table 2 Deconvoluted parameters of the FT-IR spectra of the glasses (the band centers C and the relative area A)

Glass	P1	P2		P3		P4		P7		P8
Glass	C	C	A	C	A	C	A	C	A	C	A
B0	580.4	693.2	21.9	837.3	6.1	914.6	30.4	1328.4	89.6	1464.8	25.0
L1	581.4	692.4	14.3	886.3	21.1	997.1	39.4	1343.3	36.6	1445.2	43.2
L2	581.8	695.8	15.0	870.0	13.8	965.5	41.3	1337.4	16.4	1431.7	56.1
L3	587.8	702.8	19.8	862.2	14.2	956.8	54.3	1331.2	33.8	1429.8	58.9
L4	584.9	704.3	18.9	851.4	10.0	943.2	50.1	1332.7	32.3	1430.2	49.5
Y1	585.3	692.3	9.9	883.3	17.2	988.3	33.1	1370.8	27.2	1473	43.1
Y2	585.9	696.7	18.5	871.9	15.4	965.4	41.2	1351.7	30.3	1450.2	43.0
Y3	588.3	700.4	15.2	867.7	12.4	958.7	37.2	1337.6	15.7	1433.4	59.1

图7 (a)La2O3含量对[BO3]的弯曲振动峰P2和[BO4]的伸缩振动峰P3峰值的影响; (b)Y2O3含量对[BO3]的弯曲振动峰P2和[BO4]的伸缩振动峰P3峰值的影响

Fig. 7 (a) Peak position of bending vibration of [BO3] P2 and stretching vibration of [BO4] P3 vs content of La2O3; (b) Peakposition of bending vibration of [BO3] P2 and stretching vibration of [BO4] P3 vs content of Y2O3.

图8 (a)La2O3掺杂量对N3和N4的影响; (b)Y2O3掺杂量对N3和N4的影响

Fig. 8 (a) N3 and N4 vs content of La2O3; (b) N3 and N4 vs content of Y2O3

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稀土掺杂对ZnO-B₂O₃-SiO₂玻璃热稳定性及结构的影响

Effect of Rare Earth Dopant on Thermal Stability and Structure of ZnO-B₂O₃-SiO₂ Glass

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Glass	T_g /℃	T_c /℃	T_p /℃	S
B0	570	699	727	6.3
L1	568	701	734	7.7
L2	565	692	728	8.1
L3	565	689	724	7.7
L4	565	695	728	7.6
Y1	573	708	739	7.3
Y2	575	715	744	7.1
Y3	576	724	750	6.7

Glass	T_g /℃	T_c /℃	T_p /℃	S
B0	570	699	727	6.3
L1	568	701	734	7.7
L2	565	692	728	8.1
L3	565	689	724	7.7
L4	565	695	728	7.6
Y1	573	708	739	7.3
Y2	575	715	744	7.1
Y3	576	724	750	6.7

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Glass	T_g /℃	T_c /℃	T_p /℃	S
B0	570	699	727	6.3
L1	568	701	734	7.7
L2	565	692	728	8.1
L3	565	689	724	7.7
L4	565	695	728	7.6
Y1	573	708	739	7.3
Y2	575	715	744	7.1
Y3	576	724	750	6.7

Glass	T_g /℃	T_c /℃	T_p /℃	S
B0	570	699	727	6.3
L1	568	701	734	7.7
L2	565	692	728	8.1
L3	565	689	724	7.7
L4	565	695	728	7.6
Y1	573	708	739	7.3
Y2	575	715	744	7.1
Y3	576	724	750	6.7