γ辐照及热退火对光热折变玻璃光学性能的影响

doi:10.15541/jim20200389

摘要/Abstract

摘要：

对光热折变(Photo-thermal-refractive, PTR)玻璃在总剂量分别为0.35、1、10及100 kGy的γ射线下辐照, 并进行热退火处理, 采用吸收光谱、光致发光光谱及EPR电子顺磁共振谱研究了光热折变玻璃在γ射线辐照下的辐照机理。研究结果表明, γ辐照后的PTR玻璃在可见波段的吸收主要由银原子Ag⁰、银分子簇Ag₂、银分子簇Ag₃、银纳米颗粒Ag_m⁰及非桥氧空穴中心HC₁及HC₂引起; 在不同剂量γ射线辐照下, 玻璃基质中的变价离子(Ag⁺、Ce³⁺)价态先发生变化, 同时玻璃基质中的非桥氧键发生电离, 形成了非桥氧空穴型缺陷中心HC₁、HC₂。进一步增加辐照剂量, 产生了银的分子簇Ag₂和Ag₃; 同时玻璃基质中非桥氧空穴中心HC₂的浓度增大, 导致在639 nm附近的吸收增强。分别在不同温度下对辐照后的PTR玻璃进行相同时间的热处理及在低于T_g(玻璃转变温度)的温度下进行不同时间的热处理, 观察到250 ℃退火后PTR玻璃中HC₁及HC₂缺陷中心发生漂白; 并在430 ℃退火后出现了银纳米颗粒的吸收峰, 该吸收峰随退火时间的延长发生了红移及展宽。

关键词: 光热折变玻璃, γ射线辐照, 辐照缺陷, 紫外-可见吸收谱

Abstract:

Photo-thermal-refractive (PTR) glass was irradiated with γ-ray at the total dose of 0.35, 1, 10 and 100 kGy, respectively, and then annealed. Irradiation mechanism of the photo-thermal-refractive glass was studied by absorption spectroscope, luminescence spectroscope and electron paramagnetic resonance. The results showed that the absorption of the γ-irradiated PTR glass in the visible light was mainly caused by the Ag⁰, silver molecular clusters Ag₂, Ag₃, silver nanoparticles Ag_m⁰, and non-bridge oxygen hole center HC₁ and HC₂. Under different doses of γ-ray irradiation, valence state of the ions (Ag⁺, Ce³⁺) in the glass matrix changed. At the same time, non-bridged oxygen bonds in the glass matrix broke, generating non-bridged oxygen hole defects HC₁, HC₂ and Ag⁰. With the increase of the radiation dose, silver molecular clusters Ag₂and Ag₃ generated, and the concentration of HC₂ center in the glass matrix increased, resulting in enhanced absorption near 639 nm. After being irradiated and annealed at 250 ℃, HC₁ and HC₂ defect centers was bleached. Silver molecules appeared after annealing at 430 ℃, of which absorption peak had a redshift and was broadened with the increase of annealing duration.

Key words: photo-thermal-refractive glass, γ-ray irradiation, defect center, UV-Vis absorption

中图分类号:

TQ174

朱治昱, 焦艳, 邵冲云, 何冬兵, 胡丽丽. γ辐照及热退火对光热折变玻璃光学性能的影响[J]. 无机材料学报, 2021, 36(5): 521-526.

ZHU Zhiyu, JIAO Yan, SHAO Chongyun, HE Dongbing, HU Lili. Effects of γ-Irradiation and Thermal Annealing on Photo-thermal-refractive Glass[J]. Journal of Inorganic Materials, 2021, 36(5): 521-526.

图/表 8

图1 未辐照及0.35、1、10、100 kGy γ射线辐照后的PTR玻璃和宏观照片

Fig. 1 Photos of PTR-glasses unirradiated and irradiated with 0.35, 1, 10 and 100 kGy γ-ray

图2 未辐照及0.35、1、10和100 kGy γ射线辐照后PTR玻璃的透过谱图(a)和吸收谱图(b) (厚度2 mm)

Fig. 2 (a) Transmission spectra and (b) absorbance spectra of unirradiated PTR glass and PTR glass irradiated with 0.35, 1, 10, and 100 kGy γ-ray

图3 未辐照及0.35、1、10和100 kGy γ射线辐照后PTR玻璃的光致发光光谱(激发波长为340 nm)

Fig. 3 Emission spectra of PTR glass before and after being irradiated by 0.35, 1, 10, and 100 kGy γ-ray (Excitation wavelength: 340 nm)

图4 0.35 kGy γ辐照诱导吸收RIA谱的高斯分峰图

Fig. 4 Gauss deconvolution of 0.35 kGy γ-radiation induced absorption (RIA)

图5 在不同温度下, 对100 kGy γ射线辐照后的PTR玻璃进行30 min热处理后的透过光谱(a)和实物照片(b)

Fig. 5 (a) Transmission spectra and (b) photos of PTR glass irradiated with 100 kGy γ-ray and thermal treatment at different temperatures for 30 min

图6 在430 ℃下对100 kGy γ射线辐照后的PTR玻璃进行不同时间热处理后的吸收谱(a), 30 min (b)和120 min (c)和热处理后的TEM照片

Fig. 6 Absorbance spectra of PTR glass after 100 kGy γ-irradiation and thermal treatment at 430 ℃ for different time (a), TEM images of PTR glass after 100 kGy γ-irradiation and thermal treatment at 430 ℃ for 30 min (b) and 180 min (c)

图7 经100 kGy γ射线辐照, 并于430 ℃进行30、360 min热处理前后PTR玻璃的光学吸收谱

Fig. 7 Absorption spectra of 100 kGy γ-ray irradiated PTR glass before and after thermal treatment at 430 ℃ for 30 min and 360 min

图8 经1、100kGy γ射线辐照及100 kGy γ射线辐照并于430 ℃退火120 min的PTR玻璃的EPR谱(a)以及1 kGy(b)和100 kGy(c) γ射线辐照后的TEM照片

Fig. 8 EPR spectra of PTR glass irradiated with 1, 100 kGy γ-ray, and 100 kGy γ-irradiation and thermal treatment at 430 ℃ for 120 min (a), TEM images of PTR glass after 1 kGy (b) and 100 kGy (c) γ-irradiation

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