### 固体核磁共振研究碱土金属磷硅酸盐玻璃的六配位硅结构

1. 1 上海大学材料科学与工程学院, 上海 200444;
2 中国科学院上海光学精密机械研究所, 高功率激光材料重点实验室, 上海 201800
• 收稿日期:2019-02-22 修回日期:2019-04-15 录用日期:2019-04-16 发布日期:2019-04-19
• 通讯作者: 任进军 E-mail:renjinjunsiom@163.com
• 基金资助:
国家自然科学基金（61675218）和中国科学院百人计划资助项目

### Structural Investigation of Alkaline-Earth Phosphosilicate Glasses Containing Six-Coordinated Silicon by Solid-State NMR

SHI Feng1,2, HU Lili2, REN Jinjun2, YANG Qiuhong1

1. 1 School of Materials Science and Engineering, Shanghai University, Shanghai 200444, P. R. China;
2 Key Laboratory of Materials for High Power Laser, Shanghai Institute of Optics and Fine Mechanics, Chinese Academy of Sciences, Shanghai 201800, P. R. China
• Received:2019-02-22 Revised:2019-04-15 Accepted:2019-04-16 Published:2019-04-19
• Contact: REN Jinjun E-mail:renjinjunsiom@163.com
• Supported by:
The project was supported by the National Natural Science Foundation of China (61675218) and the 100 Talents Program of Chinese Academy of Sciences.

Abstract: Phosphate glass is widely used in optical applications; however, its generally low chemical stability and poor thermal mechanical properties hinder the application of phosphate glass to the rapidly evolving laser industry. The addition of a small amount of silicon can form a six-coordinate Si (Si(6)) network and improve the above-mentioned poor properties of phosphate glass. Therefore, it is important to characterize and understand the structural details of phosphosilicate glasses. It is difficult to investigate the glass structure because of its complicated and disordered characteristics. However, solid-state nuclear magnetic resonance (NMR) spectroscopy can provide detailed local structural information, regardless of the presence of its long-range order. To study the effect of alkaline earth metals on Si(6) species formation, we prepared phosphosilicate glasses (2MO-3P2O5)(1-x)·(SiO2)x (M=Ca, Sr, Ba) by conventional melt-quenching, and the glass structure was investigated by solid-state NMR and Raman spectroscopy. The 31P and 29Si NMR spectra indicated that the glass networks consisted of P(2) and P(3) tetrahedrons linked via four-and six-fold coordinated silicon units (Si(4) and Si(6)). The fraction of six-coordinated silicon Si(6) decreased with increasing SiO2 content. Similarly, the Raman spectra showed that the vibration band of the P=O stretching mode in P(3) linked with Si(6) neighbors reduced as the silica content increased. The connectivities between various phosphorus species were probed by 31P one-and two-dimensional refocused INADEQUATE experiments. This experimental technique is based on homonuclear J-coupling and yields correlation peaks between nuclei engaged in P-O-P linkages (P(2) and P(3) units). The signals from isolated 31P nuclei are suppressed because of the absence of J-coupling, which precludes the formation of double quantum coherences. The results indicated the segregation of P(2) and P(3) units in the prepared glass, which were also compared with those in the previously reported Na2O-P2O5-SiO2 glasses. They differed from alkali phosphosilicate glasses, where each P(3) unit exhibited a maximum average of one Si(6)-O-P(3) linkage, and in the alkaline earth phosphosilicate glasses, the average was approximately 0.4-0.7. When the content of Si(6) units reached its maximum, further increase in the SiO2 content did not increase the Si(6) content, and the surplus Si were present as Si(4). Alkaline earth metal ions exhibit weaker stabilizing effects for Si(6) species. Based on the results presented herein, we constructed sketches to illustrate the local structural organization of the glass. The relationships between the compositions and structures are important for glass composition and property design. It is important to improve the performance of phosphate glass by changing its composition, particularly for large laser device applications.

MSC2000:

• O641