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三元硅酸盐玻璃相中Al3+离子结构状态的MAS NMR谱研究

李如璧1,  徐培苍1,  莫宣学2   

  1. 1.江苏技术师范学院应用材料研究所, 江苏常州 213001; 2.中国地质大学研究生院, 北京 100083
  • 收稿日期:2002-09-26 修回日期:2002-11-22 出版日期:2003-03-05 发布日期:2003-03-05
  • 作者简介:李如璧(1943-),女,上海人,研究员,长期从事矿物物理和材料化学研究及大学物理教学工作
  • 基金资助:

    国家自然科学基金资助项目(49473180).

27Al3+ IONS IN CaO-Al2O3-SiO2 ALUMINOSILICATE GLASSES STUDIED BY MAS NMR

LI Ru-bi1, XU Pei-cang, MO Xuan-xue2   

  1. 1.Institute of Applied Materials, Jiangsu Teacher's College of Technology, Changzhou 213001, China;
    2.Graduate School, China University of Geosciences (Beijing), Beijing 100083, China
  • Received:2002-09-26 Revised:2002-11-22 Online:2003-03-05 Published:2003-03-05
  • Supported by:

    国家自然科学基金资助项目(49473180).

摘要:

采用魔角旋转核磁共振谱(MAS NMR)技术对CaO-Al2O3-SiO2 三元铝硅酸盐玻璃(简称CAS) 中Al3+ 离子的占位进行了系统的定量研究,获得下列结论: 
1. Al3+在硅酸盐熔体中,大部分进入四面体替代[SiO4]4- 中的Si,成为网络形成子. 另有小部分Al3+ 在网络骨架之间,以六配位、五配位和其他配位形式成为网络的修饰子.
2. 设η=N(Al3+IV/N(ΣAl),即考察区域内,四配位Al3+离子数与全部Al3+离子数之比. 设γ=N(ΣAl)/N(ΣSi),即考察区域内全部Al3+ 离子数与全部Si4+ 离子数之比.  则单位四面体的非桥氧数(Onb/T)与η成反比. 对于不同的γ值,Onb/T下降的速率不同. γ值越大,下降的速率也越大.

关键词: 核磁共振,  魔角旋转核磁共振谱, 硅酸盐玻璃相, 27Al, 29Si

Abstract:

In this study, the coordination structure of Al3+ in CaO-Al2O3-SiO2 aluminosilicate glasses (CAS) was studied using solid-state 27Al and 29Si magic-anglespinning NMR. The results showed that: 1). most Al3+ ions in CAS aluminosilicate glasses are present in the form of AlO4 tetrahedra, and act as networkforming ions. A small part of Al3+ ions exist as network-modifying cations in the forms of six-, five- and other- coordinated aluminum. 2). Onb/T is inversely proportional to η, where Onb/T is the number of non-bridge oxygen atom per tetrahedra, and η is the ratio of the number of tetrahedral Al3+ to the total number of Al3+ in the region of interest (ROI). The slope of the Onb/T vs.η relationship is influenced by γ, where γ is the ratio of the total number of Al3+ to the total number of Si4+ in the ROI.

Key words: NMR, magic angle spinning, aluminosillicate glasses,  27Al, 29Si

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