Study on the new functionality of glasses induced by R^+/Cu^+ and R^+/Ag^+ ion-exchange

R^/Cu^和R^/Ag^离子交换诱导玻璃新功能的研究

• 批准号: 11305062
• 负责人: YAMANE Masayuki
• 金额: $ 13.57万
• 依托单位: TOKYO INSTITUTE OF TECHNOLOGY
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (A).
• 财政年份: 1999
• 资助国家: 日本
• 起止时间: 1999 至 2000
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-11305062/
• 关键词: ion-exchange; aluminosilicate glasses; Cu^+ion; Ag^+ion; electrical conductivity; glass transition; アルミノシリケートガラス

In order to develop functional glasses which are not obtainable by an ordinary glass preparation process, Na^+ ions in oxide glasses of Na_2O-Al_2O_3-SiO_2 system were replaced by Ag^+ or Na^+ ions by ion-exchange technique and the properties of the resulting glasses were discussed in relation to structural alteration induced by the ion-exchange. The Cu^+ ion introduced by Cu^+/Na^+ ion-exchange was turned out to remain mono-valent by XPS measurement, but its oxygen coordination number determined by EXAFS measurement increased from 2, which is typical of cuprous ion, to 4 which is typical of cupric ion. Thus, the high electrical couductivity and extremely low glass transition temperature of Cu^+/Na^+ ion-exchanged glasses were attributed to this structural change leading to the increase in oxygen coordination number of Cu^+ ion. In the case of Ag^+/Na^+ ion-exchange, on the other hand, no remarkable structural change was recognized by the measurement of neither ^<29>Si MAS NMR spectra and ^<27>Al MAS NMR spectra. However, the peak position of vibration spectrum obtained by IR and Raman spectroscopy shifted toward the longer wavelength side as the ion-exchange advanced, suggesting that the introduced Ag^+ ions occupy non-bridging oxygen site first, and then occupy the charge compensating site near four-fold Al^<3+> ion after the former sites were fully occupied. Based on these considerations, it was concluded that a glass of very high electrical conductivity is obtainable by Ag^+/Na^+ ion-exchange for a glass free from non-bridging oxygen.

为了开发普通玻璃制备工艺无法获得的功能玻璃，采用离子交换技术将Na_2O-Al_2O_3-SiO_2体系氧化物玻璃中的Na^+离子替换为Ag^+或Na^+离子，并讨论了所得玻璃的性能与离子交换引起的结构变化的关系。 XPS 测量结果表明，通过 Cu^+/Na^+ 离子交换引入的 Cu^+ 离子仍保持单价，但 EXAFS 测量测定其氧配位数从亚铜离子的典型值 2 增加到铜离子的典型值 4。因此，Cu^+/Na^+离子交换玻璃的高电导率和极低的玻璃化转变温度归因于这种结构变化导致Cu^+离子氧配位数的增加。另一方面，在Ag ^+ /Na ^+ 离子交换的情况下，通过 29 Si MAS NMR谱和 27 Al MAS NMR谱的测量都没有发现显着的结构变化。然而，随着离子交换的进行，IR和拉曼光谱获得的振动光谱的峰值位置向较长波长侧移动，这表明引入的Ag^+离子首先占据非桥接氧位点，然后在之前的位点被完全占据后占据四倍Al^3+离子附近的电荷补偿位点。基于这些考虑，得出的结论是，通过Ag^+/Na^+离子交换不含非桥接氧的玻璃可以获得具有非常高电导率的玻璃。