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

为了开发普通玻璃制备工艺所不能获得的功能玻璃，采用离子交换技术，用Ag^+或Na^+离子取代Na_2 O-Al_2 O_3-SiO_2系统氧化物玻璃中的Na^+离子，并讨论了离子交换引起的玻璃结构变化对玻璃性能的影响。通过XPS测量表明，通过Cu^+/Na^+离子交换引入的Cu^+离子仍然是一价的，但是通过EXAFS测量确定的其氧配位数从典型的亚铜离子的2增加到典型的二价铜离子的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^+离子的氧配位数增加。另一方面，在Ag^+/Na^+离子交换的情况下，通过测量^<29>Si MAS NMR谱和^<27>Al MAS NMR谱均未发现显著的结构变化。而红外光谱和拉曼光谱的振动谱峰位随着离子交换的进行向长波方向移动，说明引入的Ag^+离子首先占据非桥氧位，在完全占据非桥氧位后，再占据四重Al^&lt;3+&gt;离子附近的电荷补偿位.基于这些考虑，可以得出结论，通过Ag^+/Na^+离子交换，可以得到不含非桥氧的玻璃，从而获得非常高电导率的玻璃。

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.