F~-离子和Ti~(4+)离子在CaO-Al_2O_3-SiO_2系玻璃晶化时的作用

在ＣａＯ－Ａｌ２Ｏ３－ＳｉＯ２（ＣＡＳ）系玻璃中单独引入Ｆ－离子或Ｔｉ４＋离子，以及同时引入Ｆ－离子和Ｔｉ４＋离子，通过ＤＴＡ（差热分析）、ＸＲＤ（Ｘ－射线衍射）、Ｒａｍａｎ、ＸＰＳ（光电子能谱）和ＳＥＭ（扫描电镜）方法进行了研究。结果表明在ＣＡＳ系玻璃中一部分Ｆ－离子取代非桥氧离子处于玻璃网络内部，另一部分Ｆ－离子处于玻璃网络间隙，Ｆ－离子能促使ＣＡＳ系玻璃分相，在稍高于Ｔｇ的某一温度热处理时，ＣａＦ２晶体首先从玻璃中析出；Ｔｉ４＋离子对玻璃晶化影响不大，在稍高于Ｔｇ的某一温度热处理时，加Ｔｉ４＋离子和不加Ｔｉ４＋离子的玻璃首先析出的晶相均是钙长石（ＣａＡｌ２Ｓｉ２Ｏ８）；在ＣＡＳ系玻璃中同时引入Ｆ－离和Ｔｉ４＋离子时，在稍高于Ｔｇ的某一温度热处理后首先析出的晶体是ＣａＦ２和钙长石（ＣａＡｌ２Ｓｉ２Ｏ８），Ｆ－离子和Ｔｉ４＋离子混合使用能更好地促进ＣＡＳ系玻璃的晶化。

Effect of F - and Ti 4+ ions on crystallization of CaO Al 2O 3 SiO 2 system glasses

The methods of differential thermal analysis (DTA), X ray diffraction analysis (XRD), Raman, X ray photoelectron spectroscopy (XPS), and scanning electron microscopy (SEM) were used to investigate the CaO Al 2O 3 SiO 2 (CAS) system glasses. Some F - ions entered as the glass network formers by taking the place of the O 2- ions in the glass structure, and other F - ions entered as the network modifiers. The F - ions could promote the phase separation of the CAS system glasses. When the glasses were heat treated at the temperature slightly above T g, the crystal of CaF 2 came first out of the glasses with F - ions, and the crystal of CaAl 2Si 2O 8 came first out of both the glasses with Ti 4+ and the glasses without Ti 4+ . The Ti 4+ ions had a slightly effect on the crystallization of CAS system glasses. When the Ti 4+ and F - ions were together added to the CAS system glasses, the crystals of CaF 2 and CaAl 2Si 2O 8 came out from the above glasses after heat treatment at the temperature slightly above T g. The F - and Ti 4+ ions together played a more obvious role in advancing the crystallization of the CAS system glasses than either Ti 4+ or F -.