Na^+和Ti^(4+)对CaO-Al_2O_3-SiO_2系玻璃结构和晶化的影响

Effect of Na + and Ti 4+ on Structure and Crystallization of CaO-Al 2O 3-SiO 2 System Glasses

使用ＲＡＭＡＮ光谱和ＤＴＡ方法研究了含少量Ｎａ＋和Ｔｉ４＋的ＣａＯ－Ａｌ２Ｏ３－ＳｉＯ２系玻璃，发现在纯ＣＡＳ系玻璃（Ｃａ／Ａｌ≥１／２，Ａｌ／Ｓｉ≤１）中，Ａｌ３＋仅有一部分进入玻璃网络，少量Ｎａ＋的引入，有助于Ａｌ３＋进一步进入玻璃网络中，Ｎａ＋起了间接补强玻璃网络的作用，Ｎａ＋和Ｃａ２＋离子对Ａｌ３＋进入玻璃网络结构程度的影响可认为是Ｎａ＋和Ｃａ２＋离子分别以［ＡｌＯ４］Ｎａ和［ＡｌＯ４］Ｃａ［ＡｌＯ４］基团的形式进入玻璃网络中，由于结合几率和体积效应，使［ＡｌＯ４］Ｎａ较［ＡｌＯ４］Ｃａ［ＡｌＯ４］更易进入玻璃网络中。Ｔｉ４＋以［ＴｉＯ４］的形式进入玻璃网络，它对Ａｌ３＋是否能进入玻璃网络无明显影响。Ｎａ＋和Ｔｉ４＋的单独引入，均能使玻璃网络的聚合程度增强，析晶活化能提高；而当Ｎａ＋和Ｔｉ４＋同时引入时，玻璃网络聚合程度和纯ＣＡＳ系玻璃相差不大，析晶活化能有所降低。少量Ｎａ＋的引入，不会影响析出主晶相的种类和数量，而Ｔｉ４＋的引入，则会影响到所析出主晶相的种类和数量。

The methods of RAMAN and DTA were used to investigate the CaO-Al 2O 3-SiO 2 system glasses containning some Na + and Ti 4+ ions.Only a part of Al 3+ ions enter the glasses network in the pure CaO-Al 2O 2-SiO 2 system glasses,where Ca/Al≥1/2 and Al/Si≤1.When a few of Na + ions were added into the above CaO-Al 2O 3-SiO 2 system glasses,the Al 3+ ions enter the glass network further.Na + play an indirect role in improving the structure of glasses network.The influence of Na + and Ca 2+ on Al 3+ entering glass network is that Na + and [AlO 4] are combined into Na whose forming possibility is large and volume is little and which is easy to enter the glasses network,whereas Ca 2+ and [AlO 4] are combined into Ca whose forming possibility is little and volume is large and which is difficult to enter the glasses network.Ti 4+ enter glasses network in the form of and has little effect on whether Al 3+ can enter glass network.Either Ti 4+ or a few of Na + can increase the structure of glasses network and make crystallization activation energy develop,whereas when both Ti 4+ and Na + are added into CaO-Al 2O 3-SiO 2 system glasses,the structure of glasses network is almost similar to the one of pure CaO-Al 2O 3-SiO 2 system glasses and crystallization activation energy is slighely decreased.Na + has no effect on the main crystals from glasses but Ti 4+ has large effect on the main crystals.