锑掺杂钒磷封接玻璃的析晶稳定性研究

Vanadium Phosphorus Sealing Glass Crystallization Stability of Antimony-doped

以80V_2O_5-20P_2O_5-xSb_2O_3(x=0,1,3,5mol%)系统玻璃为研究对象,对其进行红外吸收光谱、拉曼光谱、X射线光电子能谱和固体静态核磁共振测试,研究玻璃的网络结构,分析钒磷玻璃中掺杂锑后析晶稳定性提高的机理.结果表明:钒磷系封接玻璃中加入少量的Sb_2O_3后,玻璃网络结构中桥氧比例增加,非桥氧比例下降;同时V^(4+)/V^(5+)增加,这两点原因导致形成V_2O_5晶相所需的V=O键大幅断裂,抑制了该晶相的生成.Sb_2O_3的引入,破坏了网络平衡态的结构,使(VO_3)_n单链逐渐转化为(V_2O_8)n锯齿状链,玻璃结构更加紧密,难以析晶,析晶稳定性提高.

Based on 80V2O5-20P2O5-xSb2O3（x=0,1,3,5mol%）system glass and heating 1hat 850℃,aglass sample was successful prepared.The mechanism of the increased crystallization stability of Sb2O3-doped vanadium phosphate sealing glass was investigated with infrared absorption spectroscopy,Raman spectroscopy,X-ray photoelectron spectroscopy（XPS）,and nuclear magnetic resonance（NMR）.The tests showed that,by introducing Sb2O3 into glass system,the amount of BO increased while NBO decreased,and part of the NBO structure broke and turned into BO structure.Meanwhile,with the increase of V^4＋/V^5＋,these two factors led to the breaking of V=O bond,which was essential for the formation of V2O5 crystalline phase and inhibited the formation of the crystalline phase.By introducing Sb2O3 into the glass system,the amount of（V2O8）nzigzag chain increased while（VO3）nsingle chain decreased.The intermediate structure of the network equilibrium was destroyed by the introduction of Sb2O3.The（VO3）nsingle chain was gradually transformed into（V2O8）nzigzag chain and the glass structure became tighter.It was difficult to crystalline.The crystallization stability of glass was improved.