Bonding State of Halide ions and Properties of Oxyhaloborate, Silicate and Tellurite Glasses

系统地讨论了卤氧化铅玻璃中卤离子的成键状态和导电机理.铅卤硅酸盐玻璃的结构和导电性对900 cm ↑ [2]<-1>拉曼谱带的分析表明，玻璃中不仅含有二聚硅酸盐阴离子Si_2O_7 ~<6->+作为主要的硅酸盐单元，而且还含有被铅离子包围的自由卤离子。电导率数据支持这一结构模型。Anderson-Stuart对电导激活能的分析表明，成键作用是影响氟离子迁移的主要因素，而网络扩展能是影响氯离子迁移的主要因素.卤硼酸盐玻璃中卤离子的成键状态和氟硼酸盐玻璃的Fls芯的电导X射线光电子能谱表明存在与硼原子成键的氟原子（F-B）以及仅与铅离子成键的自由F离子（Pb. F）。电导率的增加由F的F原子的增加来解释。铅状态。氯硼酸盐玻璃的拉曼光谱表明不存在与B键合的氯原子，而它们的较大尺寸提供较小的电导率。铝原子以六重配位的形式存在，抑制了自由离子的迁移.氟碲酸盐玻璃的组成范围窄是由于所有F原子通过形成Te-F-Te键的桥连活性实现有效的原子堆积。因此，F玻璃的电导率与F含量无关。在Cl玻璃中，桥连的氯原子对导电有贡献，而末端的氯原子对导电没有贡献。拉曼光谱表明，Te单元由三角双锥Te（O，Cl）_4变为三角锥Te（O，Cl）_3。

The bonding state of the halide ions and electrical conduction mechanism have been systematically discussed on lead oxyhalide glasses.1. Structure and conductivity for lead halosilicate glasses An analysis of a 900cm^<-1> raman band indicated that the glasses involve not only a dimeric silicate anion Si_2O_7^<6-> as the major silicate unit but free halide ions surrounded only by the lead ions. The conductivity data support this structure model. An Anderson-Stuart analysis on the activation energy for conduction has indicated that the bonding interaction is a predominate factor for fluoride ion mobility while a network-expanding energy is predominant for chloride ion migration.2. Bonding state of halide ions in haloborate glasses and electrical conduction X-ray photoelectron spectra of Fls core for the fluoroborate glasses have indicated the presence of fluorine atoms bonded to the boron atoms (F-B) as well as free F ions bonded only to lead ions (Pb..F). The increase in conductivity is explained by the increase in F atoms of F..Pb state. Raman spectra for the chloroborate glasses have indicated the absence of chlorine atoms bonded to B while their larger size provides smaller conductivity. Aluminum atoms take 6-fold coordination state and suppress the mobility of the free f ions.3. Glass formation and properties of lead halotellurite glasses A narrow glass formation composition rage for the fluorotellurite glasses is attributed to efficient atomic packing which is attained by bridging activity of all F atoms forming Te-F-Te bonds. The conductivity for the f glasses is accordingly independent of the F content. The bridging chlorine atoms contribute the conduction but not the terminal ones in the Cl glasses. Raman spectra have indicated the variation of Te units from trigonal bipyramid Te(O,Cl)_4 to trigonal pyramid Te(O,Cl)_3.