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

卤化物离子的键合状态与卤硼酸盐、硅酸盐和亚碲酸盐玻璃的性能

基本信息

批准号：
62550567
负责人：
OSAKA Akiyoshi
金额：
$ 1.28万
依托单位：
OKAYAMA UNIVERSITY
依托单位国家：
日本
项目类别：
Grant-in-Aid for General Scientific Research (C)
财政年份：
1987
资助国家：
日本
起止时间：
1987 至 1988
项目状态：
已结题

来源：
https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-62550567/
关键词：
Halide ions Bonding state Electrical conductivity Borate Silicate Tellurite Glass X-Ray photoelectron spectrum Raman spectrum 構造鉛ホウ酸塩鉛テルル酸塩 X線光量電子分光硫酸イオン

项目摘要

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.

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。