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PHYSICAL PROPERTIES AND STRUCTURE OF OXYFLUORIDE MELTS

氟氧化物熔体的物理性质和结构

基本信息

批准号：
03650541
负责人：
MORINAGA Kenji
金额：
$ 1.41万
依托单位：
KYUSHU 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：
1991
资助国家：
日本
起止时间：
1991 至 1992
项目状态：
已结题

来源：
https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-03650541/
关键词：
OXYFLUORIDE MELT ELECTRICAL CONDUCTIVITY FLUORITE OXYGEN PARTIAL PRESSURE POSITIVE HOLE MADELUNG CONSTANT SHORT RANGE ORDER 酸フッ化物系融体ク-ロン力構造 Redox反応

项目摘要

The dependence of oxygen partial pressure(OPP)on electrical conductivity have been studied for MO-MF_2(M=Ca,Sr,Ba) melts and discussed the newly observed phenomena caused by the liquid lattice of fluorite-like structure.Electrical conductivities of MO-MF_2 melts (MO<17mass%) varied with the one-quarter power of OPP in argon and oxygen atmosphere.The dependence of OPP on electrical conductivity kappa can be expressed as kappa^0_<ion>exp(-E/RT)+kappa^0_pP_<0^21/4>exp(-E'/RT), where kappa^0_<ion>exp(-E/RT) and kappa^0_pP_<O^21/4>exp(-E'/RT) are partial conductivity for ions and positive holes.The reversible change in transparency of these melts with OPP was directly observed by the hot-thermocouple method. The crystal structure of fluorite such as CaF_2,SrF_2,and BaF_2 has a high Madelung constant,therefore,the relative long range order is maintained even in liquid state. We call this state "liquid lattice". When oxide MO is added,oxide MO is incorporated into the liquid lattice.The ions M^<2+> and O^<2-> of MO are located on the M^<2+>-site and F^--site,respectively,in the liquid lattice formed by MF_2.The unequal charges of O^<2-> and F^- causes the anion vacancy in the melts. The gaseous oxygen is ionized and dissolved into the melts above a critical OPP in the atmosphere and the oxygen reacted with the anion vacancy and results in the formation of positive holes.The positive holes make the melts to be opaque by the absorption of light and contribute to the conduction.

研究了MO-MF_2体系电导率随氧分压的变化规律（M=Ca，Sr，Ba）熔体的电导率，并讨论了由类萤石结构的液格引起的新现象。在氩气和氧气气氛中，MO-MF_2熔体（MO<17mass%）的电导率随α的四分之一次方变化。α对电导率kappa的依赖关系可表示为kappa^0_<ion>exp（-E/RT）+kappa^0_pP_<0^21/4>exp（-E '/RT），其中kappa^0_ exp（-E'/RT）= 0.21/4）<ion>。exp（-E/RT）和kappa^0_pP_<0^21/4>exp（-E '/RT）是离子和空穴的部分电导率。CaF_2，SrF_2，BaF_2等萤石的晶体结构具有较高的马德隆常数，因此，即使在液态下也能保持相对的长程有序。我们称这种状态为“液体晶格”。当加入氧化物MO时，氧化物MO被引入到MF_2形成的液格中，MO的离子M^<2 +>和O^<2->分别位于M^<2+>-位和F^--位，O^和F^-的不相等电荷<2->导致熔体中阴离子空位。在大气中，当温度高于临界温度时，气态氧被电离溶解到熔体中，氧与熔体中的阴离子空位反应，形成空穴，空穴吸收光使熔体不透明，有助于熔体的导电。