FLUORIDE-ION CONDUCTION AND ITS MECHANISM IN FLUORIDE GLASSES

1. Electrical conductivity measurements by ac methods were made of Al<F_3>-、Hf<F_4>-、Sc<F_3>-、Zn<F_2>-、Zr<F_4>-、Ga<F_3>-、Fe<F_3>- and In<F_3>-based fluoride glasses。测试玻璃的作用从大约&lt;10^（-6）&gt;延伸到大约10-&lt;^2 S&gt;和&lt;cm^（-1）&gt;在200 ° C。行为的强度，可以用玻璃成分扩大到一定程度，增加在顺序上的描述。作为一个具有超能力的液体玻璃的结果，在基于该<beta>-<F_2>Pb<F_3>的玻璃系统中找到了铅。&lt;F^-&gt; ions对<F_4>Zr-Ba<F_2>-CsF和<F_3>Fe-Mn<F_2>-Pb<F_2>玻璃进行了相对高电气条件的测量，根据Tubandt和emf方法，对此。结果揭示了前玻璃纯粹是&lt;F^-&gt;-离子导体，而后玻璃混合了&lt;F^-&gt;-离子和电子导体。电化学和&lt;^（19）F&gt;-CW和核磁共振测量是由BaZr制成的 ... More <F_6>glass and<alpha>- and<beta>-BaZr <F_6>crystals。核磁共振结果，在玻璃和水晶中，有两种&lt;F^-&gt;-离子位点，具有不同的运动行为。电子行为和核磁共振结果表明&lt;F^-&gt;离子运动在BaZr<F_6>玻璃、<beta>-BaZr<F_6>和<alpha>-BaZr顺序中的容易度<F_6>，表明玻璃状态对于&lt;F^-&gt;离子行为是可取的，与crystalline状态比较。根据各种氟玻璃和<F_4>Zr-Ba<F_2>-CsF玻璃的电气条件的组合，所述的结果被用于&lt;F^-&gt;离子条件确定因素：&lt;F^-&gt;离子条件确定因素：&lt;F^-&gt;离子在氟玻璃的条件下的条件的&lt;F ^-&gt;离子条件下的条件预先被活性能量决定。通过玻璃形成疗法的平均极化性增加的作用能量，以及在玻璃形成疗法和&lt;F^-&gt; ions之间的单一粘结强度的作用。Less（低）

1. Electrical conductivity measurements by ac methods were made of Al <F_3> -, Hf <F_4> -, Sc <F_3> -, Zn <F_2> -, Zr <F_4> -, Ga <F_3> -, Fe <F_3> - and In <F_3> -based fluoride glasses. The conductivities of the examined glasses ranged from about <10^(-6)> to about 10- <^2S> ・ <cm^(-1)> at 200゜C. The magnitude of conductivity, though it varies to some extent with glass composition, increased in the order described above. As the result a fluoride glass with a conductivity superior to that <beta> -Pb <F_2> was found in the In <F_3> -based glass system.2. The transport numbers of <F^-> ions were examined of Zr <F_4> -Ba <F_2> -CsF and Fe <F_3> -Mn <F_2> -Pb <F_2> glasses with relatively high electrical conductivities by the Tubandt and emf methods, respectively. The result revealed that the former glasses are purely <F^-> -ion conductors, while the latter glasses are mixed <F^-> -ion and electron conductors.3. Electrical conductivity and <^(19)F> -CW・NMR measurements were made of a BaZr … More <F_6> glass and <alpha> - and <beta> -BaZr <F_6> crystals. The NMR result elucidated that, in the glass and the crystals, there are two kinds of <F^-> -ion sites with different behaviors of motion. The electrical conductivity and NMR results clarified that the easiness of <F^-> -ion movement are in the order BaZr <F_6> glass, <beta> -BaZr <F_6> , <alpha> -BaZr <F_6> , indicating that a glassy state is favorable for <F^-> -ion conduction, compared with a crystalline state.4. Based on the compositional dependence of electrical conductivity of various fluoride glasses and Zr <F_4> -Ba <F_2> -CsF glasses, the followings were deduced on the <F^-> -ion conduction-determining factors: The conductivity of <F^-> ions in fluoride glasses are predominantly determined by the activation energies for conduction. The activation energy for conduction decreases with an increase in the average polarizability of glass-constituting cations and with a decrease in the single bond strengths between glass-forming cations and <F^-> ions. Less