An investigation of electrical properties of two series of fluoride glasses containing simultaneously LiF and NaF has been undertaken. The alkali fluoride contents are respectively xAF = 0.10 and xAF = 0.30 : (ZrF4)0.58(BaF2)0.25(LaF3)0.07(LiF)0.10‐x(NaF)x and (ZrF4)0.50(BaF2)0.15(LaF3)0.05(LiF)0.30‐x(NaF)x.
In both series, a mixed alkali effect revealed by the existence of a conductivity minimum is apparently observed. It is shown, however, that the minima have a quite different nature and none of them is actually compatible with the classical „mixed alkali effect”︁ of mobile cations.
In the series xAF = 0.10, where charge transport is essentially assured by the F−‐ions, this effect results from the presence of non mobile alkali ions of different nature in the vicinity of the F−‐ions.
In the series xAF = 0.30, the electrical properties of the extreme compositions xLiF = 0.30 and xNaF = 0.30 are due respectively either to Li+‐ions only or to mobile F−‐ions only. The variation of the ratio r = Na/(Li + Na) from 0 to 1 corresponds to progressive cross over from a cationic conducting glass to an anionic conducting one. The presence of a minimum of conductivity for 0.50 < r < 0.75 has been explained.