It was recalled that complex perovskite-type oxides of the form, A3Nb2-xCa1-xO9, became excellent protonic conductors (if x was greater than zero) when they were exposed to water vapor. By using X-ray diffraction and transmission electron microscopy, it was shown that the 1:2 ordering of stoichiometric samples was gradually replaced by 1:1 ordering plus random order. The variously ordered regions appeared as nano-scale fluctuations. A study of the protonic conductivity (table 17) revealed that a rapid increase in the effective mobility of protons accompanied the structural changes. This could be explained in terms of percolation in a composite.
D.Yang, A.S.Nowick: Journal of the American Ceramic Society, 1995, 78[11], 3033-9
Table 17
Proton Conductivity of Ba3Nb2-xCa1-xO9
x/3 | [H] (%) | 400C (S/cm) |
0.02 | 1.0 | 0.00013 |
0.03 | 1.7 | 0.00074 |
0.06 | 6.4 | 0.00272 |
0.08 | 8.7 | 0.00394 |
0.12 | 13.1 | 0.00648 |