ABSTRACTThe rhombohedral alkaline earth-bismuth oxide phase, an oxygen ion conductor, does not coexist stably with electronic conductors in any of the three binary systems, Ca-Bi-O, Sr-Bi-O, Ba-Bi-O. A thermodynamically stable composite of a rhombohedral phase that contains Ba and Sr or Ca or both with the electronic conductor BaBiO3 may be synthesized. The rhombohedral phase appears to have complete mutual miscibility of the alkaline earth elements. The composi- tions of rhombohedral phase that coexist with BaBiO3 in the Sr-Ba-Bi ternary system and the Ca- Sr-Ba-Bi quaternary systems are described. The value of ionic conductivity of the rhombohedral phase (at a constant Bi: [Ca+Sr+Ba]) is not dependent on the relative amounts of Ca, Sr, and Ba. The temperature at which the rhombohedral phase undergoes a polymorphic transformation from a low-temperature (2) form that is a weak ion conductor to a high-temperature (β1) form that is a much better oxygen ion conductor. The temperatures of the polymorphic transformation and of the upper stability limit of the rhombohedral phase both depend strongly on Ca: Sr: Ba. The β1 form develops in the Ba-Bi system at the lowest temperatures and at the highest ones in the Ca- Bi system. On the other hand, the Ca-Bi phase has greater thermal stability than its Ba ana- logues. The temperature range over which a useful composite conductor can operate is, there- fore, strongly dependent upon the bulk composition of the system.
