Ceramic nickel-copper-manganite based negative temperature coefficient thermistors are unstable under thermal constraint, which increases the resistivity of these devices. This unstability can be reduced by the addition of a small amount of barium. These ceramics have a spinel structure, and the conduction takes place by a hopping process involving [Mn3+]/[Mn4+] octahedral ions. This study by the use of thermopower measurements points out that the resistivity change under thermal constraint is principally due to the disproportionation of [Mn3+]/[Mn4+] ions in the octahedral sites. Furthermore, it seems that some nickel ions migrate from octahedral to tetrahedral sites.