Abstract

Phase equilibria of the zinc oxide–cobalt oxide system were studied by a combination of X‐ray diffraction and in situ electrical conductivity and thermopower measurements of bulk ceramic specimens up to 1000°C in air. Rietveld refinement of X‐ray diffraction patterns demonstrated increasing solubility of Co in ZnO with increasing temperature, which is supported by the slight increase in wurtzite (Zn1−xCoxO) cell volume and lattice parameter a versus temperature determined for the phase boundary compositions. Similarly, the solubility of Zn in CoO increased with increasing temperature. In contrast, the spinel phase (ZnzCo3−zO4) exhibited retrograde solubility for Zn. Electrical measurements showed that the eutectoid temperature for transformation of rocksalt Co1−yZnyO into wurtzite and spinel is 894 ± 3°C, and the upper temperature limit of the stability of the spinel phase is 894°C–898°C for the compositions Co/(Zn+Co) = 0.82–1. The resulting composition‐temperature phase diagram is presented and compared to the earlier (1955) diagram by Robin.

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