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TSEE from Cu-primary solid solutions which were abrabed was measured using a GM counter. The glow curve of a Cu solution involving Zn or Al could hardly be observed after one heating. This result indicates that the alloy surfaces were covered with a ZnO or Al2O3 film. The formation of a ZnO or Al2O3 film was due to a displacement reaction during the oxidations of the alloy surface. This lead to an enhancement of the solute atom concentration on the oxide surface. The oxygen concentration change with the solute content in Cu–Zn and Cu–Al could be interpreted in terms of the starting temperatures and activation energies determined from the glow curves. The TSEE of Cu–Ni and Cu–Ge had similar profiles and developed within the temperature range of the pure Cu glow curve.