Samples of in the range 0<δ<0.1 were prepared by electrochemical insertion of oxygen in KOH; the oxygen content was determined by iodometric titration. The temperature variations of resistance R and Seeback coefficient α were used to monitor as a function of the compositional parameter δ not only the evolution of the superconductive transition temperature , but also the diffusion-controlled spinodal phase segregation occurring in the temperature range 200<T≤300 K. The data also show that the δ interstitial oxygen atoms per formula unit enter as ions at least in the range 0<δ≤0.070. Comparison of the transport properties of samples slow-cooled from room temperature to 77 K reveals an -atom segregation over the range 0<δ≤0.066; this segregation disappears for δ> where the atoms become ordered, and 0.066<<0.070 was determined. Analysis of neutron-diffraction data from available literature gives a spinodal decomposition temperature vs δ that falls to 200 K at (max)≊0.05; the diffusion-controlled spinodal phase segregation occurs within the phase field of the -disordered orthorhombic structure.
The oxygen-rich phase having (max)≊0.05 is superconductive with a zero-resistance temperature =26 K that is lower than the =32 K observed for δ>; falls to a minimum near δ=0.0625 within the compositional range (max)<δ<, which suggests the presence of a competitive nonsuperconductive line phase near p=1/8 holes per Cu atom as is found in the system near x=1/8. A nonsuperconductive transition at =47±1 K was found in slow-cooled samples over the range 0<δ<; it is suppressed by both high pressure and the quenching procedure. We associate it with the competitive nonsuperconductive phase stabilized near p=1/8. In the ordered- phase found for δ>, a ‘‘tail’’ in the R-vs-T curve extends into the superconductive temperature range where α=0; it is attributed to a liquid-vortex state rather than a second superconductive phase. The pressure dependences of and the -atom mobility were used to distinguish the superconductive phases found for δ< and δ>. The appearance of a nonsuperconductive line phase in the interval (max)<δ< permits reconciliation of the data, including indirect evidence for charge fluctuations stabilized below a <150 K in this interval. The indirect evidence for charge fluctuations is the same as that discussed by us elsewhere in the framework of a model developed for the system .