The oxidation states of Bi, Pb, and Cu in the BiPbSrCaCuO (BPSCCO) system have been determined by a combination of volumetric measurement technique and iodometric titration. It was found that, in contrast to previous reports, the concentration of the Cu3+ ions decreased with increasing Pb content, and Cu3+ ions were absent in samples of Bi1.6Pb0.4Sr1.6Ca2Cu3O9.8, while a Tc at 108 K and a Jc of greater than 12,000 A/cm2 at 77 K were observed. The 110 K phase in BPSCCO was stabilized and showed a high tolerance to change in oxygen partial pressure during sintering. In Pb-doped materials, Bi appears to be trivalent while Pb was determined to be mixed-valence Pb4+ Pb2+. It is suggested that superconductivity in BPSCCO may result from a dynamic transfer of holes from Bi PbO layers toward CuO2 planes
Godkänd; 1990; 20091112 (andbra)