Superconducting Bi1.5Pb0.5Sr2Ca2Cu3O(x) ceramics by rapid melt quenching and glass crystallization

A glass of nominal Bi(1.5)Pb(0.5)Sr2Ca2Cu3O(x) composition, prepared by rapid quenching of the melt, showed a glass transition temperature of 383 C, crystallization temperature of 446 C, melting temperature of 855 C, and bulk density of 5.69 g/cu cm in air. The activation energy for crystallization of the glass was estimated to be 292kJ/mol from non-isothermal DSC. On heating in oxygen, the glass showed a slow and continuous weight gain starting at approximately 530 C which reached a plateau at approximately 820 C. The weight gained during heating was retained on cooling to ambient conditions indicating an irreversible oxidation step. The influence of annealing conditions on the formation of various phases in the glass has been investigated. The Bi(2)Sr(2)Ca(0)Cu(1)O(6) phase crystallized out first followed by formation of other phases at higher temperatures. The high-T(sub c) phase, isostructural with Bi(2)Sr(2)Ca(2)Cu(3)O(10) was not detected below 840 C, but its fraction increased with the annealing time at 840 C. A sample annealed at 840 C for 243h in air and furnace cooled showed the highest T(sub c)(R=0) of 107.2K and a narrow transition width, delta T(sub c)(10 to 90 percent), of approximately 2 K. The high T(sub c) phase does not seem to crystallize out directly from the glass but is rather produced at high temperature by reaction between the phases formed at lower temperatures. The kinetics of 110K phase formation was sluggish. It appears that the presence of lead helps in the formation and/or stabilization of the 110 K phase.