Crystallization of Bi–Sr–Ca–Cu–O glasses in oxygen

Abstract

A detailed study of the crystallization process for compositions near Bi₂Sr₂Ca₁Cu₂O_y was undertaken using differential thermal analysis (DTA), transmission and scanning electron microscopy (TEM and SEM), and x-ray diffraction (XRD). Glasses prepared by a splat-quench technique were free of secondary phases in most cases. A two-step crystallization process in oxygen was observed in which partial crystallization of the glass occurs initially with the nucleation of “2201” and Cu₂O, and is completed with the formation of SrO, CaO, and Bi₂Sr_3−xCa_xO_y. No specific thermal event could be associated with the formation of the “2212” phase. Rather, formation occurs via conversion of 2201 into 2212. This was a kinetically limited process at temperatures below 800 °C as other phases were found to evolve in addition to the 2212 phase during extended anneals. In contrast, a nearly full conversion to the 2212 phase occurred after only 1 min of annealing at 800 °C and above. However, changes in resistivity data, secondary phases, and the measured 2212 composition upon extended anneals at 865 °C showed that considerably longer heat treatments were necessary for the sample to reach its equilibrium state.