Thermochimica Acta, Vol.325, No.2, 133-142, 1999
Crystallization kinetics of superconducting precursor glasses in the Bi-Pb-Sr-Ca-Cu-O system
The crystallization kinetics of Bi,Pb-based superconducting precursor glasses such as Bi1.6Pb0.4Sr2Ca2Cu3Oy (Sample A) with different copper valence states and Bi1.6Pb0.4Sr2CaxCu3Oz (Sample B) with different Ca contents have been examined by differential thermal analysis. The modified Kissinger equation for the nonisothermal crystallization process is used to evaluate the activation energy, E-a, for the crystallization,. The number of crystal nuclei is almost independent of the heating rate in all samples, and the Bi2Sr2CuOx phase appearing first grows three-dimensionally. The values of E-a of Sample A is around 320 kJ mol(-1). The values of E-a in Sample B with small Ca contents of y=0.5 and 1.0 are 299 and 287 kJ mol(-1), respectively. Compared with Bi-based glasses containing no Pb, Bi,Pb-based glasses tend to have small values of E-a. It is found that the values of E-a of Bi,Pb-based glasses are similar to those in TeO2-based and fluoride glasses which are known as fragile glass-forming systems.
Keywords:DIFFERENTIAL SCANNING CALORIMETRY;THERMAL-STABILITY;TELLURITEGLASSES;CERAMICS;RELAXATION;GROWTH;PHASE