STUDY OF THE EFFECT OF NA/CU SUBSTITUTION IN BI4SR3CA3CU4O16 GLASS-CERAMIC SUPERCONDUCTOR

The composition Bi4Sr3Ca3Cu4-xNaxO16 for x=0.2, 0.4, 0.6, 0.8 and 1.0 was examined, in order to study the effect of Na/Cu substitution on both the glass-forming ability as well as the superconducting properties of the glass-ceramic (GC) phase. Because the GC phase of the composition Bi4Sr3Ca3Cu4O16 (4334) showed superconducting properties below 78.5 K, the crystalline phases formed after heat treatment were identified by X-ray diffraction. This suggests that Na+ substituted the Cut cations. The GC phases were studied by X-ray diffraction, differential thermal analysis, infrared absorption, d.c. electrical conductivity and low-temperature a.c. magnetic susceptibility in the temperature range 77-300 K. The present results support the considerations that the addition of sodium enhances the crystallization of the 4334 phase while sacrificing the glass-forming ability. The crystalline phases precipitated from the rapidly quenched glasses in the Bi-Sr-Ca-Cu-Na-O system were greatly dependent on the heat-treatment time as well as the treatment temperature. The stability and crystallization process of the glass differ greatly depending on the sodium content which acted as fluxing agent. Considering that the formation of the 4334 phase is largely enhanced in sodium-doped samples, it is concluded that the lowering of the partial melting temperature is very important for the enhancement of the formation of the 4334 phase, well as in raising the critical transition temperature. Infrared spectroscopy measurements indicate that part of the ceramic phase is non-metallic. The two-probe method and the standard four-point probe method electrical resistivity indicate that Bi-Sr-Ca-Cu-Na-O superconductor formation was greatly dependent on heat-treatment time as well as treatment temperature. The superconducting crystalline phase, which grew upon heat treatment, was identified as a quasi-tetragonal phase 4334. Electrical resistance measurements together with thermopower results indicate that the electrical properties move from a metal region to a semiconducting region according to the magnetic phase diagram of oxide superconductors. Superconducting 4334 phase with T-c=84 K could be successfully prepared by the GC techniques within 1-2 h thermal cycling, which renders a great saving in processing costs and is a simple method of moulding superconducting articles.