Sintering and Electrical Properties According to Sb/Bi Ratio(II) : ZnO-Bi2O3-Sb2O3-Co3O4-Cr2O3 Varistor

Abstract

In this study we aimed to examine the co-doping effects of 1/6 mol% <TEX>$Co_3O_4$</TEX> and 1/4 mol% <TEX>$Cr_2O_3$</TEX> (Co:Cr = 1:1) on the reaction, microstructure, and electrical properties, such as the bulk defects and the grain boundary properties, of ZnO-<TEX>$Bi_2O_3-Sb_2O_3$</TEX> (ZBS; Sb/Bi = 0.5, 1.0, and 2.0) varistors. The sintering and electrical properties of Co,Cr-doped ZBS, ZBS(CoCr) varistors were controlled using the Sb/Bi ratio. Pyrochlore (<TEX>$Zn_2Bi_3Sb_3O_{14}$</TEX>), <TEX>${\alpha}$</TEX>-spinel (<TEX>$Zn_7Sb_2O_{12}$</TEX>), and <TEX>${\delta}-Bi_2O_3$</TEX> were formed in all systems. Pyrochlore was decomposed and promoted densification at lower temperature on heating in Sb/Bi = 1.0 by Cr rather than Co. A more homogeneous microstructure was obtained in all systems affected by <TEX>${\alpha}$</TEX>-spinel. In ZBS(CoCr), the varistor characteristics were improved (non-linear coefficient, <TEX>${\alpha}$</TEX> = 20~63), and seemed to form <TEX>${Zn_i}^{{\cdot}{\cdot}}$</TEX>(0.20 eV) and <TEX>${V_o}^{\cdot}$</TEX>(0.33 eV) as dominant defects. From impedance and modulus spectroscopy, the grain boundaries were found to be composed of an electrically single barrier (0.94~1.1 eV) that is, however, somewhat sensitive to ambient oxygen with temperature. The phase development, densification, and microstructure were controlled by Cr rather than by Co but the electrical and grain boundary properties were controlled by Co rather than by Cr.