Fig. 5
TG-DSC curves for ZrB2 precursor powder using a chitosan and b phenolic resin as carbon source
Morphology of ZrB2 precursor (chitosan as carbon source) heat treated at various temperatures is shown in Fig. 6. Figure 6a reveals the typical morphology of ceramic product for 1000 °C. The product is comprised of large lumps with distribution of a large number of smaller particles. The increase in heat treatment temperature to 1300 °C leads to the intensive transformation of ZrO2 to ZrB2 as indicated by the XRD results, which changes the morphology of the powders (Fig. 6b). The products of 1300 °C show widespread molten layers, exhibiting coral-like morphology, which are endowed with glass feature for its flowing and smooth appearance. These molten layers are believed to be the B2O3 for its low melting point and high viscosity. These widespread B2O3 molten layers have high surface contact with other components (ZrO2and carbon) to let B2O3 obtain a favorable role in the boro/carbothermal reduction over its evaporation. The intimate contact of the reaction component originates from the immobilization of zirconium ion and boric acid by complexation and promotes the formation of ZrB2 phase. The final ZrB2 powders obtained at 1500 °C are cemented in a form of large aggregates consisting of well-defined, irregular polygonal crystal particles. The well-defined crystal particles are formed as the amorphous carbon and glassy B2O3 are consumed. It can be roughly estimated from the magnified image of the inset in Fig. 6c that the particle size lies in the range of 100–500 nm. As shown in the corresponding EDS spectrum, only Zr and B are detected, indicating that the precursor has been entirely transformed into boride phase, which agrees well with XRD analysis. The ZrB2 powders of this method show advantages in the processing, product purity and final product size compared with previous works (both solid state and wet processing routes) [7, 8]. On the other hand, the SEM images of ZrB2 precursor with phenolic resin as carbon source are shown in Fig. 7 and exhibit different features. No molten layers have been observed for the products of 1000 or 1300 °C; moreover, the final products of 1500 °C have a smaller particle size and contain Zr, B, C and a trace of O elements according to the EDS results, which further confirms the XRD results.