Effect of reduction treatment on microstructure and mechanical properties of fluorite oxides.

摘要

Ceria based materials because of their high ionic conductivity at low temperatures are potential candidates as the electrolyte component in the new generation of low temperature solid oxide fuel cells (SOFCs). The effects of operation conditions in SOFCs on microstructure and mechanical integrity of ceria-based materials are evaluated in this research. Pure ceria and gadolinium doped ceria (GDC) were selected to perform this investigation. The state-of-art electrolyte material, yttria-stabilized zirconia (YSZ), was also studied for comparison purposes. The samples were heat treated at 800°C under various oxygen partial pressures ( PO2 s) until equilibrium was reached. The defect concentrations were conserved to room temperature by fast cooling. The crystal structure and the lattice parameter were evaluated by the x-ray diffraction method. Microstructural evaluations and fractographic analyses were conducted using electron microscopy techniques. The intrinsic elastic modulus was evaluated using nanoindentation techniques. The bulk elastic modulus and fracture strength were measured using the four-point-bend testing method and fracture toughness was evaluated using chevron-notched Brazilian disc samples loaded under the mode I condition.;The result of this study revealed that microcracks were formed during the reduction heat treatment in ceria and GDC when the PO2 was lower than 10-19 atm. It was also found that ceria samples upon cooling experienced phase transformation that led to the formation of several ordered pseudo-cubic phases.;The intrinsic elastic modulus of both ceria and GDC decreased drastically when heat treated at very low PO2 s while the effect was insignificant in YSZ. These results correlate well with our theoretical modeling. Further analysis suggests that an increase in the point defect concentration weakens the attractive forces between atoms. The degradation of bulk elastic modulus of ceria was more pronounced at low PO2 s due to the presence of microcracks caused by the reduction treatments. The results on fracture properties of ceria showed that the flexural strength decreased significantly after reduction in very low PO2 s; however, in contrast, fracture toughness was increased by 30--40% when the PO2 was decreased to the range of 10-20--10-22 atm. Fractographic studies showed that the microcracks developed during reduction treatment are responsible for the decreased strength. In this dissertation, the enhancement in toughness was explained by crack deflection and microcrack toughening mechanisms.