Date of Graduation


Document Type


Degree Type



Statler College of Engineering and Mineral Resources


Mechanical and Aerospace Engineering

Committee Chair

Xueyan Song


Waste heat and thermal gradients available at power plants can be harvested to power wireless networks and sensors by using thermoelectric (TE) generators that directly transform temperature differentials into electrical power. Oxide materials are promising for TE applications in harsh industrial environments for waste heat recovery at high temperatures in air, because they are lightweight, cheaply produced, highly efficient, and stable at high temperatures in air. Ca3Co4O9(CCO) with layered structure is a promising p-type thermoelectric oxide with extrapolated ZT value of 0.87 in single crystal form [1]. However the ZT values for the polycrystalline ceramics remain low of ∼0.1-0.3. In this research, nanostructure engineering approaches including doping and addition of nanoinclusions were applied to the polycrystalline CCO ceramic to improve the energy conversion efficiency.;Polycrystalline CCO samples with various Bi doping levels were prepared through the sol-gel chemical route synthesis of powders, pressing and sintering of the pellets. Microstructure features of Bi doped ceramic bulk samples such as porosity, development of crystal texture, grain boundary dislocations and segregation of Bi dopants at various grain boundaries are investigated from microns to atomic scale. The results of the present study show that the Bi-doping is affecting both the electrical conductivity and thermal conductivity simultaneously, and the optimum Bi doping level is strongly correlated with the microstructure and the processing conditions of the ceramic samples. At the optimum doping level and processing conditions of the ceramic samples, the Bi substitution of Ca results in the increase of the electrical conductivity, decrease of the thermal conductivity, and improvement of the crystal texture. The atomic resolution Scanning Transmission Electron Microscopy (STEM) Z-contrast imaging and the chemistry analysis also reveal the Bi-segregation at grain boundaries of CCO polycrystalline samples. In order to further decrease the thermal conductivity and increase the overall energy conversion efficiency of ceramic samples. The highest ZT value obtained is 0.32 at 973K for Ca and Co site Bi doping. The effect of the nanoinclusions on the performance and the microstructure of CCO were investigated as well.