Date of Graduation
The effects of calcination heating rate and ultimate calcination temperature upon calcined coke and subsequent graphitic material microstructures were studied for materials prepared from three different precursors. The pitch precursors used were Mitsubishi AR pitch (a synthetic, 100% mesophase pitch), the NMP-extracted portion of a raw coal, and the NMP-extracted fraction of a coal liquefaction residue obtained from an HTI pilot plant. These materials were all green-coked under identical conditions. Optical microscopy confirmed that the Mitsubishi coke was very anisotropic and the HTI coke was nearly as anisotropic. The coke produced from the direct coal extract was very isotropic. Crystalline development during calcination heating was verified by high-temperature x-ray diffraction. Experiments were performed to ascertain the effects of varying calcination heating rate and ultimate temperature. It was determined that calcined coke crystallite size increased with increasing temperature for all three materials but was found to be independent of heating rate. The graphene interplanar spacing decreased with increasing temperature for the isotropic NMP-extract material but increased with increasing temperature for the anisotropic materialsâ€”Mitsubishi and HTI cokes. Graphene interplanar spacing was also found to be independent of heating rate. Calcined coke real densities were, likewise, found to be independent of heating rate. The anisotropic cokes (Mitsubishi and HTI) exhibited increasing real density with increasing calcination temperature. The NMP-extract coke increased in density up to 1050Â°C and then suffered a dramatic reduction in real density when heated to 1250Â°C. This is indicative of puffing. Since there was no corresponding disruption in the crystalline structure, the puffing phenomena was determined to be intercrystalline rather than intracrystalline. After the calcined cokes were graphitized (under identical conditions), the microstructures were re-evaluated. The crystalline properties of the graphitic materials appeared to be independent of calcination conditionsâ€”both heating rate and final temperatureâ€”for all samples prepared from any given precursor. The calcination step did not influence the microstructure or graphitizability of any of the three materials. The crystallinity of a graphitic material appears to be dictated by the properties of the green coke and cannot be altered by manipulating calcination conditions.
Bennett, Barbara Ellen, "The effect of calcination conditions on the graphitizability of novel synthetic and coal-derived cokes." (2000). Graduate Theses, Dissertations, and Problem Reports. 8472.