A Theoretical Treatise on the Electronic Structure of Designer Hard Materials

Abstract: The subject of the present thesis is theoretical first principles electronic structure calculations on designer hard materials such as the transition metal carbides and oxides. The theoretical investigations have been made in close collaboration with experimental research and have addressed both bulk electronic properties and surface electronic properties of the materials.Among the bulk studies are investigations on the effects of substoichiometry on the relative phase stabilities and the electronic structure of several phases of MoC and the nature of the resulting vacancy peaks. The changes in phase stabilities and homo-geneity ranges in the group IV to VI transition metal carbides have been studied and explained, from calculations of the T=0 energies of formation and cohesive energies. The anomalous volume behavior and phase stabilities in substoichiometric TiC was studied including effects of local relaxations around the vacancy sites. The vacancy ordering problem in this compound was also studied by a combination of electronic structure calculations and statistical physics.The studies of the surface electronic properties include research on the surface energies and work functions of the transition metal carbides and an investigation on the segregation of transition metal impurities on the TiC (100) surface.Theoretical studies with the aim to facilitate the realization of novel designer hard materials were made, among these a survey of means of stabilizing potentially super-hard cubic RuO2, studying the effects of alloying, substoichiometry and lattice strains. A mechanism for enhancing hardness in the industrially important hard transition metal carbides and nitrides, from the discovery of multi-phase/polytypic alloys, has also been predicted from theoretical calculations.