Reliable, detailed characterization of internal interfaces has become a topic of increasing interest over the past decade. Naturally, both fundamental scientific interest and a wide variety of applications may benefit from improved understanding of heterogeneous interfaces. We employ pseudopotential, planewave density functional theory to investigate local structure and chemistry at several metal-ceramic interfaces. The particular systems under investigation may hold implications for technological advancement of thermal barrier coatings for jet engine turbines. Specifically, we study interfaces between nickel "alloys" and zirconia as well as the nickel-silica interface. By selectively varying the composition of the metal alloy we compare relative adhesion at these interfaces. Our results indicate that inclusion of early transition metals (Group III and IV) at the nickel-zirconia interface may dramatically increase the interface adhesion strength. The potential application of silicon additions designed to form protective oxides on nickel alloys is discussed in light of our predicted behavior of such interfaces under high temperature conditions similar to those anticipated in jet engine turbine applications. For all systems studied, we analyze the geometric structure and the behavior of the valence electron density to provide insight into the bonding character as well as the trends in adhesion at these interfaces.