One of the principal modes by which electron-beam-evaporated thermal barrier coatings fail is via the nucleation of local regions of debonding, which grow and link together until reaching a critically sized flaw for spontaneous buckling and spalling. This progressive failure mode is used as a basis for analyzing the changes that pan occur in photostimulated luminescence spectra that have been recorded from the thermally grown oxide. This process also provides a basis for the quantitative determination of the extent of local damage prior to spalling from an analysis of the shape of the luminescence spectra.