A systematic study of factors affecting the delamination energy release rate and mode mix of a thermal barrier coating attached to a substrate is presented accounting for the influence of thermal gradients combined with rapid hot surface cooling. Transient thermal gradients induce stress gradients through the coating and substrate, which produce overall bending if the substrate is not very thick and if it is not constrained. Due to their influences on the coating stresses, substrate thickness and constraint are important aspects of the mechanics of delamination of coating-substrate systems, which must be considered when laboratory tests are designed and for lifetime assessment under in-service conditions. Temperature gradients in the hot state combined with rapid cooling give rise to a maximum energy release rate for delamination that occurs in the early stage of cooling and that can be considerably larger than the driving force for delamination in the cold state. The rates of cooling that give rise to a large early stage energy release rate are identified.