Differential scanning calorimetry (DSC) and mechanical profilometry were used to study wrinkle formation in curing epoxy powder coatings. Powder coating formulations were studied that contained solid epoxy resins, methylene disalicylic acid (MDSA) crosslinker, and an amine-blocked Lewis acid catalyst. Both the crosslinker (MDSA) and the amine-blocked catalyst are required for wrinkle formation. Evaporation of the blocking amine from the free surface of the coating generated a depthwise gradient in the extent of polymerization and crosslinking, and hence in the degree of solidification, as evidenced by the formation of a mechanical skin prior to wrinkling. It is hypothesized that compressive elastic stress develops in the still swellable skin when unreacted low-molecular-weight material from beneath diffuses up into the monomer- or oligomer-depleted crosslinking skin and swells it. This compressive stress, if above a critical value, buckles the skin to produce wrinkles. Experimentally observed compositional requirements for wrinkle formation were consistent with the proposed mechanism. The size of the wrinkles can be controlled by varying formulation parameters such as the amount of catalyst or crosslinker. Increasing the amount of catalyst decreased both the wavelength and the amplitude of the wrinkle pattern. Increasing the amount of crosslinker initially increased the amplitude of the wrinkles; after reaching a maximum level, the wrinkle amplitude decreased. DSC was a useful tool to understand the critical reactions responsible for wrinkling in this system. (c) 2005 Wiley Periodicals, Inc.