For delayed crosslinking of waterborne epoxy varnishes, dicyandiamide (DICY) is often used as a latent curing agent. While, for amine-based curing agents such as diaminoethane (DAE), chemical interactions with metal oxides are well described, so far, no studies have been performed for DICY and waterborne epoxy varnishes. Hence, in this work X-ray photoelectron spectroscopy (XPS) was used to investigate reactions of DICY and varnishes with technical surfaces of Al, Zn, and Sn. To directly study the reaction of DICY with metal oxides, immersion tests in a boiling solution of DICY in pure water were performed. A clear indication of the formation of metal–organic complexes was deduced from the change in the N1s peak of DICY. To understand the interfacial interaction and consequently the interphase formation during coating of waterborne epoxy varnishes, advanced cryo ultra-low-angle microtomy (cryo-ULAM) was implemented. Interestingly, a comparable reaction mechanism and the formation of metal complexes were confirmed for varnishes. The coatings exhibited a pronounced enrichment of the DICY hardener at the metal oxide–polymer interface.

Epoxy varnishes are of high relevance to advanced steel laminates for the transformation of electric energy. Structure–property correlations of epoxy varnishes, coil coatings and electrical steel laminates are poorly described. Hence, the main objective of this paper was to develop, implement and evaluate well-defined waterborne model epoxy varnishes for electrical steel laminates, and to elucidate structure–property correlations. Adhesives with systematically varied equivalent epoxy weight (EEW) based on bisphenol-A-diglycidyl ether (DGEBA) were investigated and used to formulate waterborne varnishes. Crosslinking agent dicyandiamide (DICY) was added in an over-stoichiometric ratio. The waterborne model varnishes were prepared by shear emulsification at elevated temperatures. The model varnishes in the A-stage were applied to electrical steel using a doctoral blade. At a peak metal temperature of 210 °C, the coatings were cured to the partly crosslinked B-stage. Coated steel sheets were stacked, laminated and fully cured to C-stage at 180 °C for 2 h. For laminates with an epoxy adhesive layer in the C-stage, glass transition temperatures (T_G) in the range of 81 to 102 °C were obtained by dynamic mechanical analysis in torsional mode. Within the investigated EEW range, a negative linear correlation of EEW and T_G was ascertained. Presumably, higher EEW of the varnish is associated with a less densely crosslinked network in the fully cured state. Roll peel testing of laminates at ambient and elevated temperatures up to 140 °C confirmed the effect of EEW. However, no clear correlation of roll peel strength and glass transition temperature was discernible. In contrast, fatigue fracture mechanics investigations revealed that hydroxyl functionality and crosslinking density were affecting the crack growth resistance of laminates in a contrary manner. The energy-based fracture mechanics approach was much more sensitive than monotonic peel testing.

Epoxy coatings for stacked electrical steel are of high relevance for renewable energy and electric mobility technologies. Waterborne epoxy varnish systems for electrical steel laminates are still under development. The main objective of this study was to assess the effect of fillers on the crosslinking kinetics of epoxies and the mechanical performance of electrical steel laminates. Model varnishes based on bisphenol-A diglycidyl ether (DGEBA) with an epoxy equivalent weight (EEW) of ~ 500 g/mol were modified with CaCO ₃ fillers. The filler content was ranging from 1 to 20 wt%. The onset of gelation for CaCO ₃ modified epoxy varnishes was reduced by up to 5 °C. This effect was primarily attributed to enhanced thermal conductivity and reduced heat capacity. Interestingly, no significant effect on the glass transition temperature of the fully cured epoxy was observable. By mechanical testing of electrical epoxy laminates better roll peel strength values were deduced for laminates with CaCO ₃ modified epoxies. Moreover, crack growth rates in the stable regime and the threshold strain energy release rate were positively affected.