Search

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 (TG) 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 TG 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.

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.

Encapsulants based on ethylene-vinyl acetate copolymers (EVA) or polyolefin elastomers (POE) are essential for glass or photovoltaic module laminates. To improve their multi-functional property profile and their durability, the encapsulants are frequently peroxide crosslinked. The crosslinking kinetics are affected by the macromolecular structure and the formulation with stabilizers such as phenolic antioxidants, hindered amine light stabilizers or aromatic ultraviolet (UV) absorbers. The main objective of this study was to implement temperature-rise and isothermal dynamic mechanical analysis (DMA) approaches in torsional mode and to assess and compare the crosslinking kinetics of novel UV-transparent encapsulants based on EVA and POE. The gelation time was evaluated from the crossover of the storage and loss shear modulus. While the investigated EVA and POE encapsulants revealed quite similar activation energy values of 155 kJ/moles, the storage modulus and complex viscosity in the rubbery state were significantly higher for EVA. Moreover, the gelation of the polar EVA grade was about four times faster than for the less polar POE encapsulant. Accordingly, the curing reaction of POE was retarded up to a factor of 1.6 to achieve a progress of crosslinking of 95%. Hence, distinct differences in the crosslinking kinetics of the UV-transparent EVA and POE grades were ascertained, which is highly relevant for the lamination of modules. Version of record

The thermomechanical and mechanical behavior of electrical steel laminates was investigated by dynamic mechanical analysis (DMA) and a short beam test. These tests were implemented to evalu...

A fatigue fracture mechanics method was developed, implemented and used to characterize the crack kinetics of laminated electrical steel. Tests were carried out on double cantilever beam specimen based on electrical steel sheets and an epoxy adhesive layer with a thickness of just 10 µm. Two different crack length measurement methods based on optical measurement or compliance calculation were evaluated. As validation method specimens with different artificial initial crack length were used. The accuracy is limited to thin and stiff adhesives ensuring a small plastic zone size compared to the crack length. The accuracy of the crack length evaluation methods was higher for the compliance based approach meeting standard specifications at low to intermediate crack length values. The compliance based method was applied to investigate a specimen series varying the pre-curing temperature of the epoxy adhesive systematically. The fatigue tests were performed at ambient condition and 60 °C. At ambient temperature, laminates based on coated electrical steel pre-cured at low to intermediate temperatures revealed rather slow crack propagation rates in comparison to laminates made from coated steel pre-cured at 250 °C. The differences in the stable crack propagation rate of the investigated laminates at ambient conditions were up to two orders of magnitude higher. At 60 °C, the worst performance was also obtained for laminates based on coated steel sheets pre-cured at 250 °C. The failure mode was similar for laminates tested at 23 and 60 °C. While interfacial failure was ascertained for laminates based on coated steel sheets pre-cured at 190 and 250 °C, the better performing laminates made from sheets with epoxy coating pre-cured at 210 or 230 °C exhibited mainly cohesive failure. Hence, adequate pre-curing conditions are of utmost importance for the crack kinetics of adhesively bonded electrical steel.