Simultaneous rheology and cure kinetics dictate thermal post-curing of thermoset composite resins for material extrusion.

Thermoset composites are excellent candidates for material extrusion because they shear thin during extrusion but retain their shape once deposited via a yield stress. However, thermal post-curing is often required to solidify these materials, which can destabilize printed parts. Elevated temperatures can decrease the rheological properties responsible for stabilizing the printed structure before crosslinking solidifies the material. These properties, namely the storage modulus and yield stress, must therefore be characterized as a function of temperature and extent of reaction for various filler loadings. This work utilizes rheo-Raman spectroscopy to measure the storage modulus and dynamic yield stress as a function of temperature and conversion in epoxy-amine resins with fumed silica mass fractions up to 10 %. Both rheological properties are sensitive to conversion and particle loading, but only the dynamic yield stress is reduced by elevated temperatures early in the cure. Notably, the dynamic yield stress increases with conversion well before the chemical gel point. These findings motivate a two-step cure protocol that starts at a low temperature to mitigate the drop in dynamic yield stress, then ramps up to a high temperature when the dynamic yield stress is no longer at risk of decreasing to rapidly drive conversion to near completion. The results suggests that structural stability can be improved without resorting to increasing filler content, which limits control over the final properties, laying the groundwork for future studies to evaluate the stability improvements provided by the multi-step curing schedules.