Large-scale reactive thermoset printing: Complex interactions between temperature evolution, viscosity, and cure shrinkage

Thermoset composites are strong candidates for large-scale material extrusion additive manufacturing (AM). However, uncured thermoset composites become unstable as print height increases. Here, chemical initiation of vinyl ester immediately before deposition was used to suppress collapse and enable large-scale thermoset printing. Structural stability was assessed by printing thin walls at various layer times and monitoring thermal gradients with an infrared camera. Stable printing was observed at a layer time of 4.50 min, approximately half the gel time of the material (8 min). Self-weight collapse occurred at short layer time (0.68 min), whereas warpage occurred at long layer time (6.50 min). A new behavior was discovered at intermediate layer time (2.25 min) where the heat generated by the reaction causes new, un-gelled layers to flow. Forced convection eliminates this behavior, stabilizing the 2.25-min layer time print. These findings motivated development of a less exothermic material system, which was used to print a large-scale mold and demonstrate the value of this understanding. By presenting these challenges of large-scale reactive thermoset AM for the first time, this work motivates focused studies of the complex interplay between rheological, thermal, and chemical behaviors to improve the feasibility of large-scale thermoset AM. Tensile properties of the printed material were also measured. Longitudinal and transverse elastic moduli are 3.79 and 2.95 GPa, respectively, and corresponding tensile strengths are 36.11 and 18.83 MPa. The glass transition temperature is 93.13 °C.