Melt extrusion and additive manufacturing of a thermosetting polyimide

Additive manufacturing offers the ability to fabricate complex structures without the need for expensive tooling which is very attractive for manufacturing of structural composites. One limitation of additive manufacturing technologies hindering their adoption in high-performance structural composites is the lack of compatible high operating temperature thermosetting resins with robust thermo-oxidative stability. To address this limitation, a reactive melt extruded thermosetting polyimide filament was printed via fused filament fabrication (FFF). A crosslink chemistry has been designed with slow reaction kinetics at the printing temperature which allows printing in a similar manner to engineering thermoplastic filaments. A cure cycle for the as-printed uncrosslinked articles was developed to achieve full cure without loss of shape. The glass transition temperature of the fully cured resin is 250 °C. Comparing longitudinal and transverse tensile strengths of printed and cured coupons showed highly anisotropic behavior. Transverse and through-thickness properties for both uncured and cured printed coupons were nearly identical. The average measured tensile strength of printed and fully cured material was 86 MPa; 73% of fully cured compression molded strength. These results demonstrate the ability to 3D print high performance thermosets without changing commercially available FFF machines.