Unraveling the Print-Structure-Property Relationships in the FFF of PEEK: A Critical Assessment of Print Parameters.

Poly-ether ether ketone (PEEK) is a high-performance thermoplastic known for its excellent mechanical properties, making it relevant for aerospace and medical applications. Additive manufacturing (AM) represents a critical step towards integrating PEEK into these sectors, particularly for complex geometries and custom parts. However, the mechanical properties achieved through AM have not yet reached those obtained via conventional techniques. Recent studies have sought to optimize the printing parameters to bridge this gap, but their findings remain inconsistent and difficult to generalize-suggesting a strong dependence on the experimental conditions. This is partly due to the Fused Filament Fabrication of PEEK being an emerging technology, with many studies relying on in-house built printers. Moreover, the underlying microstructural mechanisms governing its performance have rarely been explored in depth. In this work, we establish clear processing-structure-property relationships by integrating a rigorous DoE approach with comprehensive microstructural characterization. Our results highlight the dominant role of the processing environment near the glass transition temperature in promoting chain mobility, enhancing the amorphous phase ordering, and improving the mechanical performance: crystallinity alone does not fully explain the mechanical behavior of additively manufactured PEEK. Further, higher nozzle temperatures lower the porosity and increase the filament bonding, while faster printing speeds reduce the crystallinity and increase the porosity, negatively affecting the mechanical integrity. The results of this study are generalizable to any FFF printer of PEEK. Other materials or printing technologies are out of the scope of this work.