As fused filament fabrication (FFF) continues to gain
popularity,
many studies are turning to nanomaterials or optimization of printing
parameters to improve the materials’ properties; however, many
overlook how materials formulation and additive manufacturing (AM)
processes cooperatively engineer the evolution of properties across
length scales. Evaluating the in-process evolution of the nanocomposite
using AM will provide a fundamental understanding of the material’s
microstructure, which can be tailored to create unique characteristics
in functionality and performance. In this study, the crystallinity
behavior of polyetheretherketone (PEEK) was studied in the presence
of carbon nanotubes (CNTs) as a nucleation aid for improved crystallization
during FFF processing. Using various characterization techniques and
molecular dynamics simulations, it was discovered that the crystallization
behavior of extruded filaments is very different from that of 3D printed
roads. Additionally, the printed material exhibited cold crystallization,
and the CNT addition increased the crystallization of printed roads,
which were amorphous without CNT addition. Tensile strength and modulus
were increased by as much as 42 and 51%, respectively, due to higher
crystallinity during printing. Detailed knowledge on the morphology
of PEEK–CNT used in FFF allows gaining a fundamental understanding
of the morphological evolution occurring during the AM process that
in turn enables formulating materials for the AM process to achieve
tailored mechanical and functional properties, such as crystallinity
or conductivity.