The limitation of poor mechanical stability and difficulties in printing electrically conductive components can be overcome owing to the recent introduction of nanotechnology into the field of additive manufacturing (AM) and the consequent development of nonconventional polymer nanocomposites suitable for 3D printing. In the present work, different weight percentages (up to 6 wt % in total) of carbon-based nanostructures—multiwalled carbon nanotubes (MWCNTs), graphene nanoplatelets (GNPs), and a combination of both fillers (MWCNTs/GNPs)—were incorporated into poly(lactic) acid (PLA, Ingeo™) in an attempt to overcome several limitations of conventional 3D manufacturing based on insulating materials. Solution blending and melt mixing were the two fabrication methods adopted for preparation of the samples under test. A comparison of the morphological, rheological, and electrical properties of the resulting nanocomposites was carried out. Moreover, for the same weight concentrations, the influence of physical and geometrical features (i.e., functionalization and aspect ratio) of the embedded fillers was also investigated. Rheological methods were applied to control the quality of fillers dispersion in PLA matrix. The rheological percolation threshold was considered as reference in order to evaluate the internal structure of nanodispersions. TEM visualization, combined with rheological characterizations, was used for efficient control of the nanofiller dispersion. DC characterization revealed that lower electrical percolation thresholds and higher values of electrical conductivity were achieved using fillers with a larger aspect ratio and melt mixing, respectively. Moreover, given the possibility of obtaining complex and appropriate shapes for electromagnetic compatibility (EC) applications, electromagnetic (EM) response of the nanocomposites at the highest filler concentration was investigated in GHz and THz regions. It was found that the electromagnetic shielding efficiency (EMI) of nanocomposites strongly depended on the aspect ratio of the nanofillers, whereas the type of processing technique did not have a significant effect. Therefore, a careful choice of methods and materials must be made to address the final application for which these materials and further 3D printed architectures are designed.

Poly(lactic) acid nanocomposites filled with graphene nanoplatelets (GNPs) and multiwall carbon nanotubes (MWCNTs) are studied, varying the filler size, shape, and content within 1.5–12 wt.%. The effects of the intrinsic characteristics of nanofillers and structural organization of nanocomposites on mechanical, electrical, thermal, and electromagnetic properties enhancement are investigated. Three essential rheological parameters are identified, which determine rheology–structure–property relations in nanocomposites: the degree of dispersion, percolation threshold, and interfacial interactions. Above the percolation threshold, depending on the degree of dispersion, three structural organizations are observed in nanocomposites: homogeneous network (MWCNTs), segregated network (MWCNTs), and aggregated structure (GNPs). The rheological and structural parameters depend strongly on the type, size, shape, specific surface area, and functionalization of the fillers. Consequently, the homogeneous and segregated network structures resulted in a significant enhancement of tensile mechanical properties and a very low electrical percolation threshold, in contrast to the aggregated structure. The high filler density in the polymer and the low number of graphite walls in MWCNTs are found to be determinant for the remarkable shielding efficiency (close to 100%) of nanocomposites. Moreover, the 2D shaped GNPs predominantly enhance the thermal conductivity compared to the 1D shaped MWCNTs. The proposed essential structural parameters may be successfully used for the design of polymer nanocomposites with enhanced multifunctional properties for 3D printing applications.

In the present study, polylactic acid (PLA) enriched with carbonaceous particles like multi-walled carbon nanotubes (MWCNTs), graphene nanoplates (GNPs) or a combination of both up 12 wt % of loading are used for producing 3D-printed specimens with fused deposition modeling (FDM) technology which are then experimentally and theoretically investigated. The goal is to propose a non-conventional filaments indicated for additive manufacturing process with improved dielectric and thermal properties, compared to the performances exhibited by the unfilled polymer. In the light of the above, a wide dielectric spectroscopy and a thermal analysis, supported by a morphological investigation, are performed. The results highlight that the introduction of 1-dimensional filler (MWCNTs) are more suitable for improving the dielectric properties of the resulting materials, due to the enhancement of the interfacial polarization and the presence of functionalized groups, whereas 2-dimensional nanoparticles (GNPs) better favor the thermal conduction mechanisms thanks to the lower thermal boundary resistance between the two phases, polymer/filler. In particular, with a loading of 12 wt % of MWCNTs the relative permittivity reaches the value of 5.35 × 10³ much greater than that of 3.7 measured for unfilled PLA while for the thermal conductivity the enhancement with 12 wt % of GNPs is about 261% respect the thermal behavior of the neat polymer. The experimental results are correlated to theoretical findings, whereas a design of experiment (DoE) approach is adopted for investigating how the different fillers influence the dielectric and thermal performances of the 3D-printed parts, thus assisting the design of such innovative materials that appear promising for development and applications in the electromagnetic (EM) field and heat transfer.