Thermotropic liquid crystalline polymer reinforced polypropylene composites enhanced with carbon nanotubes for use in fused filament fabrication

The objective of this research was to enhance the mechanical properties of wholly thermoplastic composites (WTCs) used in fused filament fabrication (FFF). Multiscale thermoplastic composites, which were based on the use of polypropylene (PP) reinforced with thermotropic liquid crystalline polymer (TLCP) and carbon nanotubes (CNTs), were prepared by a method combining supercritical carbon dioxide (scCO(2))-aided exfoliation and dual-extrusion technologies. Significant enhancement of tensile properties was observed by using 1 wt% exfoliated CNTs to reinforce WTCs consisting of PP with and without maleic anhydride-grafted polypropylene (MAPP, 16 wt%). With 1 wt% CNTs and 16 wt% MAPP dual reinforcement, 20 wt% TLCP reinforced WTCs based on PP exhibited 265%, 274%, and 182% improvement in the tensile modulus of the filaments, laid up specimens in the concentric pattern, and laid up specimens in +/- 45 degrees rectilinear pattern, respectively. For tensile strength, 1 wt% CNTs reinforcement combined with 16 wt% MAPP improved the 20 wt% TLCP reinforced WTC filaments, laid down parts in the concentric pattern, and +/- 45 degrees rectilinear patterns by 73%, 53%, and 65%, respectively. The tensile modulus and strength of multiscale WTC based on MAPP/PP specimens laid down with a concentric pattern are higher than those reported for PP/40 wt% short carbon fiber and PP/48.5 wt% short glass fiber laid down specimens. The advanced tensile modulus properties of 1 wt% CNTs reinforced WTCs are competitive with 9 wt% continuous carbon fiber reinforced nylon composite materials in FFF. Scanning electron microscopy analysis showed extremely strong interfacial adhesion between the TLCP fibrils and the matrix in multiscale WTC filaments and laid down parts, compared to the WTCs with no CNTs reinforcement. The advanced interfacial adhesion between TLCP fibrils and matrix resulted in an enhancement in the tensile strength. The exfoliated CNTs were premixed with the matrix, but they were trapped at and aligned with TLCP fibrils, which may be the primary reason for tensile modulus enhancement.