Generation of Multi-Scale Thermoplastic Composites for Use in Injection Molding and Fused Filament Fabrication

Thermoplastic composites that have been reinforced by thermotropic liquid crystalline (TLCP) fibrils in the microscale and by nanoparticles in the nanoscale are defined as multi-scale wholly thermoplastic composites (WTCs). Multi-scale WTCs have been proposed as lightweight replacements with high performance for some traditional glass fiber (GF) and carbon fiber (CF) reinforced composites materials in various applications. TLCPs are known for performing mechanical properties similar to those of the lower end of CF but significantly better than those of GF. To enhance the mechanical properties of TLPC reinforced WTCs, carbon nanotubes (CNTs) are considered being used as a secondary enhancement in WTCs. CNTs have gathered significant interest in the last 30 years because of their high aspect ratio, high mechanical properties, and other high-performance properties. The focus of this work is on investigating the processing conditions of generating in situ injection-molded multi-scale WTCs, then extending the technology to dual-extrusion and fused filament fabrication (FFF) and obtain high-performance multi-scale WTC products. This dissertation initially focused on investigating the processing conditions, in particular mixing histories and processing temperature profiles, of generating in situ injection-molded multi-scale WTCs, which consist of a representative TLCP, scCO2 aided exfoliated CNTs, and the thermoplastic matrix polyamide 6 (PA 6). The supercooling behavior of the TLCP and thermal stability of PA 6 are studied by applying the rheological methods of small amplitude oscillatory shear (SAOS). Multiple mixing histories with CNTs and processing temperature profiles are analyzed based on the criterion of maximizing tensile properties of multi-scale WTCs and minimizing thermal degradation of the matrix. Under the optimum processing conditions, the in situ injection-molded multi-scale WTCs exhibit a 26% and 34% tensile modulus and strength enhancement, compared to the in situ injection-molded WTCs with no CNTs. Scanning electron micrograph (SEM) images were used to understand the enhancement. The second part of this work is to extend the scCO2 aided in situ multi-scale WTCs processing technology to dual-extrusion and FFF. Multi-scale WTC filaments, which consists of TLCP, CNTs, and polyamide copolymer (PAc), are generated by dual-extrusion, and 3D printed into rectangular specimens in FFF. The 1 wt% CNTs reinforced multi-scale WTC filaments generated by the means of dual-extrusion exhibit 225% and 80% improvement in tensile modulus and strength, respectively, compared to the WTC filaments with no CNTs. In FFF, 40 wt% TLCP/1 wt% CNT/PAc 3D printed specimens with filament laid in longitudinal direction exhibited excellent tensile modulus and strength of 38.92 GPa and 127.16 MPa, respectively. The well-dispersed exfoliated CNTs show high alignment with TLCP microfibrils in the multi-scale WTC filaments and their laid-down specimens, which causes the significant tensile modulus enhancement. Bridging elements are discovered between TLCP fibrils and PAc matrix to improve interfacial adhesion, which is attributed to the well-dispersed exfoliated CNTs. Finally, the significant improvements in tensile properties attributed to scCO2 aided exfoliated CNTs in WTCs are verified on the multi-scale WTCs based on polypropylene (PP). Moreover, additional tensile properties improvements for exfoliated CNTs reinforced multi-scale WTCs are obtained with the use of maleic anhydride grafted polypropylene (MAPP). With 1 wt% CNTs and 16 wt% MAPP dual reinforcement, 20 wt% TLCP reinforced WTCs based on polypropylene (PP) exhibit 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° rectilinear pattern, respectively. The dual reinforcement also improves the tensile strength of 20 wt% TLCP reinforced WTC filaments by up to 73%. The high alignment between TLCP fibrils and CNTs are confirmed in the multi-scale WTCs based on PP. Besides the bridging elements attributed to CNTs found in the second part of this work, SEM images show that CNTs are partially trapped in TLCP fibrils.

Name thesis:degree_name

Doctor of Philosophy

Level thesis:degree_level

doctoral

Discipline thesis:degree_discipline

Chemical Engineering

Department dc:contributor.department

Chemical Engineering

Grantor dc:publisher

Virginia Tech

Year dc:date.issued

2021

Author dc:creator

• Han, Jier Yang

Chair dc:contributor.committeechair

• Baird, Donald G.

Committee members dc:contributor.committeemember

• Bortner, Michael J.
• Foster, Earl Johan
• Martin, Stephen Michael
• Barone, Justin Robert

• Wholly Thermoplastic Composites
• Thermotropic Liquid Crystalline Polymer
• Tensile Properties Enhancement
• Carbon Nanotube
• In situ Composites
• Dual Extrusion
• Fused Filament Fabrication

Statement dc:rights

• In Copyright

Licence dc:rights.uri

• http://rightsstatements.org/vocab/InC/1.0/

Dc Identifier Other

vt_gsexam:28619

OAI identifier oai:identifier

oai:vtechworks.lib.vt.edu:10919/111090