In Situ Polymerization and Synthesis of UHMWPE/Carbon Fiber Composites

Carbon-fiber-reinforced composites of ultra-high-molecular-weight polyethylene (UHMWPE) are not easily prepared because of their high viscosity, although they can be advantageous in advanced engineering applications due to their superior mechanical properties in combination with their low specific weight and versatility. Short polyacrylonitrile-based carbon-fiber-reinforced UHMWPE composites with fiber contents of 5, 10, and 15 wt.% could easily be prepared using in situ ethylene polymerization. Therefore, MgCl₂ was generated at the Brønsted acidic groups of the fiber surface by employing a reaction between the co-catalysts Mg(C₄H₉)₂ and AlEt₂Cl. Titanation with TiCl₄ resulted in a catalyst directly on the fiber surface. The catalyst polymerized ethylene (2 bar pressure at 50 °C), forming a UHMWPE matrix near the surface; its fragmentation led to polymer particles associated with the fiber. The catalyst activity on the fiber surface of untreated (CF-Pr, 3.48 ± 0.24 wt.%) and oxidized fibers (CF-Ox, 7.41 ± 0.03 wt.%) was 20% lower. CF-Pr compression-molded samples showed tensile strengths of up to 50.4 ± 1.3 MPa, while CF-Ox samples reached 39.1 ± 0.6 MPa, surpassing the performance of composites prepared by melt compounding. The stiffness of 1.58 ± 0.17 GPa for a melt-compounded material was lower than the 3.24 ± 0.10 GPa for CF-Pr and 2.19 ± 0.07 GPa for CF-Ox composites. A fracture examination showed fiber pull-outs, matrix residues on the fibers, and the formation of some extensional polymer fibrils. The latter explains the higher stress at yield and the breakage of the CF-Pr based composites in particular. The potential of in situ polymerized UHMWPE composites for the utilization in high-performance structural applications is thus demonstrated.