Design rules for enhanced interfacial shear response in functionalized carbon fiber epoxy composites

Carbon-fiber reinforced composites are ideal light-weighting candidates to replace traditional engineering materials. The mechanical performance of these composites results from a complex interplay of influences operating over several length and time scales. The mechanical performance may therefore be limited by many factors, one of which being the modest interfacial adhesion between the carbon fiber and the polymer. Chemical modification of the fiber, via surface grafting of molecules, is one possible strategy to enhance interactions across the fiber-polymer interface. To achieve systematic improvements in these modified materials, the ability to manipulate and monitor the molecular structure of the polymer interphase and the surface grafted molecules in the composite is essential, but challenging to accomplish from a purely experimental perspective. Alternatively, molecular simulations can bridge this knowledge gap by providing molecular-scale insights into the optimal design of these surface-grafted molecules to deliver superior mechanical properties. Here we use molecular dynamics simulations to predict the interfacial shear response of a typical epoxy/carbon-fiber composite for both pristine fiber and a range of surface graftings. We allow for the dynamic curing of the epoxy in the presence of the functionalized surface, including cross-link formation between the grafted molecules and the polymer matrix. Our predictions agree with recently reported experimental data for these systems and reveal the molecular-scale origins of the enhanced interfacial shear response arising from functionalization. In addition to the presence of interfacial covalent bonds, we find that the interfacial structural complexity, resulting from the presence of the grafted molecules, and a concomitant spatial homogeneity of the interphase polymer density are beneficial factors in conferring high interfacial shear stress. Our approach paves the way for computational screening processes to design, test, and rapidly identify viable surface modifications in silico, which would enable rapid systematic progress in optimizing the match between the carbon fiber treatment and the desired thermoset polymer matrix.