Interfacial strength and fracture energy of individual carbon nanofibers in epoxy matrix as a function of surface conditions

The interfacial shear strength (IFSS) and fracture energy of individual carbon nanofibers embedded in epoxy were obtained for different surface conditions and treatments by novel, MEMS-based, nanoscale fiber pull-out experiments. As-grown vapor grown carbon nanofibers (VGCNFs) with turbostratic surface and 5 nm peak-to-valley surface roughness exhibited high IFSS and interfacial fracture energy, averaging 106 ± 29 MPa and 1.9 ± 0.9 J/m2, respectively. Subsequent high temperature heat treatment and graphitization resulted in drastically reduced IFSS of 66 ± 10 MPa and interfacial fracture energy of 0.65 ± 0.14 J/m2. The smaller IFSS values and the reduced standard deviation were due to significant reduction of the fiber surface roughness to 1–2 nm, as well as a decrease in surface defect density during conversion of turbostratic and amorphous carbon to highly ordered graphitic carbon. For both grades of VGCNFs failure was adhesive with clear nanofiber surfaces after debonding. Oxidative functionalization of high temperature heat-treated VGCNFs resulted in much higher IFSS of 189 ± 15 MPa and interfacial fracture energy of 3.3 ± 1.0 J/m2. The debond surfaces of functionalized nanofibers had signs of matrix residue and/or shearing of the outer graphitic layer of the VGCNFs, namely the failure mode was a combination of cohesive matrix and/or cohesive fiber failure which contributed to the high IFSS. For all three grades of VGCNFs the IFSS was independent of fiber length and diameter. The findings of this experimental study emphasized the critical role of nanofiber surface morphology and chemistry in determining the shear strength and fracture energy of nanofiber interfaces, and shed light to prior composite-level strength and fracture toughness measurements.