No abstract

Low interface strength is a persistent problem in composite materials and cascades to limit a variety of bulk material properties such as lamina shear strength. Whiskerization has long been pursued as a method to reinforce the interphase and improve both the single fiber interface strength as well as the bulk properties. Recent developments have shown that ZnO nanowire whiskerization can effectively improve the properties of a bulk composite without requiring the high temperatures that previous deposition processes needed. Although the efficacy of a ZnO nanowire interphase has been established, the mechanism for adhesion of the interphase to the fiber has not been identified. Specifically, the addition of the ZnO nanowires to the surface of the fibers requires that the ZnO nanowires have strong chemical adhesion to the fiber surface. This work will create a variety of chemical environments on the surface of the fibers through new and common chemical functionalization procedures and quantify the surface chemistry through X-ray photoelectron spectroscopy. The effect of fiber surface chemistry on the adhesion of the ZnO is assessed through single fiber fragmentation testing. The interface strength is found to strongly correlate with the concentration of ketone groups on the surface of the fibers. Following the experimental observations, liftoff of a ZnO crystal from a graphene surface was simulated with a variety of surface functionalizations. The computational models confirm the preference for ketone groups in promoting adhesion between ZnO and graphite.

When grown on the surface of carbon fiber, vertically aligned arrays of ZnO nanowires have been shown to increase the interfacial shear strength without decreasing the in-plane properties of the composite. Analysis of the failure surface indicates that the ZnO debonds from the carbon fiber which combined with the higher interfacial shear strength, indicates that the ZnO more strongly adheres to the carbon surface than epoxy adheres to the carbon surface. Previous work was unable to identify the specific chemical interaction that enhanced the ZnOcarbon fiber interface, however it hypothesized that the presence carboxylic acid groups on the fiber were responsible. In this study an aramid fiber is used to elucidate the surface interaction since it can be produced with no carboxylic acid or with these groups through functionalization. The model fiber demonstrates that only fibers with carboxylic acid groups experience increased interfacial strength from the ZnO nanowires. The interaction between ZnO and carboxylic acid groups is verified to be critical to the enhancement of the interfacial strength in carbon fiber -ZnO nanowire -epoxy composites.

Vertically aligned zinc oxide (ZnO) nanowires have recently been utilized as an interphase to increase the interfacial strength of carbon fiber composites. It was shown that the interaction between the carbon fiber and the ZnO nanowires was a critical parameter in adhesion; however, fiber based testing techniques are dominated by local defects and cannot be used to effectively study the bonding interaction directly. Here, the strength of the interface between ZnO and graphitic carbon is directly measured with atomic force microscopy (AFM) using oxygen plasma treated highly oriented pyrolytic graphite (HOPG) and an AFM tip coated with ZnO nanoparticles. X-ray photoelectron spectroscopy analysis is used to compare the surface chemistry of HOPG and carbon fiber and to quantify the presence of various oxygen functional groups. An indirect measurement of the interfacial strength is then performed through single fiber fragmentation testing (SFF) on functionalized carbon fibers coated with ZnO nanowires to validate the AFM measurements. The SFF and AFM methods showed the same correlation, demonstrating the capacity of the AFM method to study the interfacial properties in composite materials. Additionally, the chemical interactions between oxygen functional groups and the ionic structure of ZnO suggest that intermolecular forces at the interface are responsible for the strong interface.