Using Nitroxides to Enhance Carbon Fiber Interfacial Adhesion and as an Anchor for "Graft to" Surface Modification Strategies.

Nitroxide groups covalently grafted to carbon fibers are used as anchoring sites for TEMPO-terminated polymers (poly-n-butylacrylate and polystyrene) in a "graft to" surface modification strategy. All surface-modified fibers are evaluated for their physical properties, showing that several treatments have enhanced the tensile strength and Young's modulus compared to the control fibers. Up to an 18% increase in tensile strength and 12% in Young's modulus are observed. Similarly, the evaluation of interfacial shear strength in an epoxy polymer shows improvements of up to 144% relative to the control sample. Interestingly, the polymer-grafted surfaces show smaller increases in interfacial shear strength compared to surfaces modified with a small molecule only. This counterintuitive result is attributed to the incompatibility, both chemical and physical, of the grafted polymers to the surrounding epoxy matrix. Molecular dynamics simulations of the interface suggest that the diminished increase in mechanical shear strength observed for the polymer grafted surfaces may be due to the lack of exposed chain ends, whereas the small molecule grafted interface exclusively presents chain ends to the resin interface, resulting in good improvements in mechanical properties.

From graphene to graphene oxide: the importance of extended topological defects.

Graphene oxide (GO) represents a complex family of materials related to graphene: easy to produce in large quantities, easy to process, and convenient to use as a basis for further functionalization, with the potential for wide-ranging applications such as in nanocomposites, electronic inks, biosensors and more. Despite their importance, the key structural traits of GO, and the impact of these traits on properties, are still poorly understood due to the inherently berthollide character of GO which complicates the establishment of clear structure/property relationships. Widely accepted structural models of GO frequently neglect the presence of extended topological defects, structural changes to the graphene basal plane that are not removed by reduction methods. Here, a combination of experimental approaches and molecular simulations demonstrate that extended topological defects are a common feature across GO and that the presence of these defects strongly influences the properties of GO. We show that these extended topological defects are produced following even controlled 'gentle' functionalization by atomic oxygen and are comparable to those obtained by a conventional modified Hummers' method. The presence of the extended topological defects is shown to play an important role in the retention of oxygen functional groups after reduction. As an exemplar of their effect on the physical properties, we show that the GO sheets display a dramatic decrease in strength and stiffness relative to graphene and, due to the presence of extended structural defects, no improvement is seen in the mechanical properties after reduction. These findings indicate the importance of extended topological defects to the structure and properties of functionalized graphene, which merits their inclusion as a key trait in simple structural models of GO.

Peptide-Driven Exfoliation and Dispersion Mechanisms of Graphene in Aqueous Media.

Peptide-mediated exfoliation and suspension of graphene in aqueous media is a promising strategy for bioapplications such as drug delivery, tissue engineering, and biosensors. A few peptide sequences are known as graphene exfoliators/dispersants in water, but the mechanisms underpinning this process remain underexplored. Here, molecular simulations investigate two key steps: sheet exfoliation and subsequent sheet reunification, in aqueous media. Umbrella sampling simulations predict the energy required to separate a graphene sheet from a graphite stack in both the presence/absence of the graphene-exfoliant peptide, P1. The free-energy barrier for reunification of two P1-coated graphene sheets is similarly calculated. Under sonication, the benefit from the relatively lower free-energy barrier associated with exfoliation in the absence of the peptide is negated by its facile reunification postsonication. In contrast, although P1 slightly increases the energy barrier to exfoliation under sonication, the peptides confer high-energy barriers to sheet reunification, thus ensuring stable aqueous graphene dispersions.

Moisture Ingress at the Molecular Scale in Hygrothermal Aging of Fiber-Epoxy Interfaces.

Almost all applications of carbon fiber reinforced composites are susceptible to water aging, either via ambient humidity or through direct exposure to liquid water environments. Although the impacts of water aging in composites can be readily quantified via experimental efforts, details regarding the mechanisms of moisture ingress and aging, particularly at the incipient stages of aging under hygrothermal conditions, have proven challenging to resolve using experimental techniques alone. A deeper understanding of the factors that drive incipient moisture ingress during aging is required for more targeted approaches to combat water aging. Here, molecular dynamics simulations of a novel epoxy/carbon fiber interface exposed to liquid water under hygrothermal conditions are used to elucidate molecular details of the moisture ingress mechanisms at the incipient stages of the aging process. Remarkably, the simulations show that the fiber-matrix interface is not vulnerable to a moisture-wicking type of incipient water ingress and does not readily flood in these early stages of water aging. Instead, water is preferentially absorbed via the matrix-water interface, an ingress pathway that is facilitated by the dynamic mobility of polymer chains at this interface. These chains present electronegative sites that can capture water molecules and provide a conduit to transiently exposed pores and channels on the polymer surface, which creates a presoaked staging reservoir for subsequent deeper ingress into the composite. Characterization of the absorbed water is according to hydrogen bonding to the matrix, and the distributions and transport behavior of these waters are consistent with experimental observations. This work introduces new insights regarding the molecular-level details of moisture ingress and spatial distribution of water in these materials during hygrothermal aging, informing future design directions for extending both the service life and shelf life of next-generation composites.