Nanoscale toughening of ultrathin graphene oxide-polymer composites: mechanochemical insights into hydrogen-bonding/van der Waals interactions, polymer chain alignment, and steric parameters

This paper describes a systematic, quantitative study on the nanoscale toughening of monolayer graphene oxide (GO) by an ultra-thin polymer adlayer, which impedes the propagation of cracks during intraplanar fracture. Using molecular dynamics simulations, the crack-bridging capabilities of a library of five hydrogen-bonding-capable polymers are explored against an epoxide-rich GO substrate. The best crack-bridging effect is found in polymers with functional groups that can both donate/accept hydrogen atoms and have better capability to form cooperative hydrogen bonds. Aligning the chains of poly(acrylic acid) orthogonally to the crack propagation direction significantly enhances the fracture toughness of monolayer GO (by 310%) in comparison to that for an adlayer with randomly arranged chains (180% enhancement). Notably, van der Waals interactions, which are seldom highlighted in the fabrication of strong GO-polymers interfaces, are found to also provide significant crack-bridging capabilities when the polymers possess large side groups. These results pave the way for a set of design criteria that can help in remediating the intrinsically brittle mechanical behavior of two-dimensional materials, a barrier that currently restricts their potential applications.