Atomistic explorations of mechanisms dictating the shear thinning behavior and 3D printability of graphene flake infused epoxy inks

Nanofiller-based epoxy inks have found extensive use in fabricating 3D printed nanocomposites for applications in aerospace, automobile, and marine systems. In this paper, we employ an all-atom molecular dynamic (MD) simulation to atomistically explore the mechanisms dictating the shear-thinning behavior of the graphene flake-infused (GFI) epoxy inks. We compare our findings with those for pure epoxy inks: non-equilibrium MD (NEMD) simulations reveal that both the GFI epoxy ink and pure epoxy ink demonstrate shear thinning behavior, i.e., their viscosities decrease with an increase in the shear rate. However, interestingly, the viscosity of the GFI epoxy ink is larger than that of pure epoxy for smaller shear rates, while for higher shear rates, the viscosities of these two materials are similar. This indicates a much more favorable viscosity profile for the GFI epoxy inks in the context of 3D printing. From the context of exploring the nanoscale mechanism, we identify the tendency of the bisphenol F molecules (the key constituent of the epoxy inks) and the graphene flakes (for the case of GFI epoxy inks) to align along the shear planes (in the presence of a shear flow) allowing the dissipation of viscous force among them ensuring shear-thinning behavior for both pure epoxy and GFI epoxy inks. In this context, we also identify that the bisphenol F chains prefer to localize along a given shear plane to reduce the effect of tension forces: such an alignment ensures that the radius of gyration for the bisphenol F molecules (for both pure epoxy and GFI epoxy inks) is larger for the case of finite shear and has a non-monotonic variation with the shear rate. Finally, the equilibrium MD (EMD) simulations establish that the presence of the graphene flakes significantly slows down the rotational dynamics of the bisphenol F molecules that are adsorbed to these graphene flakes and, as a result, causes the zero-shear viscosity of the GFI epoxy to be three orders of magnitude larger than that of the pure epoxy. This difference provides a qualitative justification of the viscosity of the GFI epoxy being larger than that of pure epoxy at smaller shear rate values.