Understanding Calcium-Mediated Adhesion of Nanomaterials in Reservoir Fluids by Insights from Molecular Dynamics Simulations

Interest in nanomaterials for subsurface applications has grown markedly due to their successful application in a variety of disciplines, such as biotechnology and medicine. Nevertheless, nanotechnology application in the petroleum industry presents greater challenges to implementation because of the harsh conditions (i.e. high temperature, high pressure, and high salinity) that exist in the subsurface that far exceed those present in biological applications. The most common subsurface nanomaterial failures include colloidal instability (aggregation) and sticking to mineral surfaces (irreversible retention). We previously reported an atomic force microscopy (AFM) study on the calcium-mediated adhesion of nanomaterials in reservoir fluids (S. L. Eichmann and N. A. Burnham, Sci. Rep. 7, 11613, 2017), where we discovered that the functionalized and bare AFM tips showed mitigated adhesion forces in calcium ion rich fluids. Herein, molecular dynamics reveal the molecular-level details in the AFM experiments. Special attention was given to the carboxylate-functionalized AFM tips because of their prominent ion-specific effects. The simulation results unambiguously demonstrated that in calcium ion rich fluids, the strong carboxylate-calcium ion complexes prevented direct carboxylate-calcite interactions, thus lowering the AFM adhesion forces. We performed the force measurement simulations on five representative calcite crystallographic surfaces and observed that the adhesion forces were about two to three fold higher in the calcium ion deficient fluids compared to the calcium ion rich fluids for all calcite surfaces. Moreover, in calcium ion deficient fluids, the adhesion forces were significantly stronger on the calcite surfaces with higher calcium ion exposures. This indicated that the interactions between the functionalized AFM tips and the calcite surfaces were mainly through carboxylate interactions with the calcium ions on calcite surfaces. Finally, when analyzing the order parameters of the tethered functional groups, we observed significantly different behavior of the alkanethiols depending on the absence or presence of calcium ions. These observations agreed well with AFM experiments and provided new insights for the competing carboxylate/calcite/calcium ion interactions.