Molecular Insights into the Adsorption of Deposit Control Additives from Hydrocarbon Fuels.

Engine deposits can reduce performance and increase emissions, particularly for modern direct-injection fuel delivery systems. Surfactants known as deposit control additives (DCAs) adsorb and self-assemble on the surface of deposit precursors to keep them suspended in the fuel. Here, we show how molecular simulations can be used to virtually screen the ability of surfactants to bind to polyaromatic hydrocarbons, comprising a major class of carbonaceous deposits. We use molecular dynamics with the adaptive biasing force method to generate the potential of mean force as a function of the vertical distance between the surfactants and deposits in gasoline and diesel fuel surrogates. We find that a zwitterionic surfactant outperforms a conventional polyisobutylene succinimide for binding to these aromatic species. The amine groups in the succinimide headgroup only weakly adsorb on the polyaromatic deposit, while additional functional groups in the zwitterionic surfactant, particularly the quarternary ammonium ion, markedly enhance the binding strength. We decompose the adsorption free energies of the surfactants into their entropic and enthalpic components, to find that the latter dominates the attraction from these non-aqueous solvents. The adsorption free energy of both surfactants is slightly weaker from