Surfactants at fluid interfaces: molecular modeling and deep learning

Surfactants at fluid-fluid interfaces play a critical role in numerous engineering applications, including enhanced oil recovery and fire suppression by foams. This dissertation explores surfactant-laden fluid-fluid interfaces in two applications using molecular dynamics (MD) simulations and develops deep learning models to predict the interfacial properties of sur factants. The first study investigates slippage modulation at brine–oil interfaces by surfactants, which is relevant to enhanced oil recovery operations. We identified a slip length of 1.2 nm at clean decane-brine interfaces. Introducing surfactants to the interface leads to an initial linear decrease in slippage, with nonylphenol being more effective than phenol. As surfactant concentration increases, the reduction in slip length slows, ultimately plateauing at 1.4 nm and 0.5 nm for nonylphenol and phenol, respectively. The mechanisms underlying these slip modulation behaviors and the effects of surfactant tail length on interfacial slippage are examined by analyzing the molecular structure and transport properties of the interfacial fluids and surfactants. The second study focuses on oil transport across surfactant-laden fluid-fluid interfaces, which is relevant to firefighting foam applications. Despite its importance, the molecular details of this transport are not fully understood. Through MD simulations, the potential of mean force (PMF) and local diffusivity profiles of heptane molecules across surfactant monolayers was computed to evaluate their transport resistance across the interface. It was discovered that a heptane molecule experiences significant resistance when crossing surfactant-covered water−vapor interfaces. This resistance, influenced by high PMF and low diffusion in the surfactant head group region, increases linearly with surfactant density and dramatically spikes as the monolayer reaches saturation, becoming equivalent to the resistance of a 5 nm thick layer of bulk water. These observations provide insights into the design of surfactants aimed at reducing oil transport through water−vapor interfaces. The final part of the dissertation explores the development of a quantitative structure-property relationship (QSPR) model for surfactants using a graph neural network (GNN) based approach. The model was trained on 92 surfactant data points and demonstrated high accuracy (R² = 0.86 on average) in predicting critical micelle concentration, limiting surface tension, and maximum surface excess for various surfactants. The performance of the model in capturing the relationship between molecular design parameters and surfactant properties was critically evaluated. The dataset, model development, and assessments contribute to advancing surfactant QSPR models and their rational design for diverse industrial applications