Molecular Dynamics Simulations of the Short-Chain Fluorocarbon Surfactant PFH_XA and the Anionic Surfactant SDS at the Air/Water Interface

Abstract

The research and development of alternatives to long-chain fluorocarbon surfactants are desperately needed because they are extremely toxic, difficult to break down, seriously harm the environment, and limit the use of conventional aqueous film-forming foam fire extinguishing agents. In this study, mixed surfactant systems containing the short-chain fluorocarbon surfactant perfluorohexanoic acid (PFHXA) and the hydrocarbon surfactant sodium dodecyl sulfate (SDS) were investigated by molecular dynamics simulation to investigate the microscopic properties at the air/water interface at different molar ratios. Some representative parameters, such as surface tension, degree of order, density distribution, radial distribution function, number of hydrogen bonds, and solvent-accessible surface area, were calculated. Molecular dynamics simulations show that compared with a single type of surfactant, mixtures of surfactants provide superior performance in improving the interfacial properties of the gas–liquid interface. A dense monolayer film is formed by the strong synergistic impact of the two surfactants. Compared to the pure SDS system, the addition of PFHXA caused SDS to be more vertically oriented at the air/water interface with a reduced tilt angle, and a more ordered structure of the mixed surfactants was observed. Hydrogen bonding between SDS headgroups and water molecules is enhanced with the increasing PFHXA. The surface activity is arranged in the following order: PFHXA/SDS = 1:1 > PFHXA/SDS = 3:1 > PFHXA/SDS = 1:3. These results indicate that a degree of synergistic relationship exists between PFHXA and SDS at the air/water interface.

Keywords

• short-chain fluorocarbon surfactants
• hydrocarbon surfactants
• synergy effect
• molecular dynamics simulation
• gas–liquid interface