Understanding solid–water­(vapor) interfacial systems is relevant for both industrial and academic scenarios for their presence in wide areas ranging from tribology to geochemistry. Using grand canonical Monte Carlo simulations, we have investigated the role of monovalent (lithium, Li+; sodium, Na+; and potassium, K+) and divalent (magnesium, Mg2+; calcium, Ca2+) cations on the structure and adsorption behavior of water on mica surface. The water density adjacent to the surface exhibits (a) oscillations due to hydration of surface cations (interfacial layer), (b) followed by a thick liquidlike layer. The thickness of the interfacial layer is strongly dependent on the hydration shell size and hydration energy of surface ions. Water molecules immediately next to the surface (contact layers) adsorb on ditrigonal (hexagonal) cavities of mica surface and form an ordered structure. The Li+, Na+, Mg2+, and Ca2+ surface ions are coadsorbed with water molecules on the ditrigonal cavities due to their smaller hydration shell. Majority of water molecules in the second contact layer hydrate the surface ions and, together with the rest of the water molecules, form hydrogen bonds among themselves. The structure of the water molecules in the third and subsequent layer is random and more bulk liquidlike, except those molecules that hydrate the surface ions. The adsorption isotherm of water on all ion-exposed mica surface exhibits three regimes: (a) an initial rapid increase in water loading for relative vapor pressure (p/p 0) ≤0.2 due to hydration of surface ions; (b) followed by a linear increase between p/p 0 = 0.2 and 0.7, where the hydrogen bond formation between the water molecules of the interfacial layer occurs; and (c) exponential growth beyond p/p 0 = 0.7 due to thickening of the liquidlike layer. The water loading on divalent-ion-exposed mica surface is higher compared to the monovalent ions case. Although the divalent ions have higher hydration energy, the fraction of water molecules hydrating the surface ions is less compared to nonhydrating water molecules. We found that ion hydration energy and size of hydration shell play a crucial role in their structure adjacent to mica surface. At lower water loadings, the surface ions form a hydration shell with surface bridging oxygens, whereas at higher water content, the hydration preference is shifted toward mobile water molecules. The detailed understanding obtained from this work will be useful in identifying the role of ions in cloud formation, nanotribological studies, and activities of biological molecules and catalysts.

The interaction in aqueous solutions of surfactants with amphiphilic polymers can be more complex than the surfactant interactions with homopolymers. Interactions between the common ionic surfactant sodium dodecyl sulfate (SDS) and nonionic amphiphilic polymers of the poly(ethylene oxide)–poly(propylene oxide)–poly(ethylene oxide) (PEO-PPO-PEO) type have been probed utilizing a variety of experimental techniques. The polymer amphiphiles studied here are Pluronic F127 (EO100PO65EO100) and Pluronic P123 (EO19PO69EO19), having the same length PPO block but different length PEO blocks and, accordingly, very different critical micellization concentrations (CMC). With increasing surfactant concentration in aqueous solutions of fixed polymer content, SDS interacts with unassociated PEO-PPO-PEO molecules to first form SDS-rich SDS/Pluronic assemblies and then free SDS micelles. SDS interacts with micellized PEO-PPO-PEO to form Pluronic-rich SDS/Pluronic assemblies, which upon further increase in surfactant concentration, break down and transition into SDS-rich SDS/Pluronic assemblies, followed by free SDS micelle formation. The SDS-rich SDS/Pluronic assemblies exhibit polyelectrolyte characteristics. The interactions and mode of association between nonionic macromolecular amphiphiles and short-chain ionic amphiphiles are affected by the polymer hydrophobicity and its concentration in the aqueous solution. For example, SDS binds to Pluronic F127 micelles at much lower concentrations (~0.01 mM) when compared to Pluronic P123 micelles (~1 mM). The critical association concentration (CAC) values of SDS in aqueous PEO-PPO-PEO solutions are much lower than CAC in aqueous PEO homopolymer solutions.

Fluorinated surfactants are used in a wide range of applications that involve aqueous solvents incorporating various additives. The presence of organic compounds such as urea is expected to affect the self-assembly of fluorinated surfactants, however, very little is known about this. We investigated the effect of urea on the micellization in water of the common fluorinated surfactant ammonium perfluorooctanoate (APFO), and on the structure and microenvironment of the micelles that APFO forms. Addition of urea to aqueous APFO solution decreased the critical micellization concentration (CMC) and increased the counterion dissociation. The observed increase in surface area per APFO headgroup and decrease in packing density at the micelle surface suggest the localization of urea at the micelle surface in a manner that reduces headgroup repulsions. Micropolarity data further support this picture. The results presented here indicate that significant differences exist between urea effects on fluorinated surfactant and on hydrocarbon surfactant micellization in aqueous solution. For example, the CMC of sodium dodecyl sulfate (SDS) increased with urea addition, while the increase in surface area per headgroup and packing density of SDS with urea addition are much lower than those observed for APFO. This study informs fluorinated surfactant fate and transport in the environment, and also applications involving aqueous media in which urea or similar additives are present.