Molecular dynamics simulation of a nanoscale capillary water bridge between two planar substrates is used to determine the resulting force between the substrates without arbitrariness regarding geometry and location of the free surface of the bridge. The substrates are moderately hydrophilic. The force changes continuously as the separation between the substrates changes except for small gaps where it becomes discontinuous because the bridge is unable to adopt stable configurations at any distance apart. Further exploration of the bridge and the force as the substrates approach each other reveals an underlying oscillatory force with an increasing repulsive component at separation distances equivalent to few water molecules. According to the average number of hydrogen bonds per water molecule (HBN), at very small gap sizes, water molecules which are very close to the surfaces are unable to maximize HBN thus contributing to the repulsive force. Our simulation results of force versus gap size agree with calculations based on other methods, some very different, and also reproduce the typical magnitude of the experimental force. Finally, a macroscopic force balance correctly describes the force-distance curve except for bridges constituted of water layers only.

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Polymers have interesting physicochemical characteristics such as charge density, functionalities, and molecular weight. Such attributes are of great importance for use in industrial purposes. Understanding how these characteristics are affected is still complex, but with the help of molecular dynamics (MD) and quantum calculations (QM), it is possible to understand the behavior of polymers at the molecular level with great consistency. This study was applied to polymers derived from polyacrylamide (PAM) due to its great use in various industries. The polymers studied include hydrolyzed polyacrylamide (HPAM), poly (2-acrylamido-2-methylpropanesulfonate) (PAMPS), polyacrylic acid (PAA), polyethylene oxide polymer (PEO), and guar gum polysaccharide (GUAR). Each one has different attributes, which help in understanding the effects on the polymer and the medium in which it is applied along a broad spectrum. The results include the conformation, diffusion, ion condensation, the structure of the water around the polymer, and interatomic polymer interactions. Such characteristics are important to selecting a polymer depending on the environment in which it is found and its purpose. The effect caused by salinity is particular to each polymer, where polymers with an explicit charge or polyelectrolytes are more susceptible to changes due to salinity, increasing their coiling and reducing their mobility in solution. This naturally reduces its ability to form polymeric bridges due to having a polymer with a smaller gyration radius. In contrast, neutral polymers are less affected in their structure, making them favorable in media with high ionic charges.

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Methyl isobutyl carbinol (MIBC) is a high-performance surfactant with unusual interfacial properties much appreciated in industrial applications, particularly in mineral flotation. In this study, the structure of air–liquid interfaces of aqueous solutions of MIBC-NaCl is determined by using molecular dynamics simulations employing polarizable and nonpolarizable force fields. Density profiles at the interfaces and surface tension for a wide range of MIBC concentrations reveal the key role of polarizability in determining the surface solvation of Cl− ions and the expulsion of non-polarizable Na+ ions from the interface to the liquid bulk, in agreement with spectroscopic experiments. The orientation of MIBC molecules at the water liquid–vapor interface changes as the concentration of MIBC increases, from parallel to the interface to perpendicular, leading to a well-packed monolayer. Surface tension curves of fresh water and aqueous NaCl solutions in the presence of MIBC intersect at a reproducible surfactant concentration for a wide range of salt concentrations. The simulation results for a 1 M NaCl aqueous solution with polarizable water and ions closely capture the MIBC concentration at the intercept. The increase in surface tension of the aqueous MIBC/NaCl mixture below the concentration of MIBC at the intersection seems to originate in a disturbance of the interfacial hydrogen bonding structure of the surface liquid water caused by Na+ ions acting at a distance and not by its presence on the interface.

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