Here we examine how the force on an atomic force microscope (AFM) tip varies as it approaches micellar surfactant films, and use this information to discern the film's surface structure and Young's modulus. Rows of wormlike hemimicelles were created at a graphite interface using 10 mM sodium dodecyl sulfate (SDS). We found that the repulsive force on a silicon nitride tip as it approached the surface was exponential, with a decay length of 2.0 ± 0.1 nm. The addition of Na₂SO₄ was found to cause a change in this behavior, with a clear split into two exponential regions at concentrations above 1 mM. We also observed that the range of these forces increased with added salt from ∼15 nm in pure SDS to ∼20 nm at a Na₂SO₄ concentration of 1.34 mM. These forces were inconsistent with electrostatic repulsion, and were determined to be steric in nature. We show that the behavior at higher salt concentrations is consistent with the theory of polyelectrolyte brushes in the osmotic regime. From this, we hypothesize the presence of micellar brushes at the surface that behave similarly to adsorbed polymer chains. In addition, the Young's modulus of the film was taken from data near the interface using Sneddon's model, and found to be 80 ± 40 MPa. Similar experiments were performed with 10 mM dodecylamine hydrochloride (DAH) solutions in the presence of added magnesium chloride. The decay length for the pure DAH solution was found to be 2.6 ± 0.3 nm, and the addition of 1.34 mM of MgCl₂ caused this to increase to 3.7 ± 0.3 nm. No decay length splitting was observed for DAH. We conclude that the behavior at the surface resembles that of an uncharged polymer brush, as the ionic and surface charge densities are much lower for DAH than for SDS.

In this work, we study the mechanical properties of sodium dodecyl sulfate (SDS) and dodecylamine hydrochloride (DAH) micellar films at a graphite surface via atomic force microscopy (AFM). Breakthrough forces for these films were measured using silicon nitride cantilevers and were found to be 1.1 ± 0.1 nN for a 10 mM DAH film and 3.0 ± 0.3 nN for a 10 mM SDS film. For 10 mM SDS films, it was found that the addition of 1.5 mM of NaCl, Na₂SO₄, or MgCl₂ produced a 50-70% increase in the measured breakthrough force. Similar results were found for 10 mM DAH films when NaCl and MgCl₂ were added. A model was developed on the basis of previous work on lipid films and CMC data gathered via spectrofluorometry measurements to predict the change in normalized breakthrough forces with added salt concentrations for SDS and DAH films. Using this model, it was found that the activation volume required to initiate the breakthrough was roughly 0.4 nm³ for SDS and 0.3 nm³ for DAH, roughly the volume of a single molecule. Normalized breakthrough force data for SDS films with added MgCl₂ showed an unexpected dip at low added salt concentrations. The model was adapted to account for changing activation volumes, and a curve of activation volume versus magnesium concentration was obtained, showing a minimum volume of 0.21 nm³. The addition of 0.2 mM SDS to a 10 mM DAH solution was found to double the measured breakthrough force of the film. Images taken of the surface showed a phase change from cylindrical hemimicelles to a planar film that may have produced the observed differences. The pH of the bulk solution was varied for both 10 mM SDS and DAH films and was found to have little effect on the breakthrough force.