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The self-assembly of nanoparticles (NPs) at interfaces is currently a topic of increasing interest due to numerous applications in food technology, pharmaceuticals, cosmetology, and oil recovery. It is possible to create tunable interfacial structures with desired characteristics using tailored nanoparticles that can be precisely controlled with respect to shape, size, and surface chemistry. To address these functionalities, it is essential to develop techniques to study the properties of the underlying structure. In this work, we propose an experimental approach utilizing the standard deviation of drop profiles calculated by the Laplace equation from experimental drop profiles (STD), as an alternative to the Langmuir trough or precise microscopic methods, to detect the initiation of closely packed conditions and the collapse of the adsorbed layers of CTAB-nanosilica complexes. The experiments consist of dynamic surface/interfacial tension measurements using drop profile analysis tensiometry (PAT) and large-amplitude drop surface area compression/expansion cycles. The results demonstrate significant changes in STD values at the onset of the closely packed state of nanoparticle-surfactant complexes and the monolayer collapse. The STD trend was explained in detail and shown to be a powerful tool for analyzing the adsorption and interfacial structuring of nanoparticles. Different collapse mechanisms were reported for NP monolayers at the liquid/liquid and air/liquid interfaces. We show that the interfacial tension (IFT) is solely dependent on the extent of interfacial coverage by nanoparticles, while the surfactants regulate only the hydrophobicity of the self-assembled complexes. Also, the irreversible adsorption of nanoparticles and the increasing number of adsorbed complexes after the collapse were observed by performing consecutive drop surface compression/expansion cycles. In addition to a qualitative characterization of adsorption layers, the potential of a quantitative calculation of the parameter STD such as the number of adsorbed nanoparticles at the interface and the distance between them at different states of the interfacial layer was discussed.

Experimental data for tridecyl dimethyl phosphine oxide (C13DMPO) adsorption layers at the water/air interface, including equilibrium surface tension and surface dilational viscoelasticity, are measured by bubble and drop profile analysis tensiometry at different solution concentrations and surface area oscillation frequencies. The results are used to assess the applicability of a multistate model with more than two possible adsorption states. For the experiments with single drops, the depletion of surfactant molecules due to adsorption at the drop surface is taken into account. For the assessment, the same set of model parameters is used for the description of all obtained experimental dependencies. The agreement between the proposed model and the experimental data shows that for the nonionic surfactant C13DMPO, the description of the adsorption layer behavior by three adsorption states is superior to that with only two adsorption states.