Unveiling Texture and Topography of Fatty Acid Langmuir Films: Domain Stability and Isotherm Analysis

3D texturing by self-assembly at the air–water interface has recently been proposed. The hypothesis of this work is that, if this is true, such domain formation should be inferable directly from pressure–area isotherms and be thermodynamically stable. Monolayers of branched fatty acid mixtures with straight chain analogues and their stability are thus studied using a combination of pressure–area isotherms, thermodynamic analysis, in situ Brewster angle microscopy, and atomic force microscopy of both LB-deposited and drop-cast films on silicon wafers. Isotherms reflecting the behavior of monodisperse 3D domains are shown to be independent of compression rate and display long-term stability. Gibbs analysis further confirms the thermodynamic rather than kinetic origin of such novel species by revealing that deviations from ideal mixing can be explained only a priori by differences in the topography of the water surface, thus also indirectly confirming the self-assembly deformation of the water interface. The intrinsic self-assembly curvature and miscibility of the two fatty acids is confirmed by drop-casting, which also provides a rapid, tunable thin-film preparation approach. Finally, the longevity of the nanostructured films is extraordinary, the long-range order of the deposited films increases with equilibration time at the water interface, and the integrity of the nanopatterns remains intact on the scale of years.