Use of a Geometric Parameter for Characterizing Rigid Films at Oil-Water Interfaces

Interfacial tension and dilatational rheology are often used to characterize the mechanical response of a liquid interface using axisymmetric drop shape analysis (ADSA). It is important to note that for systems dominated by adsorption/desorption of surfactants, the contributions of extra mechanical stresses are negligible; thus, the Young-Laplace equation remains valid. However, for interfaces dominated by extra stresses, as in the case of particle monolayers or asphaltenes that clearly exhibit a skin (a rigid film), the nature of the elastic response is fundamentally different and the validity of the equation is questionable. Calculation of the interfacial tension and dilatational elasticity using drop shape analysis depends critically on the drop shape following the Young-Laplace equation. If the interface becomes more like a solid, the drop shape will deviate from being purely Laplacian. Indeed, the drop will exhibit a wrinkled surface as collapse continues. The geometric parameter R, defined as the ratio (dV/V)/(dA/A) with V is the volume of the drop and A is the area of the interface), allows one to measure the deviation of the drop shape from purely Laplacian. For a simple interface (pure liquids or surfactant solutions), R is quite close to the theoretical value of 1.5 of a perfect sphere. Nevertheless, if the molecules adsorbed at the interface begin to interact strongly, the ratio can vary. In the limit of long-time-scale experiments, R of some drops approaches 2. We studied the evolution of the parameter R for different systems, from simple to complex, as a function of oscillation frequencies and amplitudes of drop volume. The results obtained were compared to the values of the interfacial moduli and drop shape behavior to better characterize the regime change.