Ion effects on co-existing pseudo-phases in aqueous surfactant solutions: cryo-TEM, rheometry, and quantification

Specific alkaline cation effects control the area per headgroup of alkylester sulphates, which modifies the spontaneous packing of the surfactants. The resulting effective packing minimizes the total bending energy frustration and results in a Boltzmann distribution of coexisting pseudo-phases. These pseudo-phases constitute of micelles and other structures of complex morphology: cylindrical sections, end-caps, branching points, and bilayers, all in dynamic equilibrium. According to our model, excess of end-caps or excess of branching points lead to low viscosity, whereas comparable amounts of both structures lead to viscosity maxima. Relative occurrence of branching points and end-caps is the molecular mechanism at the origin of the salt-sensitive viscosity peak in the "salt-curve" (viscosity against salt concentration at fixed surfactant concentration). Up to now, and as indicated in former papers, this has been a pure model without microscopic verification.

In this work, we introduce explicit counting of the number of coexisting pseudo-phases as observed by state-of-the-art cryogenic transmission electron microscopy (cryo-TEM). The model system used, i.e., sodium laurylethersulfate (SLES)/salt/water, is very common as part of cosmetic formulations. As added salts, we used Li⁺, Na⁺, K⁺, and Cs⁺ chlorides. In parallel to imaging, we measured the macroscopic viscosities of the different solutions.

With cryogenic transmission electron microscopy (cryo-TEM), we imaged a variety of morphologies (pseudo-phases) in the different aqueous surfactant/salt solutions: cylindrical micelles with end-caps, discs surrounded by "rims", entangled thread-like micelles with branching points, networks with gliding branching points, and bilayers. The relative chemical potentials of these morphologies could be approximated simply by counting the relative proportion of their occurrence. This simple multi-scale approach avoids any ad-hoc "specificity" assumption of ions, and is based on the bending energy model in an extended version of the Benedek "ladder model". It is capable of explaining and even quantifying the location of all viscosity peaks in the "salt-curves" for the different cations investigated, thus confirming the previously proposed model experimentally, and - thanks to cryo-TEM - for the first time on a microscopic scale. Moreover, this approach can also be applied when the added cations lead to newly observed pseudo-phases, such as discs and vesicles. To the best of our knowledge, this is the first time that cryo-TEM is used, together with a mesoscopic model, to describe a macroscopic property such as viscosity and specific ion effects on it, without any a priori assumption about these effects. So, in total, we could a) confirm the predictions of the previously developed model, b) use cryo-TEM imaging and viscosity measurements to predict and find unusual morphologies when varying the cations of the added salt, and c) count the pseudo-phases in cryo-TEM micrographs to quantitatively explain the different nanostructures.