Demonstration of a Novel Charge-Free Reverse Wormlike Micelle System

We demonstrate a novel charge-free reverse wormlike micelle (RWLM) consisting of a ternary mixture of a nonionic amphiphilic block copolymer, fatty acid alkyl ester oil, and water under ambient conditions. Nonionic amphiphile tetra-[poly­(oxyethylene)-poly­(oxybutylene)]­pentaerythrityl ether (TEBPE) self-assembled into spheroid-type micelles in nonaqueous media isopropyl myristate (IPM) with viscosity comparable to that of IPM. The addition of water increases viscosity only slightly up to a certain concentration of water and then drastically, demonstrating the sphere-to-wormlike micelle transition as confirmed by small-angle X-ray scattering. Further increase in water decreases the viscosity after attaining a maximum value. The zero shear viscosity (η₀) of the 10 wt % TEBPE/IPM system reached the maximum at 2.6 wt % water and ca. 56 Pa·s, which is ∼fivefold higher than that of water. Dynamic rheological measurements on the highly viscous solutions confirmed the viscoelastic behavior and could be described by the Maxwell model. Conductivity, measured in the presence of a conductive probe, 1-ethyl-3-methylimidazolium tetrafluoroborate, was found to be higher for viscous samples compared to the nonviscous samples, suggesting the static percolation caused by the RWLM formation. Decrease in η₀ and conductivity beyond a maximum suggests the shortening of reverse micelles. A similar behavior has been observed in other fatty acid alkyl ester oils of different alkyl chain lengths. Note that most of the RWLM systems previously reported are based on phosphatidylcholine (PC). Formulation and structure–properties related to non-PC-based RWLMs have been rarely explored. Non-PC-based RWLMs using chemically stable and low-cost synthetic molecules can be applied not only in pharmaceuticals and cosmetics but also in a wide range of applications including drag reduction agents for nonaqueous fluids and as a template for nanomaterial synthesis