Highly Viscoelastic Wormlike Micellar Solutions Formed by Cationic Surfactants with Long Unsaturated Tails

Srinivasa R. Raghavan, Eric W. Kaler

Langmuir · 2000 · 482 citations · 28 references

Concepts

TL;DR

The study examined cationic surfactants with long C22 mono‑unsaturated tails in salt solutions via steady and dynamic rheology. The erucyl bis(hydroxyethyl)methylammonium chloride surfactant self‑assembles into giant wormlike micelles, producing a factor‑of‑10⁷ viscosity increase, gel‑like solids at low temperatures that become Maxwellian viscoelastic at higher temperatures, viscosities exceeding 10 Pa·s up to 90 °C, and its self‑assembly is strongly enhanced by penetrating counterions such as sodium salicylate, while a trimethylammonium headgroup reduces high‑temperature viscosity.

Abstract

Cationic surfactants having long (C22) mono-unsaturated tails were studied in aqueous solutions containing salt using steady and dynamic rheology. The surfactant erucyl bis(hydroxyethyl)methylammonium chloride self-assembles into giant wormlike micelles, giving rise to unusually strong viscoelasticity. Under ambient conditions, the viscosity enhancement due to surfactant exceeds a factor of 107. Some samples behave as gel-like solids at low temperatures and revert to the viscoelastic (Maxwellian) response only at higher temperatures. These samples display appreciable viscosities (>10 Pa·s) up to very high temperatures (ca. 90 °C). Salts with counterions that penetrate into the hydrophobic interior of the micelles, such as sodium salicylate, are much more efficient at promoting self-assembly than salts with nonbinding counterions, such as sodium chloride. Changing the surfactant headgroup to the more conventional trimethylammonium group reduces the viscosity at high temperatures.

References

28