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Persistence of Birefringence in Sheared Solutions of Wormlike Micelles

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posted on 06.01.2009, 00:00 authored by Bradley D. Frounfelker, Gokul C. Kalur, Bani H. Cipriano, Dganit Danino, Srinivasa R. Raghavan
When aqueous solutions containing wormlike micelles (worms) are sheared, the micellar chains tend to align with the flow, which in turn leads to flow-birefringence. When shear is stopped, the worms rapidly revert to an isotropic state in typical samples, and the birefringence disappears. In this study, we present a system of cationic worms that shows a different behavior: not only do the samples become intensely birefringent when sheared but the birefringence also persists for hours (and even days) after shear is stopped. These results suggest that shear-aligned worms in the sample are trapped in their aligned state for long periods of time, an aspect that is confirmed by cryo-transmission electron microscopy (cryo-TEM). We seek to determine the origin of this unusual behavior. Our results show that the persistent birefringence is observed for cationic worms induced by hydroxy-naphthoate but not salicylate counterions. These observations suggest that the micellar alignment is stabilized by intermicellar attractive interactions (such as π−π and cation−π) that arise when large aromatic counterions are anchored within the micelles.