Addition of small amounts of lauric acid (LA) to a micellar solution of sodium dodecyl sulfate (SDS, 11.5 wt%) and cocamidopropyl betaine (CAPB, 3 wt%) has a dramatic effect on the rheological properties and phase behaviour of the system. The viscosity increases by more than one order of magnitude up to a weight ratio LA/SDS = 0.17 and decreases for further LA loading. The decrease in viscosity is associated to the formation of a birefringent liquid crystalline phase. The evolution of the system from isotropic micelles in absence of LA to lyotropic liquid crystals up to a weight ratio LA/SDS = 0.30 was probed by a combination of 23Na NMR quadrupolar splitting, measurements of water and surfactant self-diffusion coefficients via 1H-PGSE-NMR and rheology. The evolution of the water self-diffusion coefficients indicates that LA induced a dramatic increase in the anisotropy of disk shaped micelles. Birefringent samples always showed a well developed 23Na quadrupolar splitting with a line shape typical of monodomain samples. This suggests that the whole sample is easily oriented within the spectrometer electromagnet as usually observed for nematic liquid crystals. Sample spinning first destroys the alignment (only a single peak is discernible in the 23Na NMR spectrum). Then, upon prolonged spinning, the alignment develops again. This indicates that the system is composed by disk-like micelles aligning themselves with their normal perpendicular to the magnetic field. On the other hand, the linear viscoelastic response close to the nematic transition shows features usually observed in wormlike micellar systems (e.g. nearly Maxwellian behaviour). To reconciliate the rheological data and the NMR evidences of discoid micelles, the formation of columnar stacks of discoid micelles is proposed. The rheology of the isotropic phase can therefore be interpreted in terms of entanglements of “living columnar stacks” of discoid micelles, and the nematic phase observed at high LA content could be attributed to a nematic columnar phase NCol formed by the alignment of such stacks.

Lauric acid-induced formation of a lyotropic nematic phase of disk-shaped micelles

COLAFEMMINA, Giuseppe;PALAZZO, Gerardo
2010

Abstract

Addition of small amounts of lauric acid (LA) to a micellar solution of sodium dodecyl sulfate (SDS, 11.5 wt%) and cocamidopropyl betaine (CAPB, 3 wt%) has a dramatic effect on the rheological properties and phase behaviour of the system. The viscosity increases by more than one order of magnitude up to a weight ratio LA/SDS = 0.17 and decreases for further LA loading. The decrease in viscosity is associated to the formation of a birefringent liquid crystalline phase. The evolution of the system from isotropic micelles in absence of LA to lyotropic liquid crystals up to a weight ratio LA/SDS = 0.30 was probed by a combination of 23Na NMR quadrupolar splitting, measurements of water and surfactant self-diffusion coefficients via 1H-PGSE-NMR and rheology. The evolution of the water self-diffusion coefficients indicates that LA induced a dramatic increase in the anisotropy of disk shaped micelles. Birefringent samples always showed a well developed 23Na quadrupolar splitting with a line shape typical of monodomain samples. This suggests that the whole sample is easily oriented within the spectrometer electromagnet as usually observed for nematic liquid crystals. Sample spinning first destroys the alignment (only a single peak is discernible in the 23Na NMR spectrum). Then, upon prolonged spinning, the alignment develops again. This indicates that the system is composed by disk-like micelles aligning themselves with their normal perpendicular to the magnetic field. On the other hand, the linear viscoelastic response close to the nematic transition shows features usually observed in wormlike micellar systems (e.g. nearly Maxwellian behaviour). To reconciliate the rheological data and the NMR evidences of discoid micelles, the formation of columnar stacks of discoid micelles is proposed. The rheology of the isotropic phase can therefore be interpreted in terms of entanglements of “living columnar stacks” of discoid micelles, and the nematic phase observed at high LA content could be attributed to a nematic columnar phase NCol formed by the alignment of such stacks.
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Utilizza questo identificativo per citare o creare un link a questo documento: http://hdl.handle.net/11586/81641
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