Lamellar-to-onion transition with increasing temperature under shear flow in a nonionic surfactant/water system

Langmuir. 2010 Mar 16;26(6):3835-42. doi: 10.1021/la903251v.

Abstract

Simultaneous measurements of small-angle light scattering/shear stress (Rheo-SALS) and small-angle X-ray scattering/shear stress (Rheo-SAXS) have been performed in the lamellar phase of the C(16)E(7)/D(2)O system. As the temperature is increased and exceeds 67 degrees C at constant shear rates (at 1 and 3 s(-1)), the shear stress increases abruptly and a four-lobe pattern is observed in the depolarized SALS. These results suggest that the lamellar-to-onion transition occurs with increasing temperature, which has not yet been reported. The diameter of onions obtained from the depolarized SALS pattern at 3 s(-1) increases with increasing temperature. The transition is reversible against the change in temperature. The Rheo-SALS measurements have also been made with a stepwise increase in shear rate at constant temperature. The results are consistent with the above temperature-scan experiments at constant shear rate, suggesting that the transition does not depend on the path. The variation of the SAXS pattern at 3 s(-1) indicates that the orientation of lamellae becomes isotropic as the temperature is increased from 67 to 69 degrees C, which also supports the lamellar-to-onion transition. The transition temperature at constant shear rate (at 3 s(-1)) increases rapidly with a slight increase in surfactant concentration. From this, together with the SAXS results at rest in our previous study, we deduce that an increase in the water-layer thickness is necessary for the lamellar-to-onion transition with increasing temperature.