Transition processes from the lamellar to the onion state with increasing temperature under shear flow in a nonionic surfactant/water system studied by Rheo-SAXS.

In a previous paper, we reported for the first time the lamellar-to-onion transition with increasing temperature at around 67 °C under a constant shear rate (0.3-10 s(-1)) in a nonionic surfactant C(16)E(7)/water system. In this study, the first temperature-shear rate diagram has been constructed in a wider range of shear rate (0.05-30 s(-1)) than in our previous study based on the temperature dependence of the shear stress at constant shear rate. The results suggest that the critical temperature above which the transition begins does not depend on the shear rate very much, although it takes a very shallow minimum. Then we have performed simultaneous measurements of small-angle X-ray scattering/shear stress (rheo-SAXS) with a stepwise increase in temperature of 0.1 K per 15 min at a constant shear rate of 3 s(-1) near the transition temperature. When the temperature exceeds 67 °C, just before the increase in the shear stress, the intensity of the Bragg peak for the velocity gradient direction (approximately proportional to the number of lamellae with their normal along this direction) is suddenly increased. As the temperature increases by 0.2 K, the shear stress begins to increase. At the same time, the peak intensity in the velocity gradient direction rapidly decreases and instead the intensity in the neutral direction increases. As the temperature increases further, the intensities in both the neutral and gradient directions decrease whereas the intensity in the flow direction increases, corresponding to the formation of onions. We have also performed rheo-SAXS experiments with a stepwise increase in shear rate at 72 °C. The sequence of the change in the intensity in each direction is almost the same in the temperature scan experiments at constant shear rate, suggesting that the transition mechanisms along these two paths are similar. The abrupt enhancement of the lamellar orientation with the layer normal along the velocity gradient direction just before the transition is the first finding and strongly supports the coherent buckling mechanism in the lamellar-to-onion transition proposed by Zilman and Granek (Zilman, A. G.; Granek, R. Eur. Phys. J. B 1999, 11, 593).