Hideki Seto

2D-Ising critical behavior in mixtures of water and 3-methylpyridine

The effect of an antagonistic salt on the phase behavior and nanoscale structure of a mixture of D{sub 2}O and 3-methylpyridine was investigated by visual inspection and small-angle neutron scattering (SANS). The addition of the antagonistic salt, namely sodium tetraphenylborate (NaBPh{sub 4}), induces the shrinking of the two-phase region in contrast to the case in which a normal (hydrophilic) salt is added. Below the phase separation point, the SANS profiles cannot be described by the Ornstein-Zernike function owing to the existence of a long-range periodic structure. With increasing salt concentration, the critical exponents change from the values of 3D-Ising and approach those of 2D-Ising. These results suggest that the concentration fluctuation of the mixture of solvents is limited to a quasi two-dimensional space by the periodic structure induced by the adding the salt. The same behaviors were also observed in mixtures composed of water, 3-methylpyridine, and ionic surfactant.

Effect of interlamellar interactions on shear induced multilamellar vesicle formation

Shear-induced multilamellar vesicle (MLV) formation has been studied by coupling the small-angle neutron scattering (SANS) technique with neutron spin echo (NSE) spectroscopy. A 10% mass fraction of the nonionic surfactant pentaethylene glycol dodecyl ether (C12E5) in water was selected as a model system for studying weak inter-lamellar interactions. These interactions are controlled either by adding an anionic surfactant, sodium dodecyl sulfate, or an antagonistic salt, rubidium tetraphenylborate. Increasing the charge density in the bilayer induces an enhanced ordering of the lamellar structure. The charge density dependence of the membrane bending modulus was determined by NSE and showed an increasing trend with charge. This behavior is well explained by a classical theoretical model. By considering the Caillé parameters calculated from the SANS data, the layer compressibility modulus B¯ is estimated and the nature of the dominant inter-lamellar interaction is determined. Shear flow induces MLV formation around a shear rate of 10 s-1, when a small amount of charge is included in the membrane. The flow-induced layer undulations are in-phase between neighboring layers when the inter-lamellar interaction is sufficiently strong. Under these conditions, MLV formation can occur without significantly changing the inter-lamellar spacing. On the other hand, in the case of weak inter-lamellar interactions, the flow-induced undulations are not in-phase, and greater steric repulsion leads to an increase in the inter-lamellar spacing with shear rate. In this case, MLV formation occurs as the amplitude of the undulations gets larger and the steric interaction leads to in-phase undulations between neighboring membranes.