Ghazi Kassab

Simple-Complex Fluid Transition in Microemulsions

The aim of this work was to study the rheological behavior of water in-oil microemulsion formulated with AOT (sodium bis(2-ethylhexyl) sulfoccinate) in isooctane over a temperature range from 25°C to 55°C for the oil/AOT volume fraction φ m =0.1 and various AOT and H2O molar ratios, W0, ranging from 0 to 45. The apparent viscosity was measured vs. shear rate by a rotational concentric cylinder viscometer. It was shown that above s−1, the solutions utilized behaved as Newtonian liquids. The absolute viscosities were deduced from the shear stress- shear rate rheograms. For W0 < 17, the solutions behaved as simple fluids, where the viscosities decrease as the temperature increases. However, an opposite behavior was observed for W0 > 17; the viscosity remained constant and then increased above a critical temperature, Tc, depending on W0. For the molar ratio W0,c = 17; the studied viscosity remained constant, η(W0,c) = (1.17 ± 0.04) cP, for the temperature range studied. Thus, a simple–complex fluid transition was evident in the studied system. For the simple fluids, W0 < W0,c, the total activation energy vs. W0 showed three linear parts. The different slopes were attributed to the change of the microscopic structure of the formed micelles. For the critical molar ratio W0,c = 17, the total activation energy vanished. So, according to the Eyring lattice model, the jump of the formed micelles from one site to another was not permitted and the entire molecular groups were in vibration and rotation motions. For W0 > W0,c, where the formed micelles were fully hydrated, the relative viscosity of the studied solutions vs. temperature was fitted according a polynomial law, where the exponent was found to be dependent on W0.

Study by 1H NMR of the Influence of the Porosity and Solvent on the Conformations of Macromolecules at an Interface: Poly(Ethylene Oxide) Grafted on Silica

ABSTRACT The 1H NMR technique was used to study the behaviour of poly(ethylene oxide) chains grafted chemically on silica. A noticeable influence of the nature of the surface and solvent on the conformation of the grafted macromolecules was observed. For precipitated silica the chains adopted a disordered conformation whereas for pyrogenic silica they formed a more uniform layer. The grafting ratio and the solvent can both modify the conformations of the chains. The dependence of the relaxation times (T1 and T2) on the grafting ratios is discussed qualitatively from a phenomenological point of view. Different models are proposed for the two extreme grafting ratio levels in both the absence and the presence of solvent. Without solvent, for both grafting ratios, the macromolecules lie very flat on the silica and the layer is more organized, especially at high grafting ratio. In the presence of solvent the chains spread out in the solvent, adopt a more extended conformation and the local concentration of monomers at the surface decreases.