Effect of Temperature on Cononsolvency of Polyvinylpyrrolidone in Water/Methanol Mixture

The behavior of polyvinylpyrrolidone in mixed water/methanol solvents was studied by rheoviscosimetry over a temperature range of 20°C–40°C. For the lower temperatures of this range, the intrinsic viscosity variation of the polymer vs. methanol molar fraction shows structural transitions (coil–globule–coil). This transition, which is usually attributed to the cononsolvency phenomenon, agrees with our previously published results obtained by dynamic light scattering. For higher temperatures, near 40°C, the intrinsic viscosity increase shows an expansion of the polymer over the alcohol molar fraction range 0.2 < X _A < 0.5. This last result can be attributed to the water/alcohol complex destruction under temperature increase. The “excess viscosity” of the polymer-mixed solvents vanishes with increasing temperature and becomes positive at 40°C. So, the polymer chain tends to transit from a globular to an ideal chain in the middle composition range of the mixed solvents.     

Quantification of the Effect of an Impurity Addition on the Interaction Between Unlike Molecules in Mixed Liquids: A Theoretical Study

Journal of Solution Chemistry - The aim of this work is to develop a simple theory to study the effect of the addition of an impurity on the interaction between unlike molecules in mixed liquids....     

Polyvinylpyrrolidone Behavior in Water/Ethanol Mixed Solvents: Comparison of Modeling Predictions with Experimental Results

The objective of this work is to study the behavior of a neutral polymer, polyvinylpyrrolidone (PVP), in a mixture of water and ethanol. A comparison of the experimental results with a theoretical model of effective solvent interaction with polymer (ESIP) was made. To do so, dynamic light scattering experiments were used to measure the hydrodynamic radius of PVP (M _w = 3.6 × 10⁵ g·mol^?1) as a function of the ethanol fraction, x _A, in the medium at 25 °C. We show that the polymer adopts an ideal chain–globule–coil conformation transition as the ethanol molar fraction varies. This transition is attributed to the change of the solvent quality which results from water and ethanol complex formation. On the other hand, the ternary PVP/water/ethanol system was described by the ESIP model. From the polymer–effective solvent interaction, the second virial coefficient of the polymer/effective solvent and the preferential adsorption parameter were calculated. The obtained results are in agreement with the reported experiments.     

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, T_c, depending on W₀. For the molar ratio W_0,c = 17; the studied viscosity remained constant, η(W_0,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 < W_0,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 W_0,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 > W_0,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

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.     

Determination of the Water/AOT/Isooctane Reverse Micelles Size Parameters from Their Refractive Index Data

The present paper aims to study the proprieties of water confined in water/AOT/isooctane reverse micelles from their refractive indices at 298.5 K. The refractive indices of the microemulsions were investigated at increasing water concentration and at different micellar volume fractions, Φ _d. The refractive index of micellar water was deduced for a large water to AOT molar ratio, W ₀. The refractive index of interfacial water was also calculated. Then, the molar faction of interfacial water, α, was deduced for different W ₀ values and compared with those measured by NMR as reported in the literature. The results show qualitative agreement. Finally, the average aggregation number, n _agg, the area per surfactant headgroup, σ, as well as the interfacial thickness, d _i, of the reverse micelles were determined for the W ₀ values studied. The values of these structural parameters also show good qualitative agreement with NMR and small angle X-ray scattering data reported in the literature. Thus, the refractive index method can be a cheap and fast alternative for these two methods.