Macromolecules, Vol.30, No.8, 2377-2385, 1997
Microviscosity in Clusters of Ethyl Hydroxyethyl Cellulose and Sodium Dodecyl-Sulfate Formed in Dilute Aqueous-Solutions as Determined with Fluorescence Probe Techniques
The microviscosity has been measured in dilute aqueous solutions of ethyl hydroxyethyl cellulose (EHEC) and sodium dodecyl sulfate (SDS) by utilizing three steady-state fluorescence probe techniques : intramolecular excimer formation by 1,3-di(1-pyrenyl)propane (P3P), fluorescence depolarization of perylene, and intramolecular rotational relaxation about bonds with (p-(dimethylamino)benzylidene)malononitrile (BMN). Results obtained by the three techniques are compared. They all detect qualitatively the same behavior with a well-developed maximum in microviscosity and rigidity of the EHEC/SDS clusters formed at a surfactant concentration close to or slightly higher than the critical surfactant concentration where adsorption to the polymer starts. The EHEC/SDS clusters have, independent of composition, higher microviscosities than ordinary SDS micelles. The microviscosity is also compared with other EHEC/SDS/water system features such as the bulk viscosity, the actual adsorption isotherm, the average aggregation numbers, and the micropolarity as sensed by pyrene of the EHEC/SDS clusters formed. The maximum in microviscosity corresponds to a rather low degree of SDS adsorption to EHEC (approximate to 0.5 mmol of SDS per gram of EHEC) and a low aggregation number (approximate to 10) where the polymer content of each polymer-bound surfactant cluster is high. It coincides (according to the surfactant concentration) with a maximum in bulk viscosity for polymer concentrations higher than the critical overlap concentration (c*). It is suggested that the maximum in bulk viscosity is due to a three-dimensional network of polymer and cluster tie points while the maximum in microviscosity is related to a high content of hydrophobic polymer segments which stabilizes the surfactant clusters.
Keywords:HYDROPHOBICALLY MODIFIED POLY(N-ISOPROPYLACRYLAMIDES);AGGREGATION NUMBERS;POLY(ETHYLENE OXIDE);TORSIONAL RELAXATION;METHYL CELLULOSE;MICELLES;WATER;SURFACTANTS;MEMBRANES;SYSTEM