Abstract

Aggregation properties of sodium dodecyl sulfate (SDS) on a cationic hydroxyethyl cellulose, Polyquaternium-10 (PQ-10), of low charge density were studied by potentiometric and pyrene fluorescence methods and compared with those of poly(diallyldimethylammomium chloride) (PDADMAC) of high charge density. The critical aggregation concentration (cac) was measured with the potentiometric method and further confirmed with the fluorescence method. The former was found to be more accurate. The value of the cac for the SDS/PQ-10 system was measured at 100, 200, and 400 ppm polymer and at 288.2,298.2, and 308.2 K. They showed almost the same cac value, 0.04 mmol dm-3. The I1/I3 value of the pyrene fluorescence spectrum in the SDS/PQ-10 system at higher SDS concentration was smaller than that in SDS/PDADMAC solution and much larger than that of water. From the binding isotherm by the potentiometric method, the free DS- concentration (Cf) and the bound DS- concentration (Cb) could be evaluated with ease over the SDS concentration range above the cac. The aggregation number of DS- aggregates for both the above polymers was evaluated from the fluorescence quenching method using the values of Cf and Cb from the potentiometric method. Because Cf in the SDS/PQ-10 system above the cac did not maintain a constant value contrary to that in the SDS/PDADMAC system but increased quite a lot, Cb should not be regarded as [SDS] - cac above the cac. The aggregation number in the SDS/PQ-10 system increased almost linearly with increasing total concentration of SDS, while that in the SDS/PDADMAC system reached a plateau. With increasing temperature, the aggregation number of the SDS/PDADMAC system decreased more rapidly than that of the SDS/PQ-10 system.

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