The flexibility of rodlike micelles in aqueous solutions and the crossover concentrations among dilute, semidilute, and concentrated regimes

Abstract

A flexibility parameter, the persistence length, has been evaluated from the radii of gyration and the contour lengths for rodlike micelles of heptaoxyethylene alkyl ethers (C _n E₇,n=12, 14, 16) and tetradecyldimethylammonium chloride (C₁₄DAC) and bromide (C₁₄DAB) at the observed crossover concentrations between dilute and semidilute regimes. The persistence length range is 43–73 nm, except for C₁₂E₇, for which it is 32 nm. The crossover concentrations between dilute and semidilute regimes for the semiflexible rodlike micelles calculated according to Ying and Chu as a function of the molecular weight, the contour length, and the persistence length are consistent with the observed values. The crossover concentration between semidilute and concentrated regimes was, on the other hand, calculated by using the same micelle parameters, including the value of thickness of cross-section of the rodlike micelles. The obtained values are at variance with the observed values. This means that rodlike micelles in semidilute and concentrated solutions might differ in size and/or flexibility from those in dilute solution.