This paper reports a small-angle neutron scattering (SANS) characterization of perfluoropolyether (PFPE) aqueous micellar solutions with lithium, sodium, cesium and diethanol ammonium salts obtained from a chlorine terminated carboxylic acid and with two perfluoroisopropoxy units in the tail (n2). The counterion and temperature effects on the micelle formation and micellar growth extend our previous work on ammonium and potassium salts n2 micellar solutions. Lithium, sodium, cesium and diethanol ammonium salts are studied at 0.1 and 0.2 M surfactant concentration in the temperature interval 28−67 °C. SANS spectra have been analyzed by a two-shell model for the micellar form factor and a screened Coulombic plus steric repulsion potential for the structure factor in the frame of the mean spherical approximation of a multicomponent system reduced to a generalized one component macroions system (GOCM). At 28 °C, for all the salts, the micelles are ellipsoidal with an axial ratio that increases from 1.6 to 4.2 as the counterion volume increases. The micellar core short axis is 13 Å and the shell thickness 4.0 Å for the alkali micelles, and 14 and 5.1 Å for the diethanol ammonium micelles. Therefore, the core short axis mainly depends on the surfactant tail length and the shell thickness on the carboxylate polar head. The bulky diethanol ammonium counterion solely influences the shell thickness. Micellar charge and average aggregation number depend on concentration, temperature and counterion. At 28 °C, the fractional ionization decreases vs the counterion volume (or molecular weight) increase at constant concentration for both C = 0.1 M and C = 0.2 M. The increase of the counterion volume leads also to more ellipsoidal shapes. At C = 0.2 M, at 67 °C, for sodium and cesium micelles the axial ratio changes significantly, leading to spherical micelles with a core radius of 15 Å, lower average aggregation number, and larger fractional ionization.
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