Effect of stiffness on the micellization behavior of model H4T4 surfactant chains

Michele Floriano, Vanessa Firetto, Athanassios Z. Panagiotopoulos

Risultato della ricerca: Articlepeer review

19 Citazioni (Scopus)

Abstract

The micellization behavior of a series of model surfactants, all with four head and tail groups (H4T4) but with different degrees of chain stiffness, was studied using grand canonical Monte Carlo simulations on a cubic lattice. The critical micelle concentration, micellar size, and thermodynamics of micellization were examined. In all cases investigated, the critical micelle concentration was found to increase with increasing temperature as observed for nonionic surfactants in apolar or slightly polar solvents. At a fixed reduced temperature and increasing chain stiffness, in agreement with previous observations, it was found that the critical micelle concentration decreased and the average micelle size increased. This behavior is qualitatively consistent with that experimentally observed when comparing hydrogenated and homologous fluorinated surfactants. Thermodynamic considerations based on the analysis of the temperature dependence of the critical micelle concentration indicated that both effects could be interpreted as arising from an increased number of heterocontacts between hydrophobic portions of stiff surfactants and a lower entropic cost on packing rigid chains. Structural analysis that was also based on considering the inner micellar radial dependence of the surfactant head and tail site fraction distributions suggested that, on stiffening the molecular backbone, the resulting micellar aggregates grew, without appreciable deviations from spherical symmetry. Stiffer surfactants led to a slightly denser micellar core because of better packing.
Lingua originaleEnglish
pagine (da-a)6514-6522
Numero di pagine9
RivistaLangmuir
Volume22
Stato di pubblicazionePublished - 2006

All Science Journal Classification (ASJC) codes

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  • Condensed Matter Physics
  • Surfaces and Interfaces
  • Spectroscopy
  • Electrochemistry

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