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Surfactants, named for their behavior at interfaces, positively adsorb at the interfaces of two phases, reducing interfacial tension. Their versatility as emulsifiers, detergents, and foaming agents stems from this ability. Surfactants, often termed amphiphiles, share the property of amphipathy, with molecules having both hydrophilic and hydrophobic portions. The hydrophilic part is called the head, and the hydrophobic part, including an elongated alkyl substituent, forms the tail.Surfactants...
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Polymer-surfactant vesicular complexes in aqueous medium.

Antonios Kelarakis1, Valeria Castelletto, Marta J Krysmann

  • 1Physical Chemistry Laboratory, Department of Chemistry, National and Kapodistrian University of Athens, Panepistimiopolis, Athens, Greece. akelar@cc.uoa.gr

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Ionic surfactants form vesicles in poly(ethylene oxide)-poly(1,2-butylene oxide) solutions, with aggregate size independent of head group charge. Increasing surfactant concentration suppresses vesicles and alters gel properties.

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Area of Science:

  • Materials Science
  • Physical Chemistry
  • Polymer Science

Background:

  • Amphiphilic block copolymers like poly(ethylene oxide)-poly(1,2-butylene oxide) (EO(18)BO(10)) self-assemble in solution.
  • Ionic surfactants are widely used to modify the properties of polymer solutions.

Purpose of the Study:

  • To investigate the self-assembly behavior of EO(18)BO(10) block copolymers in the presence of ionic surfactants.
  • To understand the impact of surfactant concentration and charge on the resulting aggregate structures and properties of hybrid gels.

Main Methods:

  • Laser scanning confocal microscopy to visualize vesicle formation.
  • Dynamic light scattering to determine aggregate dimensions.
  • Small-angle X-ray scattering (SAXS) to analyze micelle and mesophase structures.
  • Rheological measurements to assess gel properties (storage modulus, thermal stability).

Main Results:

  • Ionic surfactants induce the formation of vesicles in EO(18)BO(10) solutions.
  • Aggregate dimensions are initially independent of surfactant head group charge.
  • SAXS reveals coexistence of micelles with varying polymer content.
  • Increasing surfactant concentration leads to reduced d-spacing in mesophases, suppressing vesicle formation due to ionic strength.
  • Optimal gel properties (storage modulus, thermal stability) are achieved at different compositions, reflecting a balance between polymer-poor aggregates and polymer-surfactant complexes.

Conclusions:

  • Ionic surfactants significantly influence the self-assembly of EO(18)BO(10) copolymers, leading to vesicle formation and subsequent suppression at higher concentrations.
  • The properties of the resulting hybrid gels are governed by a complex interplay between aggregate population, size, and composition, which is tunable via surfactant loading.