Glycerol-induced swollen lamellar phases with siloxane copolymers

J Colloid Interface Sci. 2007 Dec 15;316(2):723-9. doi: 10.1016/j.jcis.2007.08.064. Epub 2007 Sep 1.

Abstract

Phase behavior is established for a block copolymer polyethyleneoxide-b-dimethylsiloxane-polyethylenoxide (EO)(15)-(PDMS)(15)-(EO)(15) (IM-22) a in glycerol/water mixed solvent. In water alone, the block copolymer forms biphasic micellar/lamellar (L(1)/L(alpha)) systems over the range 10-70 wt%, with single L(alpha)-phases between 70-90 wt%. Strong solvent effects on the phase behavior were noted. For example, using a mixed 60:40 vol% glycerol/water solvent, the single L(alpha)-phase region appears at much lower concentrations, only 20 wt% IM-22, as compared to the biphasic L(1)/L(alpha) system observed in water alone. This interesting observation of L(alpha)-phase swelling on addition of glycerol may be explained by a decrease in attraction between the bilayers, as it is also found that in this mixed glycerol/water solvent there is a close refractive index matching with IM-22. Rheological measurements show the L(alpha)-phases with added glycerol have low shear moduli. The influence of added ionic surfactant sodium dodecylsulfate (SDS) on these swollen IM-22 L(alpha)-phases was studied. Small-angle X-ray scattering (SAXS) indicated the interlamellar distance d remains essentially constant up to 3 mM SDS, and then decreases with increasing SDS content. This weak effect is consistent with the fact that the L(alpha)-phases are most swollen when the mixed solvent contains 60 vol% glycerol. The results suggest that glycerol/water solvent mixtures can be used to tune the refractive index of the background solvent, modifying DLVO-type interactions, and causing significant effects on the phase stability of simple block-copolymer systems.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Chemical Phenomena
  • Chemistry, Physical
  • Dimethylpolysiloxanes / chemistry*
  • Glycerol / chemistry*
  • Micelles
  • Polyethylene Glycols / chemistry*
  • Rheology
  • Scattering, Small Angle
  • Sodium Dodecyl Sulfate / chemistry
  • Solvents / chemistry
  • Water / chemistry
  • X-Ray Diffraction

Substances

  • Dimethylpolysiloxanes
  • Micelles
  • Solvents
  • Water
  • Sodium Dodecyl Sulfate
  • Polyethylene Glycols
  • Glycerol