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Interplay between cubic and hexagonal phases in block copolymer solutions.

Moon Jeong Park1, Kookheon Char, Joona Bang

  • 1School of Chemical Engineering & Nanosystems Institute-National Core Research Center (NCRC), Seoul National University, Seoul 151-744, Korea.

Langmuir : the ACS Journal of Surfaces and Colloids
|February 9, 2005
PubMed
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Researchers studied styrene-isoprene diblock copolymer phase behavior in a solvent. They discovered a new phase coexistence and observed supercooled cylinders that resist transformation, but shear can restore equilibrium sphere phases.

Area of Science:

  • Polymer Science
  • Materials Science
  • Soft Matter Physics

Background:

  • Diblock copolymers exhibit complex phase behavior influenced by molecular architecture and solvent interactions.
  • Understanding phase transitions is crucial for controlling material properties and applications.

Purpose of the Study:

  • To investigate the phase behavior of a symmetric styrene-isoprene (SI) diblock copolymer in a styrene-selective solvent (diethylphthalate).
  • To characterize the coexistence of body-centered cubic (bcc) and hexagonally close-packed (hcp) sphere phases.
  • To examine the kinetics and hysteresis of phase transitions, particularly the persistence of supercooled cylinders.

Main Methods:

  • In situ small-angle X-ray scattering (SAXS) on isotropic and shear-oriented solutions.

Related Experiment Videos

  • Rheology measurements to probe flow properties and transitions.
  • Birefringence to detect orientational order.

    • Main Results:

    • A novel phase diagram region showing coexistence of bcc and hcp sphere phases between close-packed spheres (cps) and hexagonally packed cylinders (hex) for concentrations (phi) of approximately 0.33-0.45.
    • Significant hysteresis observed during heating/cooling cycles, with supercooled cylinders persisting upon cooling.
    • Supercooled cylinders showed concentration-dependent stability, resisting reversion to spheres even after prolonged annealing at phi >= 0.40.
    • Spontaneous sphere formation from cylinders was kinetically hindered, unlike melt transitions.
    • Large amplitude shear effectively restored equilibrium sphere phases from supercooled cylinders.

    Conclusions:

    • The SI diblock copolymer system exhibits complex phase behavior with a unique bcc/hcp sphere phase coexistence region.
    • Kinetically trapped supercooled cylinder phases present challenges for achieving equilibrium states, particularly at higher concentrations.
    • Shear application provides a viable method to overcome kinetic barriers and induce transitions to equilibrium sphere phases.