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Entropy-induced microphase separation in hard diblock copolymers.

Paul P F Wessels1, Bela M Mulder

  • 1FOM Institute for Atomic and Molecular Physics, Kruislaan 407, 1098 SJ Amsterdam, The Netherlands. wessels@thphy.uni-duesseldorf.nl

Physical Review. E, Statistical, Nonlinear, and Soft Matter Physics
|November 5, 2004
PubMed
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Entropy can drive microphase separation in block copolymers, a rare phenomenon. This study uses a density functional approach to model hard rod diblock copolymers, revealing phase diagrams and conditions for observing this entropy-induced separation.

Area of Science:

  • Polymer Physics
  • Soft Matter Physics
  • Statistical Mechanics

Background:

  • Microphase separation is typically driven by energetic interactions, not entropy.
  • Entropic forces in polymer systems can lead to complex phase behavior, but microphase separation is uncommon.
  • Diblock copolymers offer a platform to explore entropic effects on phase transitions.

Purpose of the Study:

  • To investigate the possibility of entropy-driven microphase separation in diblock copolymers.
  • To model a system of freely jointed hard rods with differing segment diameters.
  • To analytically determine the conditions for microphase separation and liquid crystalline phases.

Main Methods:

  • Density functional theory approach.
  • Generalization of the Onsager approximation for chain-like particles.

Related Experiment Videos

  • Linear stability (bifurcation) analysis to determine phase transitions.

    • Main Results:

    • Analytical determination of the onset of microseparated and nematic phases for long chains.
    • Microseparated phase found to preempt the nematic phase for very long chains.
    • Phase diagrams generated as a function of diameter, length, and number ratios of segments.

    Conclusions:

    • Entropy can indeed drive microphase separation in specific diblock copolymer systems.
    • The study provides a theoretical framework and parameters for experimental observation.
    • The Gaussian limit offers a simplified analytical approach to study competition between microphase separation and liquid crystallinity.