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Possible explanation of the Lambda-shape anomaly in polymer surface diffusion.

Debashish Mukherji1, Martin H Müser

  • 1Department of Physics & Astronomy, University of Western Ontario, London, Ontario N6A 3K7, Canada.

Physical Review. E, Statistical, Nonlinear, and Soft Matter Physics
|August 16, 2006
PubMed
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Polymer surface diffusion (D) increases with concentration (Gamma) then drops. Molecular dynamics simulations reveal this is due to a transition from single to double-layered structures, hindering diffusion.

Area of Science:

  • Polymer Physics
  • Surface Science
  • Computational Materials Science

Background:

  • The surface diffusion coefficient (D) of polymers exhibits anomalous concentration-dependent behavior.
  • Previous studies reported a non-monotonic trend where D initially increases and then sharply decreases at a critical surface concentration (Gamma*).

Purpose of the Study:

  • To elucidate the mechanism behind the anomalous polymer surface diffusion.
  • To investigate the structural transitions governing the observed diffusion behavior.

Main Methods:

  • Conducting molecular dynamics (MD) simulations.
  • Analyzing polymer structural arrangements at varying surface concentrations (Gamma).

Main Results:

  • Simulations replicate the anomalous D behavior, showing an increase followed by a drop at Gamma*.

Related Experiment Videos

  • Polymers form single-layered 'pancake' structures below Gamma*.
  • Above Gamma*, polymers form double-layered structures, adapting better to substrate corrugation.

    • Conclusions:

    • The transition to double-layered structures at Gamma* impedes polymer lateral diffusion.
    • This structural change explains the observed decrease in surface diffusion coefficient at higher polymer concentrations.