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This study introduces solvent vapor annealing (SVA) with sorption isotherms to control block copolymer complex morphology. This method allows for understanding swelling and guiding self-assembly pathways for advanced material design.

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Area of Science:

  • Materials Science
  • Polymer Chemistry
  • Self-Assembly

Background:

  • Controlling block copolymer (BCP) morphologies relies on molecular architecture and processing.
  • Solvent vapor annealing (SVA) is effective for high chi (χ) BCPs and supramolecular complexes.
  • Controlled SVA in BCP complexes remains underexplored due to their multicomponent complexity.

Purpose of the Study:

  • To investigate controlled solvent vapor annealing (SVA) in block copolymer complexes.
  • To establish a method for understanding swelling behavior and morphological evolution in BCP complexes.
  • To develop effective annealing pathways for BCP complexes using sorption isotherms.

Main Methods:

  • Introduction of absorption-desorption solvent vapor isotherms for BCP complexes.
  • Analysis of sorption isotherms to determine glass transition points and polymer-solvent interaction parameters.
  • Application of findings to develop SVA pathways for grain coarsening and prevent film dewetting.

Main Results:

  • Sorption isotherms effectively characterize swelling and morphological evolution in polystyrene-block-poly(4-vinylpyridine) complexed with pentadecylphenol (PS-b-P4VP(PDP)).
  • Complexation was found to completely screen polymer interchain interactions.
  • Grain coarsening under SVA followed a power law, indicating a kinetic transition point for rapid self-assembly.

Conclusions:

  • SVA-based sorption isotherms provide critical insights into the behavior of BCP complexes.
  • This approach enables the development of tailored annealing pathways for precise morphological control.
  • The method offers a pathway to overcome challenges in processing complex BCP systems.