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Thermal Properties and Segmental Dynamics of Polymer Melt Chains Adsorbed on Solid Surfaces
Naisheng Jiang1, Mani Sen1, Maya K Endoh1
1Department of Materials Science and Chemical Engineering , Stony Brook University , Stony Brook , New York 11794-2275 , United States.
Langmuir : the ACS Journal of Surfaces and Colloids
|March 13, 2018
Summary
Investigating supported polystyrene (PS) and poly(2-vinylpyridine) (P2VP) thin films using nanoplasmonic sensing revealed a higher glass transition temperature (Tg,high) for adsorbed polymer chains, distinct from the bulk Tg. This phenomenon is linked to increased chain density at the substrate interface.
Area of Science:
- Polymer Science
- Materials Science
- Surface Science
Background:
- Thin polymer films exhibit altered thermal properties compared to bulk materials.
- The substrate interface significantly influences polymer chain behavior and transitions.
- Understanding interfacial effects is crucial for designing advanced polymer-based materials.
Purpose of the Study:
- To investigate the glass transition behavior of supported polystyrene (PS) and poly(2-vinylpyridine) (P2VP) thin films.
- To identify the origin of the elevated glass transition temperature observed in these films.
- To elucidate the role of polymer-substrate interactions on thermal transitions.
Main Methods:
- Nanoplasmonic sensing (NPS) for nanocalorimetric analysis of thin films.
- Solvent rinsing to isolate and study adsorbed polymer chains.
- Molecular dynamics simulations on PS films adsorbed on different substrates.
Main Results:
- NPS detected a high glass transition temperature (Tg,high) alongside the bulk Tg (Tg,bulk) for PS and P2VP thin films.
- Tg,high was attributed to strongly adsorbed polymer chains on the substrate.
- Molecular dynamics simulations showed increased polymer density near the interface, reducing free volume and increasing Tg.
- The magnitude of Tg deviation correlated with polymer-substrate interaction strength.
Conclusions:
- Adsorbed polymer chains exhibit an elevated glass transition temperature due to increased packing density at the substrate interface.
- Polymer-substrate interactions play a critical role in modifying interfacial thermal properties.
- The findings provide insights into the behavior of thin polymer films and inform the design of interfacial polymer systems.
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