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Published on: June 12, 2019
Brush-sheathed particles diffusing at brush-coated surfaces in the thermally responsive PNIPAAm system.
Huilin Tu1, Liang Hong, Stephen M Anthony
1Department of Materials Science and Engineering, Beckman Institute for Advanced Science and Technology, University of Illinois at Urbana-Champaign, Urbana, IL 61801, USA.
Near-surface diffusion of polymer-coated microspheres is slower than bulk diffusion below 32°C. Above this temperature, diffusion increases, suggesting reduced hydrodynamic coupling and potential electrostatic repulsion effects.
Area of Science:
- Surface Science
- Polymer Chemistry
- Colloid Science
Background:
- Poly(N-isopropylacrylamide) (PNIPAAm) exhibits a lower critical solution temperature (LCST) around 32°C.
- Polymer brushes influence particle-surface interactions and dynamics.
- Understanding near-surface diffusion is crucial for applications involving confined colloids.
Purpose of the Study:
- To investigate the near-surface translational diffusion of PNIPAAm brush-functionalized silica microspheres.
- To compare near-surface diffusion with bulk diffusion across the PNIPAAm LCST.
- To elucidate the factors affecting diffusion dynamics near a polymer-coated surface.
Main Methods:
- Phase-contrast microscopy and particle tracking algorithms were employed.
- Sedimentation of silica microspheres onto polymer-coated substrates was studied.
- Dynamic light scattering was used to measure bulk diffusion coefficients.
Main Results:
- Near-surface diffusion coefficient (D(surface)) was approximately 0.6 times the bulk diffusion coefficient (D(bulk)) below 32°C.
- D(surface)/D(bulk) ratio increased to 0.8-0.9 above 32°C.
- A small negative surface charge (zeta potential = -6 mV) prevented particle adhesion.
Conclusions:
- Near-surface diffusion is significantly influenced by temperature relative to the PNIPAAm LCST.
- Enhanced diffusion above the LCST suggests reduced hydrodynamic coupling to the surface.
- Electrostatic repulsion may play a role in mediating diffusion changes above the LCST.
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