1. The Topology of Polymer Brushes Determines Their Nanoscale Hydration
- Author
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Apostolos Vagias, Andrew Nelson, Peixi Wang, Julija Reitenbach, Christina Geiger, Lucas Philipp Kreuzer, Thomas Saerbeck, Robert Cubitt, Edmondo Maria Benetti, and Peter Müller‐Buschbaum
- Subjects
swelling ,neutron reflectometry ,Polymers and Plastics ,grafted brushes ,Organic Chemistry ,Materials Chemistry ,cyclic polymers - Abstract
Time-of-flight neutron reflectometry (ToF-NR) performed under different relative humidity conditions demonstrates that polymer brushes constituted by hydrophilic, cyclic macromolecules exhibit a more compact conformation with lower roughness as compared to linear brush analogues, due to the absence of dangling chain ends extending at the polymer-vapor interface. In addition, cyclic brushes feature a larger swelling ratio and an increased solvent uptake with respect to their linear counterparts as a consequence of the increased interchain steric repulsions. It is proposed that differences in swelling ratios between linear and cyclic brushes come from differences in osmotic pressure experienced by each brush topology. These differences stem from entropic constraints. The findings suggest that to correlate the equilibrium swelling ratios at different relative humidity for different topologies a new form of the Flory-like expression for equilibrium thicknesses of grafted brushes is needed., Macromolecular Rapid Communications, 44 (9), ISSN:1022-1336, ISSN:1521-3927
- Published
- 2023
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