Surface interaction parameter measurement of solvated polymers via model end-tethered chains

Published

August 11, 2017

Author(s)

Richard J. Sheridan, Sara V. Orski, Ronald L. Jones, Sushil K. Satija, Kathryn L. Beers

Abstract

We present a method for the direct measurement of the relative energy of interaction between a solvated polymer and a solid interface. By tethering linear chains covalently to the surface, we ensured the idealized and constant configuration of polymer molecules for measurement, modeling, and parameter estimation. For the case of amine-terminated polystyrene bound to a glycidoxypropyl silane film submerged in cyclohexane-d12, we estimated the χ parameter for the temperature range 10.7 °C to 52.0 °C, and found a downward sloping trend that crosses the χ=0.5 threshold at 37 °C to 40 °C, in agreement with solution estimates for the same system. We simultaneously estimated the surface interaction parameter χ_s at each temperature, finding a decreasing affinity of the chains for the surface with increasing temperature, consistent with empirical observations. The theoretical model shows some limitations in a stronger solvent (toluene-d8) that prevent rigorous parameter estimation, but we demonstrate a qualitative change in χ and χ_s towards stronger solvency and weaker surface interaction with increasing temperature.

Citation

ACS Nano

Pub Type

Journals

Download Paper

https://doi.org/10.1021/acs.macromol.7b00639

Keywords

polymer brush, end-tethered polymer, neutron reflectivity, small angle neutron scattering, surface interaction, chromatography, self-consistent field theory

Citation

Sheridan, R. , Orski, S. , Jones, R. , , S. and Beers, K. (2017), Surface interaction parameter measurement of solvated polymers via model end-tethered chains, ACS Nano, [online], https://doi.org/10.1021/acs.macromol.7b00639 (Accessed October 14, 2025)